Manufacturing method for synthesizing, functionalizing, surface treating and / or encapsulating powder, and application thereof

Abstract

To provide a system, an apparatus and a method for treating an article.SOLUTION: A system includes a sub-system for synthesizing, pretreating, vapor-phase coating and post-treating a powdery and solid or porous work-piece shaped article. An apparatus can perform gas-phase synthesis, treatment and deposition process with high efficiency and high total throughput. A method includes converting a solid, liquid or a gas into a gas flow and a solid flow to be separated or exchanged irrespective of existence of the treatment and / or the coating process to manufacture a composite material article optimized for specific applications.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED PATENT APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 62 / 549,601, filed August 24, 2017, and U.S. Provisional Application No. 62 / 672,289, filed May 16, 2018, the disclosures of each of which are incorporated herein by reference in their entireties.

[0002] Field TECHNICAL FIELD This technology relates generally to systems, apparatus, and methods used to process articles, and more particularly to systems, apparatus, and methods for depositing layers on articles. [Background technology]

[0003] background The incorporation of particles, powders and flowable objects from millimeter scale to nanometer size is ubiquitous in end-use products. A significant percentage of these materials used in all industries can be improved by upgrading or post-treatment processes that modify the surface properties of the bulk material without adversely affecting the properties of the bulk material itself. For various reasons, each field or industry has determined that the incorporation of coated particles, powders or flowable objects into the end-use product adds enough value to the product's performance to justify the costs associated with each coating process. Significant efforts have been made over the past decades to increase the number and variety of vaporizable precursors available for such systems. However, significant challenges remain in delivering appreciable quantities of some of these materials to synthesis or encapsulation unit operations in a reliable manner. Summary of the Invention

[0004] The present technology is directed to overcoming these and other shortcomings.

[0005] overview One aspect of many embodiments of the present invention relates to an apparatus for treating surfaces of a plurality of flowable articles with a vaporous precursor, the apparatus including: a) a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first vapor phase inlet, and a first vapor phase outlet; b) a first solid phase valve or pump assembly in fluid communication with the first solid phase inlet of the first chamber; c) a first vapor phase valve or pump assembly adjacent to and in fluid communication with the first vapor phase inlet of the first chamber; d) a common signal hub; and e) at least one control system.

[0006] In at least one embodiment, the at least one first solid phase inlet and the at least one first solid phase outlet include a solid phase valve assembly or a solid phase pump assembly having at least two actuation mechanisms configured to be in bidirectional control signal communication with a signal hub. In at least one embodiment, the at least one first gas phase inlet and the at least one first gas phase outlet include a gas phase valve assembly or a gas phase pump assembly having at least one actuation mechanism configured to be in bidirectional control signal communication with a signal hub. In at least one embodiment, the first chamber further includes a first sensor network including two or more sensors, each sensor in the first sensor network configured to transmit one or more signals to a signal hub, the first sensor network configured to monitor a temperature, pressure, and / or composition of a gas environment surrounding the article. In at least one embodiment, the at least one control system is configured to simultaneously transmit multiple signals to and receive multiple signals from one or more signal hubs, and provides a controllable unit for regulating material flow.

[0007] In at least one embodiment, the first chamber is configured to a) receive a solid phase comprising flowable articles having a definable specific surface area through one or more first solid phase inlets, b) dispense a solid phase comprising flowable articles having a treated surface with a definable specific surface area through one or more first solid phase outlets, c) receive, create and / or contain a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through one or more first gas phase inlets, and d) dispense a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through one or more first gas phase outlets.

[0008] In at least one embodiment, the apparatus further includes at least one transport unit having one or more actuation mechanisms and configured to control the temperature, pressure, and composition of the gaseous environment while regulating the material flow rate of the plurality of flowable articles. In at least one embodiment, the inlet of the transport unit i) is in fluid communication with at least one first solid phase outlet valve assembly or solid phase pump assembly, and ii) is in bidirectional control signal communication with the signal hub, and the one or more transport unit actuation mechanisms are configured for synchronous actuation with the one or more first solid phase outlet valve assembly or solid phase pump assembly actuation mechanisms.

[0009] In at least one embodiment, the device includes a second chamber including: a) at least one each of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet; b) a second solid phase valve or pump assembly in fluid communication with the second solid phase inlet of the second chamber; c) a second gas phase valve or pump assembly adjacent to and in fluid communication with the second gas phase inlet of the second chamber; and d) a common signal hub. In at least one embodiment, the at least one second solid phase inlet and the at least one second solid phase outlet include a solid phase valve assembly or a solid phase pump assembly having at least two actuation mechanisms configured for bidirectional control signal communication with the signal hub. In at least one embodiment, the at least one second gas phase inlet and the at least one second gas phase outlet include a gas phase valve assembly or a gas phase pump assembly having at least one actuation mechanism configured for bidirectional control signal communication with the signal hub. In at least one embodiment, the second chamber further includes a second sensor network including two or more sensors, each sensor in the second sensor network configured to deliver one or more signals to a signal hub, the second sensor network configured to monitor a temperature, a pressure, and / or a composition of a gaseous environment surrounding the article. In at least one embodiment, at least one control system is configured to simultaneously send and receive multiple signals to one or more signal hubs to provide a controllable unit for regulating material flow.

[0010] In at least one embodiment, the second chamber is configured to a) receive a solid phase comprising flowable articles having a definable specific surface area through one or more second solid phase inlets, b) dispense a solid phase comprising flowable articles having a treated surface with a definable specific surface area through one or more second solid phase outlets, c) receive, create and / or contain a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through one or more second gas phase inlets, and d) dispense a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through one or more second gas phase outlets.

[0011] In at least one embodiment, the apparatus further includes at least one transport unit having one or more actuation mechanisms and configured to control the temperature, pressure, and composition of the gaseous environment while regulating the material flow rate of the plurality of flowable articles. In at least one embodiment, the inlet of the transport unit i) is in fluid communication with at least one first solid phase outlet valve assembly or solid phase pump assembly, and ii) is in bidirectional control signal communication with the signal hub, and the one or more transport unit actuation mechanisms are synchronously actuated with the one or more first solid phase outlet valve assembly or solid phase pump assembly actuation mechanisms.

[0012] In at least one embodiment, the outlet of the transport unit i) is in fluid communication with at least one second solid phase inlet valve assembly or solid phase pump assembly, and ii) is in bidirectional control signal communication with a signal hub. In at least one embodiment, the one or more transport unit actuation mechanisms are synchronously actuated with the one or more second solid phase inlet valve assembly or solid phase pump assembly actuation mechanisms.

[0013] In at least one embodiment, the one or more transport unit actuation mechanisms are synchronously actuated with one or more first solid phase outlet valve assemblies or solid phase pump assembly actuation mechanisms and one or more second solid phase inlet valve assemblies or solid phase pump assembly actuation mechanisms.

[0014] In at least one embodiment, the apparatus further includes a plurality of control systems and a master control system configured to simultaneously control the plurality of control systems.

[0015] In at least one embodiment, the apparatus further includes a plurality of signal hubs and a common signal hub configured to aggregate signals between the plurality of signal hubs.

[0016] In at least one embodiment, each actuation mechanism of the valve or pump assembly includes one or more of: i) instantaneous opening; ii) instantaneous closing; iii) controlled opening over a programmable time constant; iv) controlled closing over a programmable time constant; v) expansion of a subcomponent to reduce conductance through the assembly; vi) contraction of a subcomponent to increase conductance through the assembly; vii) concave or convex deflection of a subcomponent; viii) rotation of a subcomponent collinear with the direction of solid material flow; ix) rotation of a subcomponent tangential to the direction of solid material flow; x) instantaneous increase in conductance to a position less than a fully open position; xi) instantaneous decrease in conductance to a position greater than a fully closed position; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to facilitate aeration, contraction or expansion of a primary phase unit volume; or xiv) actuation mechanisms initiated by electrical application of a sine wave, Dirac function, triangle wave, or square wave over one or more programmable time constants.

[0017] In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies is configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve or pump assemblies.

[0018] In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the first chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve assemblies or gas phase pump assemblies of the first chamber. In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the second chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve or pump assemblies of the second chamber. In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the second chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more solid phase valve assemblies or solid phase pump assemblies of the first chamber.

[0019] In at least one embodiment, the at least one control system is configured for machine learning.

[0020] Another aspect of many embodiments of the invention relates to a method of performing a first surface treatment process on a plurality of fluent articles, comprising: a) providing a plurality of fluent articles having provided, estimated, measured or known specific surface areas in a first chamber and inputting the specific surface areas into at least one control system; b) inputting a nominal target for the amount, mass or unit volume of fluent articles to be treated into a control system of a surface treatment system, thereby defining a first total surface area target; c) providing a reactive precursor to treat surfaces of the plurality of fluent articles and inputting into the control system, using empirical or estimated process conditions, a provided, estimated, measured or known number of moles of reactive precursor needed to saturate, react with or treat the entirety of the first total surface area target, thereby defining a fully saturated amount; and d) selecting a target saturation ratio to obtain a process recipe for a batch, semi-batch, semi-continuous or continuous surface treatment process, the process recipe including at least one target pressure level related to the target saturation ratio.

[0021] In at least one embodiment, the method further includes e) dispensing a target amount, mass or unit volume of flowable article and gas phase environment into the first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects delivery of a gas / solid composition comprising primarily a gas phase and a second actuation mechanism effects delivery of a gas / solid composition comprising primarily a solid phase, and f) then dispensing a target number of moles of a gas phase comprising one or more reactive or non-reactive gases or precursors into said first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where a first actuation mechanism effects delivery of said gas phase under conditions suitable for carrying out a surface treatment reaction while preventing said solid phase from exiting the first chamber.

[0022] In at least one embodiment, the method includes g) administering a gas phase comprising a target number of moles of one or more reactive or non-reactive gases or precursors to the first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the one or more actuation mechanisms effect delivery of the gas phase under conditions suitable for carrying out a surface treatment reaction; h) then administering a target amount, mass or unit volume of flowable article and gas phase environment to the first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects delivery of a gas / solid composition comprising primarily or entirely a gas phase and a second actuation mechanism effects delivery of a gas / solid composition comprising primarily a solid phase.

[0023] In at least one embodiment, the method further comprises: i) dispensing a target amount, mass or unit volume of flowable article and gas phase environment into a first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects delivery of a gas / solid composition comprising primarily a gas phase and a second actuation mechanism effects delivery of a gas / solid composition comprising primarily a solid phase; and j) synchronously dispensing a target number of moles of a gas phase comprising one or more reactive or non-reactive gases or precursors into said first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where a first actuation mechanism effects delivery of said gas phase under conditions suitable for carrying out a surface treatment reaction while preventing a solid phase from exiting said first chamber.

[0024] In at least one embodiment, the method further comprises one or more of: k) incorporating a unit for monitoring signals from one or more pressure measurement sensors and increasing the residence time, the allowed mixing time and / or the interdiffusion rate between the gas and solid phases until said target pressure level is reached; l) synchronously, asynchronously, sequentially and / or cyclically discharging the gas and solid material through one or more outlets to a transport unit in relation to the main actuation mechanism due to each phase; and m) characterizing the treated solid material in terms of one or more of surface treatment loading, specific surface area after treatment or particle size or size distribution after treatment and inputting these into a control system to incorporate machine learning.

[0025] In at least one embodiment, the method further comprises: n) discharging the gas and solid materials synchronously, asynchronously, sequentially and / or cyclically through one or more outlets to a transport unit in relation to a primary actuation mechanism attributable to each phase, and o) initiating a second surface treatment process by dispensing a target amount, mass or unit volume of flowable article and gas phase environment into a second chamber through one or more second solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects the transport of a gas / solid composition comprising primarily a gas phase and a second actuation mechanism effects the transport of a gas / solid composition comprising primarily a solid phase. In at least one embodiment, the second surface treatment process in the second reactor chamber utilizes one or more of a different reactive precursor, a different operating pressure, a different operating temperature, a different residence time or different other process parameters than those used in the first surface treatment process.

[0026] In at least one embodiment, the first surface treatment process comprises one or more of atomic layer deposition, molecular layer deposition, chemical vapor deposition, physical vapor deposition, molecular layering process, atomic layer chemical vapor deposition, epitaxial deposition, chemical grafting, atomic layer etching, atomic layer etching, atomic layer combustion, or combinations thereof.

[0027] In at least one embodiment, the method further includes a subsystem configured to perform one or more of a flame spray process, a combustion spray process, a plasma spray process, a spray drying process, or a combination thereof.

[0028] In at least one embodiment, the method further includes a subsystem configured to control nominal values ​​and rates of change of one or more of: i) process pressure, ii) process temperature, iiii) gas phase composition or flow rate, iv) liquid phase composition or flow rate, v) solute or solvent composition or flow rate, and vi) solid phase composition or flow rate.

[0029] In at least one embodiment, the method includes a subsystem for synthesizing or receiving the article, a subsystem for treating a surface of the article, and a subsystem for applying a coating to the surface of the article.

[0030] In at least one embodiment, the method is suitable for synchronously processing a plurality of composite articles, the flowable articles including one or more of discrete particles, powders, extrudates, granules, and flowable objects. In at least one embodiment, the method is suitable for processing objects having a maximum dimension less than 125 millimeters in size, wherein at least 75% of the surface of said composite articles is coated or treated upon exiting the system.

[0031] In at least one embodiment, the method is configured to produce a material suitable for use in a battery, a fuel cell, a catalyst, a capacitor, a pharmaceutical ingredient, a passive electronic component, a solar cell, a 3D printer, a semiconductor device, an integrated circuit, an optoelectronic device, a thermoelectric device, a thermionic device, an electrochemical device, a biomedical device, or an electromechanical device.

[0032] In at least one embodiment, the method is configured to utilize a precursor that includes phosphorus, sulfur, nitrogen, carbon, fluorine, chlorine, bromine, or iodine, hi at least one embodiment, the precursor includes a phosphide, phosphate, sulfide, sulfate, nitrate, fluoride, chloride, bromide, or iodide.

[0033] In at least one embodiment, the method further includes one or more of a common precursor delivery subsystem, a precursor delivery enhancement subsystem, or an effluent treatment or recycling subsystem.

[0034] In at least one embodiment, the machine learning algorithm calculates sub-process deviations from modeled or empirical data using information derived from one or more of direct in-situ signals, indirect in-situ signals, direct external signals, or indirect external signals.

[0035] Another aspect of many embodiments of the present invention is a method for producing a liquid phase comprising: a) a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet; b) a second chamber having at least one each of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet; c) a first solid phase valve assembly or solid phase pump assembly in fluid communication with the first solid phase inlet of the first chamber, the first solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms; d) a first gas phase valve assembly or solid phase pump assembly adjacent to and in fluid communication with the first gas phase inlet of the first chamber; a first gas-phase valve assembly or gas-phase pump assembly having at least one actuation mechanism; e) a second solid-phase valve assembly or solid-phase pump assembly in fluid communication with the second solid-phase inlet of the second chamber, wherein the second solid-phase valve assembly or solid-phase pump assembly has at least two actuation mechanisms; f) a second gas-phase valve assembly or gas-phase pump assembly adjacent to and in fluid communication with the second gas-phase inlet of the first chamber, wherein the second gas-phase valve assembly or gas-phase pump assembly has at least one actuation mechanism; and g) a common signal hub.

[0036] In at least one embodiment, each actuation mechanism of the atomic layer deposition apparatus is configured in bidirectional signal communication with a common signal hub and is operable to: i) instantaneous opening; ii) instantaneous closing; iii) controlled opening over a programmable time constant; iv) controlled closing over a programmable time constant; v) expansion of the subcomponent to reduce conductance through the assembly; vi) contraction of the subcomponent to increase conductance through the assembly; vii) concave or convex deflection of the subcomponent; deflection; viii) rotation of the subcomponent collinear with the direction of solid material flow; ix) rotation of the subcomponent tangential to the direction of solid material flow; x) an instantaneous increase in conductance to a position less than fully open; xi) an instantaneous decrease in conductance to a position greater than fully closed; xii) actuation of a piston or piston-like subcomponent; xiii) actuation that delivers a secondary phase to promote aeration, contraction or expansion of a primary phase unit volume; or xiv) an actuation mechanism initiated by electrical application of a sine wave, Dirac function, triangle wave or square wave over one or more programmable time constants.

[0037] In at least one embodiment, the first and second chambers of the atomic layer deposition apparatus are each configured to: a) receive a solid phase comprising the article having a definable specific surface area through a respective solid phase inlet; b) dispense a solid phase comprising the article having a treated surface with a definable specific surface area through a respective solid phase outlet; c) receive, create and / or contain a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through a respective gas phase inlet; and d) dispense a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through a respective gas phase outlet.

[0038] In at least one embodiment, the first chamber of the atomic layer deposition apparatus further includes a first sensor network including two or more sensors, each sensor in the first sensor network configured to deliver one or more signals to the common signal hub, and the first sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the article.

[0039] In at least one embodiment, the atomic layer deposition apparatus further includes at least one control system configured to simultaneously transmit a plurality of signals to and receive a plurality of signals from a common signal hub, said control system configured to provide a controllable unit for regulating material flow throughout the apparatus.

[0040] In at least one embodiment, the atomic layer deposition apparatus further includes a third solid phase valve assembly or solid phase pump assembly in fluid communication with a) a second solid phase outlet of the second chamber, where the third solid phase valve assembly or solid phase pump assembly has at least two actuation mechanisms, and b) a first transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the article. In at least one embodiment, the first transport unit of the atomic layer deposition apparatus is in bidirectional control signal communication with a signal hub, and the one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the third solid phase valve assembly or solid phase pump assembly actuation mechanisms.

[0041] In at least one embodiment, the outlet of the first transport unit is in fluid communication with a fourth solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms, and one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the fourth solid phase valve assembly or solid phase pump assembly actuation mechanism.

[0042] In at least one embodiment, the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the third solid phase valve assembly or solid phase pump assembly, and the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the fourth solid phase valve assembly or solid phase pump assembly are the same.

[0043] In at least one embodiment, the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the third solid phase valve assembly or solid phase pump assembly and the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the fourth solid phase valve assembly or solid phase pump assembly are different.

[0044] In at least one embodiment, the atomic layer deposition apparatus further includes a second transport unit in fluid communication with the third solid phase valve assembly or solid phase pump assembly and in parallel with the first transport unit, the second transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the article. In at least one embodiment, the second transport unit of the atomic layer deposition apparatus is in bidirectional control signal communication with a signal hub, and the one or more actuation mechanisms of the second transport unit are configured to operate synchronously with the third solid phase valve assembly or solid phase pump assembly actuation mechanisms.

[0045] In at least one embodiment, the apparatus is further configured to adjust the flow rate of the solid phase comprising the article having a treated surface to each transport unit such that the specific surface area flowing through each transport unit is defined.

[0046] In at least one embodiment, the atomic layer deposition apparatus further includes a third gas-phase valve assembly or gas-phase pump assembly adjacent to, in fluid communication with, and interposed between a) the first gas-phase outlet of the first chamber and b) the first exhaust return manifold. In at least one embodiment, the third gas-phase valve assembly or gas-phase pump assembly having at least one actuation mechanism in bidirectional signal communication with the common signal hub is configured to control a pressure of a gaseous environment in the first chamber.

[0047] In at least one embodiment, the atomic layer deposition apparatus further comprises a fourth gas phase valve assembly or gas phase pump assembly adjacent to, in fluid communication with, and interposed between a) the second gas phase outlet of the second chamber and b) the second exhaust return manifold. In at least one embodiment, the fourth gas phase valve assembly or gas phase pump assembly has at least one actuation mechanism in bidirectional signal communication with the common signal hub, and is configured to control the pressure of the gas environment in the second chamber. In at least one embodiment, the at least one actuation mechanism of the fourth gas phase valve assembly or gas phase pump assembly is configured to operate synchronously with at least one actuation mechanism of the third gas phase valve assembly or gas phase pump assembly.

[0048] In at least one embodiment, the atomic layer deposition apparatus further comprises a first precursor delivery system having one or more actuation mechanisms and in fluid communication with the first gas-phase valve assembly or gas-phase pump assembly, the precursor delivery system including: i) an evaporator unit having an external heating mechanism; ii) an evaporator unit having an external cooling mechanism; iii) an evaporator unit having an internal heating mechanism; iv) an evaporator unit having an internal cooling mechanism; v) a precursor volume controller configurable for a particular article and process to be performed in the first chamber; vi) a liquid precursor injection pump system; vii) a solid precursor metering system; viii) one or more first capillary nozzles sized for a number of moles of precursor intended for delivery to the first chamber; ix) one or more first expansion tanks each having a definable total internal surface area, where the combined total surface area of ​​all first expansion tanks is greater than a total active surface area of ​​an article to be saturated in the first chamber; and x) a first evaporator unit having a rapid thermal processing system.

[0049] In at least one embodiment, the apparatus further includes a second precursor delivery system having one or more actuation mechanisms and in fluid communication with the second gas-phase valve assembly or gas-phase pump assembly, the precursor delivery system including: i) a second evaporator unit having an external heating mechanism; ii) a second evaporator unit having an external cooling mechanism; iii) a second evaporator unit having an internal heating mechanism; iv) a second evaporator unit having an internal cooling mechanism; v) a second precursor volume controller configurable for a particular article and process to be performed in the second chamber; vi) a second liquid precursor injection pump system; vii) a second solid precursor metering system; viii) one or more second capillary nozzles sized for the number of moles of precursor intended for delivery to the second chamber; ix) one or more second expansion tanks each having a definable total internal surface area, where the combined total surface area of ​​all second expansion tanks is greater than the total active surface area of ​​the article to be saturated in the second chamber; and x) a second evaporator unit having a rapid thermal processing system. In at least one embodiment, at least one actuation mechanism of a first precursor delivery system is synchronously actuated with at least one actuation mechanism of said second precursor delivery system.

[0050] In at least one embodiment, the atomic layer deposition apparatus is configured to perform one or more of batch, semi-batch, semi-continuous, and continuous atomic layer deposition processes or sub-processes.

[0051] In at least one embodiment, the second chamber is below the first chamber.

[0052] In at least one embodiment, at least a portion of the fourth solid phase valve assembly or pump assembly is disposed in the same horizontal plane as at least a portion of the first solid phase valve assembly or solid phase pump assembly.

[0053] In at least one embodiment, the actuation mechanism of the fourth solid phase valve assembly or pump assembly is configured to operate synchronously with the actuation mechanism of the first solid phase valve assembly or solid phase pump assembly.

[0054] In at least one embodiment, the outlet of the first transport unit is fluidly connected to the first solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms, and one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the first solid phase valve assembly or solid phase pump assembly actuation mechanism.

[0055] In at least one embodiment, the article is selected from the group consisting of a particle, a powder, and a porous support.

[0056] In at least one embodiment, the device is configured to operate at a minimum pressure of about 0.1 Torr. In at least one embodiment, the device is configured to accommodate a pressure drop of about 1,500 Torr or less.

[0057] These and other features, together with the organization and method of operation thereof, will become apparent from the following detailed description when taken in conjunction with the accompanying drawings. [Brief description of the drawings]

[0058] BRIEF DESCRIPTION OF THE DRAWINGS The details of one or more embodiments are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages of the disclosure will become apparent from the description, drawings, and claims. In the drawings, like reference numerals are used throughout the various views to indicate like elements.

[0059] [Figure 1] 1A-1D show a multi-step method for producing coated powders with optimized sub- and surface structures, including a coating step along with optional synthesis, pre-treatment and post-treatment steps, according to an exemplary embodiment of the present technology.

[0060] [Diagram 2] FIG. 2 is an operational flow diagram illustrating the process flow of FIG. 1A, in accordance with an exemplary embodiment of the present technique.

[0061] [Diagram 3] FIG. 3 is an operational flow diagram illustrating the coating subsystem shown in FIG. 2 with a common signal hub and a control scheme for machine learning with multi-sensor control in accordance with an exemplary embodiment of the present technique.

[0062] [Figure 4] FIG. 4 is an operational flow diagram illustrating a multi-zone chemical precursor storage, delivery and recycling system in accordance with an exemplary embodiment of the present technique.

[0063] [Diagram 5] FIG. 5 is an operational flow diagram illustrating a series of two-stage rotational processing systems configured to perform pre-treatment, surface coating or post-treatment operations for low vapor pressure liquid and solid precursors, according to an exemplary embodiment of the present technique.

[0064] [Figure 6] FIG. 6 is an operational flow diagram illustrating a multi-stage continuous processing and / or coating system in accordance with an exemplary embodiment of the present technique.

[0065] [Figure 7] FIG. 7 is an operational flow diagram illustrating a multi-stage batch, semi-batch, semi-continuous or continuous processing and / or coating system according to an exemplary embodiment of the present technique.

[0066] [Figure 8] FIG. 8 is an operational flow diagram illustrating a common synthesis subsystem, a common first processing subsystem, and a distributed and / or parallel and synchronized coating system according to an exemplary embodiment of the present technique.

[0067] [Figure 9] FIG. 9 is an operational flow diagram illustrating an asynchronous gas / solid coating or treatment system, in accordance with an exemplary embodiment of the present technique.

[0068] [Figure 10] FIG. 10 is an operational flow diagram illustrating a synchronous gas / solid coating or treatment system in accordance with an exemplary embodiment of the present technique.

[0069] [Figure 11] FIG. 11 is an operational flow diagram illustrating an asynchronous gas / solid coating or treatment system, in accordance with another exemplary embodiment of the present technique.

[0070] [Figure 12] FIG. 12 is an operational flow diagram illustrating an asynchronous gas / solid coating or treatment system in accordance with yet another exemplary embodiment of the present technique.

[0071] [Figure 13] FIG. 13 is an operational flow diagram illustrating a process flow for producing an optimized lithium-ion battery cathode powder in accordance with an exemplary embodiment of the present technique.

[0072] [Figure 14] Fig. 14A is a schematic diagram of a TEM image of a substrate powder of the method of Fig. 1D that has been pre-treated according to an exemplary embodiment of the present technology, Fig. 14B is a schematic diagram of a TEM image of a substrate powder of the method of Fig. 1D that has been pre-treated and then surface-coated using an ALD method according to an exemplary embodiment of the present technology, Fig. 14C is a schematic diagram of a TEM image of a substrate powder of the method of Fig. 1D that has been pre-treated and then surface-coated using an ALD method and then subjected to a post-treatment process according to an exemplary embodiment of the present technology.

[0073] [Figure 15]FIG. 15 is a block diagram illustrating the interrelationship between a common signal hub and computer controlled processes in accordance with an exemplary embodiment of the present technique.

[0074] [Figure 16] FIG. 16 is a block diagram illustrating a method used to provide process control to one or more valve-dependent subsystems based on critical inputs stored in an electronic database server in accordance with an exemplary embodiment of the present technique.

[0075] [Figure 17] FIG. 17 is a block diagram illustrating the temperature signal and the control scheme behind the control loop, in accordance with an exemplary embodiment of the present technique.

[0076] It will be appreciated that some or all of the figures are schematic for illustrative purposes. It is expressly understood that the drawings are provided for the purpose of illustrating one or more embodiments, and are not used to limit the scope or meaning of the claims. The depiction of specific heights, lengths, widths, relative sizes, number of chambers, subchambers, etc. are intended to serve as examples only, and are not intended to limit the scope of the present technology. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0077] Detailed Description Various embodiments are described below. It should be noted that the specific embodiments are not intended as an exhaustive description or as limitations to the broader aspects discussed herein. An aspect described in connection with a specific embodiment is not necessarily limited to that embodiment and can be implemented in any other embodiment.

[0078] Features may be described herein as part of the same or separate aspects or embodiments of the technology for purposes of clarity and conciseness. Those skilled in the art will appreciate that the scope of the technology may include embodiments having all or some combination of the features described herein as part of the same or separate embodiments.

[0079] Various techniques and features of the present technology are sometimes described in the singular for clarity. However, it should be noted that some embodiments include multiple iterations of a technique or multiple instantiations of a feature unless otherwise specified. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present technology. Certain exemplary embodiments of the present technology may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail in order not to unnecessarily obscure the present technology.

[0080] The following terms are used throughout and are defined below.

[0081] As used herein and in the appended claims, singular articles such as "a" and "an" and "the" and similar referents in the context of describing elements (particularly in the context of the claims below) are intended to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The recitation of ranges of values ​​herein is intended only to serve as a shorthand method of individually referring to each individual value falling within the range, unless otherwise indicated herein, and each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order, unless otherwise indicated herein or clearly contradicted by context. The use of any and all examples or exemplary language (e.g., "etc.") provided herein is intended only to better illuminate the embodiments and does not limit the scope of the claims, unless otherwise indicated. No language in the specification should be construed as indicating that any non-claimed element is required.

[0082] The embodiments illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations not specifically disclosed herein. Thus, for example, terms such as "comprising," "including," "containing," and the like, should be read broadly and not limiting. Furthermore, the terms and expressions used herein are used as terms of description and not of limitation. The use of such terms and expressions is not intended to exclude equivalents of the features shown and described or portions thereof, but it is understood that various modifications are possible within the scope of the claimed technology. In addition, the phrase "consisting essentially of" is understood to include the elements specifically recited, as well as additional elements that do not materially affect the basic and novel characteristics of the claimed technology. The phrase "consisting of" excludes elements not specified. The term "comprising" means "including, but not limited to." Thus, other materials, additives, carriers, or steps not mentioned may be present. Unless otherwise specified, "a" or "an" means one or more.

[0083] Unless otherwise indicated, all numbers expressing quantities of properties, parameters, conditions, and the like used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and the appended claims are approximations. Numerical parameters should be interpreted, at least in light of the reported significant digits and by applying rounding techniques. The term "about", when used prior to a numerical designation, indicates approximations, e.g., temperature, time, amounts, and concentrations, including ranges, may vary by (+) or (-) 10%, 5% or 1%.

[0084] As will be understood by those skilled in the art, for any and all purposes, particularly with respect to providing a written description, all ranges disclosed herein also encompass any and all possible subranges and combinations thereof. The ranges set forth are fully descriptive and readily identifiable as allowing the same range to be divided into at least one half, one third, one quarter, one fifth, one tenth, etc. As a non-limiting example, each range discussed herein can be readily divided into a lower third, a middle third, and an upper third. As will be understood by those skilled in the art, all language such as "up to," "at least," "greater than," "less than," etc., includes the recited numbers and refers to a range that can then be divided into subranges as discussed above. Finally, as will be understood by those skilled in the art, a range includes each individual element.

[0085] As used herein, "synchronization" refers to two or more events sharing one or more of a common starting point, a common ending point, a common rate or speed, a common frequency, or a common acceleration or rate of change of speed.

[0086] As used herein, "asynchronous" refers to two or more occurrences that do not share one or more of a common beginning, a common end, a common rate or speed, a common frequency, or a common acceleration or rate of change of speed.

[0087] The terms "adjacent," "superjacent," and "subjacent" may be used interchangeably herein.

[0088] The terms "substrate", "article" and "material" are used interchangeably herein. Suitable substrates, articles or materials include, but are not limited to, particles, powders, porous supports, flowable articles, bodies, composite workpieces, extrudates, extrudates, packing media, fillers, grains, precipitates, granules, and the like. In at least one embodiment, the articles described herein include flowable articles. Suitable flowable articles include, but are not limited to, metal powders, ceramic particles, catalyst supports including extrudates, additively manufactured alloy powders, polymer particles, electrochemically active precipitates, fly ash and other silicate fillers, carbon granules, extruded workpieces, thermal fillers, electrical fillers, base metal particles, separation media, electronic components such as circuit boards, metal shot powders, and the like.

[0089] The substrate or article may be any material that is chemically and / or thermally stable under the conditions of the deposition reaction. By "chemically" stable we mean that more than 15% of the surface of the article does not undergo undesirable chemical reactions during the deposition process, except in some cases bonding to the applied coating. By "thermally" stable we mean that more than 30% of the article does not melt, sublime, volatilize, degrade or otherwise dramatically change physical state under the conditions of the deposition reaction. In certain applications, powders that are typically ceramic or metallic in nature are used. Suitable materials include, but are not limited to, silica, alumina, glass, metals, phosphors, silicon, iron oxides, other metal oxides, nitrides such as tungsten nitride or boron nitride, and a wide range of other materials. Organic materials, including powdered organic polymers, can be used when the deposition temperature is somewhat lower.

[0090] The size of the article will depend on various factors, such as the particular end use application. In an exemplary embodiment, the powder can have a particle size as small as 5 nanometers up to a micron size or larger, such as up to 100 microns, or even up to 1 micron. Thus, the particle size can range from about 5 nm to about 1000 microns, including about 5 nm to about 100 microns, about 50 nm to about 50 microns, about 500 nm to about 25 microns, or about 1 micron to about 20 microns, and ranges between any two of these values, or ranges less than any one of these values. In at least one embodiment, the powder can have a particle size of up to 100 microns. Porous workpieces configured for use as catalyst supports, sometimes characterized as Geldart Class D particles, or sometimes characterized as Class A, Class B, or Class C particles, and sometimes in the form of extrudates or extrudates, can also be coated using one or more of the systems described herein. Such porous workpieces can have dimensions ranging from about 10 microns to about 5 centimeters in any characteristic dimension, and can be round, cylindrical, spherical, elliptical, oval, rectangular, smooth, rough or angular. Flowable solid workpieces such as small passive electronic components, thermoelectric devices or even gemstones can also be readily processed using the systems described herein.

[0091] As used herein, "precursor" refers to a reactant or starting material used at the beginning of a chemical process, which is typically reactive, but sometimes inert under certain operating conditions.

[0092] Suitable precursors include aluminum sec-butoxide, aluminum tribromide, aluminum trichloride, diethylaluminum ethoxide, dimethylaluminum isopropoxide, tris(ethylmethylamido)aluminum, tris(dimethylamido)aluminum, triethylaluminum, triisobutylaluminum, trimethylaluminum, tris(diethylamido)aluminum, tris(ethylmethylamido)aluminum, trimethylantimony(III), triethylantimony(III), triphenylantimony(III), tris(dimethylamido)antimony(III), trimethylarsine, triphenylarsine, triphenylarsine oxide, barium bis(2,2,6,6-tetramethyl-3,5-heptanedionate) hydrate, barium nitrate, bis(pentamethylcyclopentadienyl)barium tetrahydrofuran, bis(triisopropylcyclopentadienyl)barium tetrahydrofuran, bis(acetate), (O)triphenylbismuth(V), triphenylbismuth, tris(2-methoxyphenyl)bismuthine, diborane, trimethylboron, triethylboron, triisopropylborate, triphenylborane, tris(pentafluorophenyl)borane, cadmium acetylacetonate, calcium bis(2,2,6,6-tetramethyl-3,5-heptanedionate), carbon tetrabromide, carbon tetrachloride, cerium(III) trifluoroacetylacetonate, tetrakis( 2,2,6,6-tetramethyl-3,5-heptanedionato)cerium(IV), tris(cyclopentadienyl)cerium(III), tris(isopropylcyclopentadienyl)cerium(III), tris(1,2,3,4-tetramethyl-2,4-cyclopentadienyl)cerium(III), bis(cyclopentadienyl)chromium(II), bis(pentamethylcyclopentadienyl)chromium(II), chromium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), chromium(II) chloride, chromium(III) chloride, carbonylchromium(II), carbonylchromium(III), cyclopentadienyl(II)chromium carbonyl, bis(cyclopentadienyl)cobalt(II), bis(ethylcyclopentadienyl)cobalt(II), bis(pentamethylcyclopentadienyl)cobalt(II), tribis(N,N'-diisopropylacetominato)cobalt(II), dicarbonyl(cyclopentadienyl)cobalt(III), cyclopentadienylcobalt(II) carbonyl, copper bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate) , copper bis(2,2,6,6-tetramethyl-3,5-heptanedionate, (N,N'-diisopropylacetaminato)copper(II), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)dysprosium(III), tris(isopropylcyclopentadienyl)dysprosium(III), erbium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(butylcyclopentadienyl)erbium(III), tris(N,N-bis(trimethylsilyl))amido)europium(III), tris(tetramethylcyclopentadienyl)europium(III), nitrogen trifluoride, tris(N,N-bis(trimethylsilyl)amido)gadolinium(III), tris(cyclopentadienyl)gadolinium(III), tris(tetramethylcyclopentadienyl)gadolinium(III), gallium tribromide, gallium trichloride, triethylgallium, triisopropylgallium, trimethylgallium, tris(dimethylamido)gallium, tri-tert-butylgallium, digermane, germane, tetramethylgermanium, germanium(IV) fluoride, germanium(IV) chloride, hexaethyldigermanium(IV), hexaphenyldigermanium(IV), Germanium(IV), tributylgermanium hydride, triphenylgermanium hydride, dimethyl(acetylacetonate)gold(III), dimethyl(trifluoroacetylacetonate)gold(III), hafnium(IV) chloride, hafnium(IV) tert-butoxide, tetrakis(diethylamido)hafnium(IV), tetrakis(dimethylamido)hafnium(IV), tetrakis(ethylmethylamido)hafnium(IV), bis(tert-butylcyclopentadienyl)dimethylhafnium(IV), bis(methyl-n- cyclopentadienyl)dimethylhafnium, bis(trimethylsilyl)amidohafnium(IV) chloride, dimethylbis(cyclopentadienyl)hafnium(IV), hafnium isopropoxide, tris(N,N-bis(trimethylsilyl)amido)holmium(III), indium trichloride, indium iodide(I), indium acetylacetonate, triethylindium, tris(dimethylamido)indium, tris(diethylamido)indium, tris(cyclopentadienyl)indium, 1,5-cyclooctadiene(acetylacetonate) 1,5-cyclooctadiene(hexafluoroacetylacetonato)iridium(I), 1-ethylcyclopentadienyl-1,3-cyclohexadieneiridium(I), (methylcyclopentadienyl)(1,5-cyclooctadiene)iridium(I), bis(N,N'-di-tert-butylacetamidinato)iron(II), bis(pentamethylcyclopentadienyl)iron(II), ferrocene, 1,1'-diethylferrocene, iron pentacarbonyl, iron(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(N,N'-di-tert-butylacetamidinato)lanthanum(III), lanthanum(III) isopropoxide, tris(N,N-bis(trimethylsilyl)amido)lanthanum(III), tris(cyclopentadienyl)lanthanum(III), tris(tetramethylcyclopentadienyl)lanthanum(III), tetraethyllead, tetramethyllead, tetraphenyllead, titanium t-butoxide, lithium trimethylsilylamide, lithium(2,2,6,6-tetramethyl-3,5-heptanedionate) nate), tris(N,N-diisopropylacetamidinato)lutetium(III), lutetium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)magnesium(II), bis(pentamethylcyclopentadienyl)magnesium(II), bis(pentaethylcyclopentadienyl)magnesium(II), bis(cyclopentadienyl)manganese(II), bis(N,N-diisopropylpentylamidinato)manganese(II), bis(ethylcyclopentadienyl) Bis(pentamethylcyclopentadienyl)manganese(II), bis(isopropylcyclopentadienyl)manganese(II), cyclopentadienyl manganese tricarbonyl, manganese carbonyl, methylcyclopentadienyl manganese tricarbonyl, mangantricarbonyl, mangantris(2,2,6,6-tetramethyl-3,5-heptanedionate), molybdenum hexacarbonyl, molybdenum(V) chloride, molybdenum(VI) fluoride, bis(cyclopentadienyl)molybdenum(IV) dichloride, cyclopentadienyl cyclopentadienylmolybdenum(II) tricarbonyl, propylcyclopentadienylmolybdenum(I) tricarbonyl, tris(N,N-bis(trimethylsilyl)amido)neodymium(III), bis(methylcyclopentadienyl)nickel(II), allyl(cyclopentadienyl)nickel(II), bis(cyclopentadienyl)nickel(II), bis(ethylcyclopentadienyl)nickel(II), bis(triphenylphosphine)nickel(II) dichloride, nickel(II) bis(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)niobium(IV) dichloride, niobium(V) chloride, niobium(V) isopropoxide, niobium(V) ethoxide, N,N-dimethylhydrazine, ammonia, hydrazine, ammonium fluoride, azidotrimethylsilane, triosmium dodecacarbonyl, allyl(cyclopentadienyl)palladium(II), palladium(II) hexafluoroacetylacetonate, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)palladium(II), phosphine, tert-butylphosphine Sphines, tris(trimethylsilyl)phosphine, phosphorus oxychloride, triethyl phosphate, trimethyl phosphate, methylcyclopentadienyl(trimethyl)platinum(IV), chloroplatinic acid, praseodymium(III) hexafluoroacetylacetonate hydrate, dirhenium decacarbonyl, acetylacetonato(1,5-cyclooctadiene)rhodium(I), bis(ethylcyclopentadienyl)ruthenium(II), bis(cyclopentadienyl)ruthenium(II), bis(pentamethylcyclopentadienyl)ruthenium(II), tolyl dodecacarbonyl, tris(N,N-bis(trimethylsilyl))amido)samarium(III), tris(tetramethylcyclopentadienyl)samarium(III), tris(2,2,6,6-tetramethyl-3,5-heptanedionato)scandium(III), dimethyl selenide, diethyl selenide, 2,4,6,8-tetramethylcyclotetrasiloxane, dimethoxydimethylsilane, disilane, methylsilane, octamethylcyclotetrasiloxane, silane, tris(isopropoxy)silanol, tris(tert-butoxy)silane nol, tris(tert-pentoxy)silanol, (3-aminopropyl)triethoxysilane, N-sec-butyl(trimethylsilyl)amine, chloropentamethyldisilane, hexamethyldisilazane, silicon(IV) chloride, silicon(IV) bromide, pentamethyldisilane, tetraethylsilane, N,N',N''-tri-tert-butylsilanetriamine, (2,2,6,6-tetramethyl-3,5-heptanedionato)silver(I), triethoxyphosphine(trifluoroacetylacetonate)silver(I), silver(I) triethylphosphine(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate), trimethylphosphine(hexafluoroacetylacetonate)silver(I), vinyltriethylsilane(hexafluoroacetylacetonate)silver(I), strontium tetramethylheptanedionate, pentakis(dimethylamido)tantalum(V), tantalum(V) chloride, tantalum(V) ethoxide, tantalum(V) fluoride, thionium Tris(ethylmethylamido)tert-butylimido)tantalum(V), tris(diethylamido)(tert-butylimido)tantalum(V), tellurium tetrabromide, tellurium tetrachloride, terbium(2,2,6,6-tetramethyl-3,5-heptanedionate), tris(cyclopentadienyl)terbium(III), tris(tetramethylcyclopentadienyl)terbium(III), thallium(I) ethoxide, thallium (I) hexafluoroacetylacetonate, cyclopentadienylthallium, 2,2,6,6-tetramethyl-3,5-heptanedithionatothallium(I), tris(N,N-bis(trimethylsilyl)amido)thulium(III), tris(cyclopentadienyl)thulium(III), tin(IV) chloride, tetramethyltin, tin(II) acetylacetonate, tin(IV) tert-butoxide, tin(II) hexafluoroacetylacetonate, bis(N,N'-diisopropylacetamidinato)tin(II), N,N-di-tert-butyl-2,3-diamidinobutanetin(II), tetrakis(dimethylamino)tin(IV), bis(diethylamido)bis(dimethylamido)titanium(IV), tetrakis(diethylamido)titanium(IV), tetrakis(dimethylamido)titanium(IV), tetrakis(ethylmethylamido), titanium(IV), titanium(IV) bromide, titanium(IV) chloride, titanium(IV) fluoride, titanium(IV) tert-butoxide, titanium(IV) isopropoxide, titanium(IV) ethoxide, titanium(IV) methoxide, titanium(IV) isopropoxide bis(2,2,6,6-tetramethyl-3,5-heptanedionate), dichlorotitanium(IV) oxide, bis(tert-butylimido)bis(dimethylamido)tungsten(VI), tungsten hexacarbonyl, tungsten(VI) Chloride, tungsten(VI) fluoride, triaminetungsten(IV) tricarbonyl, cyclopentadienyltungsten(II) tricarbonyl hydride, bis(isopropylcyclopentadienyl)tungsten(IV) dihydride, bis(cyclopentadienyl)tungsten(IV) dihydride, bis(cyclopentadienyl)tungsten(IV) dichloride, bis(butylcyclopentadienyl)tungsten(IV) diiodide, bis(cyclopentadienyl)vanadium(II), trichloride oxide Vanadium(V), Vanadium(V) oxytriisopropoxide, Tris(N,N-bis(trimethylsilyl)amido)ytterbium(III), Tris(cyclopentadienyl)ytterbium(III), Tris(N,N-bis(trimethylsilyl)amido)yttrium(III), Yttrium(III) tris(tert-butoxide), Yttrium(III) triisopropoxide, Yttrium(III) tris(2,2,6,6-tetramethyl-3,5-heptanedionate), Tris(butyl cyclopentadienyl)yttrium(III), tris(cyclopentadienyl)yttrium(III), yttrium 2-methoxyethoxide, diethylzinc, dimethylzinc, diphenylzinc, bis(2,2,6,6-tetramethyl-3,5-heptanedionate)zinc(II), bis(pentafluorophenyl)zinc, zirconium(IV) dibutoxide (bis-2,4-pentanedionate), zirconium(IV) 2-ethylhexanoate, zirconium tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionate), bis(cyclopentadienyl)zirconium(IV) dihydride, bis(methyl-n-cyclopentadienyl)methoxymethylzirconium, tetrakis(diethylamido)zirconium(IV), dimethylbis(pentamethylcyclopentadienyl)zirconium(IV), tetrakis(dimethylamido)zirconium(IV), tetrakis(ethylmethylamido)zirconium(IV), zirconium(IV) bromide, zirconium(IV) chloride, zirconium(IV) tert-butoxide, and mixtures of two or more thereof. Precursors for the synthesis of powders and particles, and sometimes their encapsulation, often include metal salts and hydroxides, and are administered as dry powders, liquid or gas feedstocks, or dissolved in a suitable solvent, via an injection device, nozzle, spray device, vaporizer, sonicator, or other known subcomponents. Metal salts include Ac, Ag, Al, Am, As, At, Au, B, Ba, Be, Bh, Bi, Bk, Br, C, Ca, Cd, Ce, Cf, Cm, Cn, Co, Cr, Cs, Cu, Db, Ds, Dy, Er, Es, Eu , Fe, Fl, Fm, Fr, Ga, Gd, Ge, H, Hf, Hg, Ho, Hs, In, K, La, Li, Lr, Lu, Lv, Mc, Md, Mg, Mn, Mo, Mt, N, Na, Nb, Nd, Nh, Ni, No, Np , O, Og, Os, P, Pa, Pb, Pd, Pm, Po, Pr, Pt, Pu, Ra, Rb, Re, Rf, Rg, Rh, Ru, S, Sb, Sc, Se, Sg, Si, Sm, Sn, Sr, Ta, Tb, Tc, Te, Th, Ti, Tl, Tm, Ts, U, V, W, Y, Yb, Zn, Zr, or combinations thereof, in the form of a halide, sulfate, nitrate, oxalate, phosphate, or other inorganic or organic compound.

[0093] In at least one embodiment, the precursor comprises one or more of phosphorus, sulfur, nitrogen, carbon, fluorine, chlorine, bromine, or iodine, hi at least one embodiment, the precursor comprises a phosphide, a phosphate, a sulfide, a sulfate, a nitrate, a fluoride, a chloride, a bromide, or an iodide.

[0094] Various embodiments of the technology described herein relate to systems, devices, and methods for treating articles. The treatment may include, but is not limited to, one or more of the following: synthesis, functionalization, surface treatment, and encapsulation of the article. In one aspect, the technology provides an apparatus for treating an article. The apparatus is suitable for performing various treatment steps on various articles. By way of example, the system, device, or method is configured to apply a layer to an article or substrate by various vapor deposition techniques. Examples of vapor deposition techniques may include molecular layering (ML), chemical vapor deposition (CVD), physical vapor deposition (PVD), atomic layer deposition (ALD), molecular layer deposition (MLD), vapor phase epitaxy (VPE), atomic layer chemical vapor deposition (ALCVD), ion implantation, or similar techniques. In each of these, a coating is formed by exposing a powder to reactive precursors, which react in the gas phase (e.g., in the case of CVD) or on the surface of the powder particles (such as ALD and MLD).

[0095] In one aspect, disclosed herein is a system for controlling a plurality of cellular networks controlled from a common signal hub, A system and method for synthetically processing, functionalizing, and / or encapsulating an article, substrate, or object, comprising one or more of the following: 1. Inlet, outlet and, at the same time, a controllable unit for regulating the material flow, controlling the conversion of precursors to products and controlling the nominal operating pressure, a synthesis subsystem having at least one chamber comprising: 2. A pre-treatment subsystem having at least one chamber with an inlet, an outlet and, at the same time, a controllable unit for regulating the material flow and controlling the pre-treatment process (which may include one or more of plasma treatment, thermal treatment, microwave treatment, oxidation treatment, reduction treatment, pH adjustment treatment, molecular grafting treatment, etching treatment or a combination thereof), and means for controlling one or more of the nominal operating pressure, gas concentration, temperature and / or flow rate; 3. A functionalization subsystem having at least one chamber with an inlet, an outlet and, at the same time, a controllable unit for regulating the material flow, controlling the conversion of the precursors into functionalized products and controlling the nominal operating pressure; 4. A post-treatment subsystem having at least one chamber including an inlet, an outlet and simultaneously a controllable unit for adjusting the material flow and controlling the post-treatment process (which may include one or more of plasma treatment, thermal treatment, microwave treatment, oxidation treatment, reduction treatment, pH adjustment treatment, molecular grafting treatment, etching treatment or a combination thereof) and means (units) for controlling one or more of the nominal operating pressure, gas concentration, temperature and / or flow rate; 5. A valve or pump assembly with at least two actuating mechanisms, which may control two or more separate sub-valves or sub-pumps within a valve or pump assembly, or separate features of a common valve or pump, where at least one actuating mechanism is predominantly dependent on the properties of the solid phase, at least one is predominantly dependent on the properties of the gas phase, and where applicable, at least one is predominantly dependent on the properties of the liquid phase. In the case of a valve assembly, each actuation mechanism represents one or more of: i) instantaneous opening; ii) instantaneous closing; iii) controlled opening over a programmable time constant; iv) controlled closing over a programmable time constant; v) expansion of a subcomponent to reduce conductance through the assembly; vi) contraction of a subcomponent to increase conductance through the assembly; vii) concave or convex deflection of a subcomponent; viii) rotation of a subcomponent collinear with the direction of solid material flow; ix) rotation of a subcomponent tangential to the direction of solid material flow; x) instantaneous increase in conductance to a position less than fully open; xi) instantaneous decrease in conductance to a position greater than fully closed; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to facilitate venting, contraction or expansion of a primary phase unit volume; or xiv) actuation mechanisms initiated by electrical application of a sine wave, Dirac function, triangle wave, or square wave over one or more programmable time constants. 6. One or more vertical transport operating means, each having an inlet, an outlet, and a controllable unit for supplying and regulating material flow and for transiently controlling the ambient environment before and after each inlet and outlet, at least one transport operating means facing downward and depositing material into an underlying receiver, and at least one transport operating means facing upward and depositing material into an underlying receiver, the supply operations of the vertical transport operations commonly controlling and maintaining a substantially uniform transport rate. 7. A control system configured for machine learning designed for simultaneous or synchronous feedback and / or feedforward control of chemical reaction reactant flows, chemical reaction product flows, chemical reaction operating conditions, system health, transfer timing and programmable steps, batching considerations for monitored physicochemical parameters, looping considerations, and continuous monitoring of mass or volumetric transport of materials during production; 8. Typically one or more subsystems suitable for operation in a continuous mode, and preferably one or more subsystems operating in a semi-continuous or batch mode; 9. At least one yield enhancing structural or functional design feature required for the manufacture of a particular material combination suitable for use in a commercial or industrial product, including precursor delivery units, chamber geometries, analytical monitoring instrumentation connectivity, flow enhancers, stirrers, vibrators, agitators, heaters, filters, actuators, valves, control systems, control intelligence, or other unique design features determined to be essential to the manufacture of a product with high yields, and 10. Any one or more sub-components, configurations and / or services of other systems.

[0096] The apparatus can include a plurality of solid phase inlets, solid phase outlets, gas phase inlets, gas phase outlets, solid phase valve assemblies, gas phase valve assemblies, a signal hub, and a control system. In at least one embodiment, the article can include a powder or a flowable article.

[0097] In another aspect, disclosed herein is an apparatus including at least a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet, including at least a first solid phase valve or pump assembly in fluid communication with the first solid phase inlet of the first chamber, including at least a first gas phase valve or pump assembly adjacent to and in fluid communication with the first gas phase inlet of the first chamber, and including a common signal hub.

[0098] In yet another aspect, disclosed herein is an apparatus for treating an article or for treating a surface of an article with a gaseous precursor, the apparatus including: a) a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet, b) a first solid phase valve or pump assembly in fluid communication with the first solid phase inlet of the first chamber, c) a first gas phase valve or pump assembly adjacent to and in fluid communication with the first gas phase inlet of the first chamber, and d) a common signal hub. In at least one embodiment, the article includes a plurality of flowable articles.

[0099] In the apparatus, the at least one first solid phase inlet and the at least one first solid phase outlet include a solid phase valve assembly or a solid phase pump assembly having at least two actuation mechanisms configured to enable bidirectional control signal communication with a signal hub.

[0100] In the device, at least one first gas phase inlet and at least one first gas phase outlet include a gas phase valve assembly or a gas phase pump assembly having at least one actuation mechanism configured for bidirectional control signal communication with a signal hub.

[0101] In the apparatus, the first chamber further includes a first sensor network including two or more sensors, each sensor in the first sensor network configurable to deliver one or more signals to a signal hub, the first sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the item.

[0102] The apparatus includes at least one control system configured to simultaneously transmit a plurality of signals to and receive a plurality of signals from one or more signal hubs to provide a controllable unit or means for regulating material flow.

[0103] The apparatus may further include at least one transport means or transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the plurality of articles. The inlet of the transport unit may be configured to be in fluid communication with at least one first solid phase outlet valve assembly or solid phase pump assembly. The inlet of the transport unit may be configured to be in bidirectional control signal communication with the signal hub. The one or more transport unit actuation mechanisms are configured to synchronously operate with the one or more first solid phase outlet valve assembly or solid phase pump assembly actuation mechanisms.

[0104] The apparatus may further include a second chamber similar or different to the first chamber, the second chamber may include one or more of: a) at least one each of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet, b) a second solid phase valve or pump assembly in fluid communication with the second solid phase inlet of the second chamber, c) a second gas phase valve or pump assembly adjacent to and in fluid communication with the second gas phase inlet of the second chamber, and d) a common signal hub.

[0105] In the apparatus, the at least one second solid phase inlet and the at least one second solid phase outlet include a solid phase valve assembly or a solid phase pump assembly having at least two actuation mechanisms configured in bidirectional control signal communication with the signal hub.

[0106] In the device, the at least one second gas phase inlet and the at least one second gas phase outlet include a gas phase valve assembly or a gas phase pump assembly having at least one actuation mechanism configured to be in bidirectional control signal communication with the signal hub.

[0107] In the apparatus, the second chamber further includes a second sensor network including two or more sensors, each sensor in the second sensor network configured to deliver one or more signals to a signal hub, the second sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the item.

[0108] The apparatus further includes at least one control system for the second chamber, the control system configured to simultaneously transmit and receive a plurality of signals to and from the one or more signal hubs to provide a controllable unit for regulating the material flow.

[0109] The apparatus having a second chamber further includes a second transport means or transport unit. The second transport unit may include at least one transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the plurality of articles. In at least one embodiment, the inlet of the second transport unit is in fluid communication with at least one first solid phase outlet valve assembly or solid phase pump assembly. In at least one embodiment, the inlet of the second transport unit is in bidirectional control signal communication with a signal hub. In at least one embodiment, the one or more transport unit actuation mechanisms can be actuated in synchrony with the one or more first solid phase outlet valve assembly or solid phase pump assembly actuation mechanisms. In at least one embodiment, the outlet of the second transport unit is in fluid communication with at least one second solid phase inlet valve assembly or solid phase pump assembly. In at least one embodiment, the outlet of the second transport unit is in bidirectional control signal communication with a signal hub. In at least one embodiment, the one or more transport unit actuation mechanisms can be actuated in synchrony with the one or more second solid phase inlet valve assembly or solid phase pump assembly actuation mechanisms. In at least one embodiment, the one or more transport unit actuation mechanisms can be actuated in synchronization with one or more first solid phase outlet valve assemblies or solid phase pump assembly actuation mechanisms and one or more second solid phase inlet valve assemblies or solid phase pump assembly actuation mechanisms.

[0110] The apparatus can include multiple control systems. In at least one embodiment, the apparatus includes a master control system configured to simultaneously control the multiple control systems. In at least one embodiment, the apparatus includes at least one control system configured for machine learning. The apparatus can include multiple signal hubs. In at least one embodiment, the apparatus includes a common signal hub configured to aggregate signals between the multiple signal hubs.

[0111] In at least one embodiment, an apparatus described herein is configured to receive a solid phase comprising an article having a definable specific surface area through one or more solid phase inlets, dispense a solid phase comprising an article having a treated surface with a definable specific surface area through one or more solid phase outlets, receive, create and / or contain a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through one or more gas phase inlets, and / or dispense a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through one or more gas phase outlets.

[0112] In at least one embodiment, the actuation mechanism of the valve assembly or pump assembly of the device is configured for bidirectional control signal communication with the signal hub. In at least one embodiment, the actuation mechanism of the valve or pump assembly includes one or more of: i) instantaneous opening; ii) instantaneous closing; iii) controlled opening over a programmable time constant; iv) controlled closing over a programmable time constant; v) expansion of a subcomponent to reduce conductance through the assembly; vi) contraction of a subcomponent to increase conductance through the assembly; vii) concave or convex deflection of a subcomponent; viii) rotation of a subcomponent collinear with the direction of solid material flow; ix) rotation of a subcomponent tangential to the direction of solid material flow; x) instantaneous increase in conductance to a position less than a fully open position; xi) instantaneous decrease in conductance to a position greater than a fully closed position; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to facilitate aeration, contraction or expansion of a primary phase unit volume; or xiv) actuation mechanism initiated by electrical application of a sine wave, Dirac function, triangle wave, or square wave over one or more programmable time constants.

[0113] In one aspect, the present invention relates to a method for producing a liquid-liquid separator comprising: at least a first chamber having at least one of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet; at least a second chamber having at least one of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet; a first solid phase valve or pump assembly in fluid communication with the first solid phase inlet of the first chamber, the first solid phase valve or pump assembly having at least two actuation mechanisms; and a first gas phase valve or pump assembly adjacent to and in fluid communication with the first gas phase inlet of the first chamber. An apparatus is provided comprising a valve or pump assembly, the valve or pump assembly including at least a first gas phase valve or pump assembly having at least one actuation mechanism, a second solid phase valve or pump assembly in fluid communication with the second solid phase inlet of the second chamber, the second solid phase valve or pump assembly having at least two actuation mechanisms, a second gas phase valve or pump assembly adjacent to and in fluid communication with the second gas phase inlet of the first chamber, the second gas phase valve or pump assembly having at least one actuation mechanism, and g) a common signal hub.

[0114] The actuation mechanisms of the devices may be configured for bidirectional signal communication with the common signal hub. The actuation mechanism may be selected from one or more of: i) instantaneous opening; ii) instantaneous closing; iii) controlled opening over a programmable time constant; iv) controlled closing over a programmable time constant; v) expansion of a subcomponent to reduce conductance through the assembly; vi) contraction of a subcomponent to increase conductance through the assembly; vii) concave or convex deflection of a subcomponent; viii) rotation of a subcomponent collinear with the direction of solid material flow; ix) rotation of a subcomponent tangential to the direction of solid material flow; x) instantaneous increase in conductance to a position less than a fully open position; xi) instantaneous decrease in conductance to a position greater than a fully closed position; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to facilitate aeration, contraction or expansion of a primary phase unit volume; or xiv) actuation mechanism initiated by electrical application of a sine wave, Dirac function, triangle wave or square wave over one or more programmable time constants. In at least one embodiment, the apparatus is an atomic layer deposition apparatus for processing an article. The article can include, for example, a particle, a powder, or a porous support.

[0115] Each of the first and second chambers may be configured to perform one or more functions. For example, the first and second chambers may receive a solid phase including an article having a definable specific surface area through a respective solid phase inlet, dispense a solid phase including an article having a treated surface having a definable specific surface area through a respective solid phase outlet, receive, create and / or contain a gas phase including one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through a respective gas phase inlet, and / or dispense a gas phase including one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through a respective gas phase outlet. In at least one embodiment, the first chamber further includes a first sensor network including two or more sensors. Each sensor may be configured to deliver one or more signals to the common signal hub. Additionally, the first sensor network may be configured to monitor various characteristics, such as, for example, temperature, pressure, and / or composition, of the gaseous environment surrounding the article. In at least one embodiment, the apparatus further includes at least one control system. The control system may be configured to simultaneously transmit multiple signals to and receive multiple signals from a common signal hub. The control system may further be configured to provide a controllable unit for regulating material flow. The apparatus described herein may perform one or more of batch, semi-batch, semi-continuous, and continuous processes, such as, for example, an atomic layer deposition process or sub-process.

[0116] The various actuation mechanisms may be configured to be actuated simultaneously, synchronously or asynchronously with respect to each other. In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve or gas phase pump assemblies. In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies in a first chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve or gas phase pump assemblies in a first chamber. In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies in a second chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve or pump assemblies in said second chamber. In at least one embodiment, at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the second chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more solid phase valve assemblies or solid phase pump assemblies of the first chamber.

[0117] In yet another aspect, disclosed herein is a method of treating a surface of an article with a gaseous precursor, the method including receiving a solid phase including an article having a definable specific surface area through one or more first solid phase inlets of a first chamber, dispensing the solid phase including the article having a treated surface with a definable specific surface area through one or more first solid phase outlets of the first chamber, receiving, creating and / or containing a gas phase including one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through one or more first gas phase inlets of the first chamber, and dispensing a gas phase including one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through one or more first gas phase outlets of the first chamber.

[0118] In another aspect, disclosed herein is a method of performing a surface treatment process on a plurality of articles with reactive precursors in a surface treatment system including at least one chamber and at least one control system, the method including providing a plurality of articles, the articles having a provided, estimated, measured, or known specific surface area, and inputting the specific surface area into a control system and inputting a nominal target for the amount, mass, or unit volume of the articles to be treated into the control system of the surface treatment system, thereby defining a first total surface area target, providing reactive precursors to treat surfaces of the plurality of articles, and inputting into the control system, using empirical or estimated process conditions, the number of moles of one or more provided, estimated, measured, or known reactive precursors required to saturate, react with, or treat all of the first total surface area target, defining a full saturation amount, and selecting a target saturation ratio to obtain a process recipe for a batch, semi-batch, semi-continuous, or continuous surface treatment process including at least one target pressure level associated with the target saturation ratio.

[0119] The methods described herein can include additional steps, such as administering a target amount, mass or unit volume of the article and gas phase environment to the first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects delivery of a gas / solid composition comprising primarily a gas phase and a second actuation mechanism effects delivery of a gas / solid composition comprising primarily a solid phase, and then administering a target number of moles of a gas phase comprising one or more reactive or non-reactive gases or precursors to the first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the first actuation mechanism effects delivery of the gas phase under conditions suitable for carrying out a surface treatment reaction while preventing the solid phase from exiting the first chamber.

[0120] The method further includes dispensing a gas phase comprising a target number of moles of one or more reactive or non-reactive gases or precursors into the first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the first actuation mechanisms effect delivery of the gas phase under conditions suitable for effecting a surface treatment reaction, and then dispensing a target amount, mass or unit volume of flowable articles and gas phase environment into the first chamber through one or more first solid phase inlets having two or more actuation mechanisms. Suitable actuation mechanisms can include actuation mechanisms that effect delivery of a gas / solid composition comprising primarily or entirely a gas phase, and / or actuation mechanisms that effect delivery of a gas / solid composition comprising primarily a solid phase.

[0121] The method further includes dispensing a target amount, mass or unit volume of the article and gas phase environment into the first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects transport of a gas / solid composition comprising primarily a gas phase and a second actuation mechanism effects transport of a gas / solid composition comprising primarily a solid phase, and synchronously dispensing a target number of moles of a gas phase comprising one or more reactive or non-reactive gases or precursors into the first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the first actuation mechanism effects transport of the gas phase under conditions suitable for carrying out a surface treatment reaction while preventing the solid phase from exiting the first chamber.

[0122] The method may include additional steps, such as monitoring signals from one or more pressure measurement sensors and incorporating means to increase residence time, allowable mixing time and / or interdiffusion rate of the gas and solid phases until at least one target pressure level is achieved, discharging the gas and solid material synchronously, asynchronously, sequentially and / or periodically into a transport unit through one or more outlets in relation to the primary actuation mechanism due to each phase, characterizing the treated solid material for one or more of surface treatment loading, post-treatment specific surface area or post-treatment particle size or size distribution, and inputting the characteristic values ​​into a control system for incorporating machine learning.

[0123] The method may further include one or more of: discharging the gas and solid materials synchronously, asynchronously, sequentially and / or cyclically in relation to a primary actuation mechanism attributable to each phase into a transport unit through one or more outlets, and initiating a second surface treatment process by administering a target amount, mass or unit volume of the article and gas phase environment into the second chamber through one or more second solid phase inlets having two or more actuation mechanisms. The first actuation mechanism may effect the transport of a gas / solid composition comprising primarily a gas phase, and the second actuation mechanism may effect the transport of a gas / solid composition comprising primarily a solid phase. In at least one embodiment, the second surface treatment process in the second reactor chamber utilizes one or more of a different reactive precursor, a different operating pressure, a different operating temperature, a different residence time or different other process parameters than those used for the first surface treatment process.

[0124] Suitable surface treatment processes include, but are not limited to, atomic layer deposition, molecular layer deposition, chemical vapor deposition, physical vapor deposition, molecular layering, atomic layer chemical vapor deposition, epitaxial deposition, chemical grafting, atomic layer etching, atomic layer etching, atomic layer combustion, or any combination thereof.

[0125] In at least one embodiment, the method further includes a subsystem configured to perform one or more of a flame spray process, a combustion spray process, a plasma spray process, a spray drying process, or a combination thereof.

[0126] In at least one embodiment, the method further includes a subsystem configured to control nominal values ​​and rates of change of one or more of: i) process pressure, ii) process temperature, iiii) gas phase composition or flow rate, iv) liquid phase composition or flow rate, v) solute or solvent composition or flow rate, and vi) solid phase composition or flow rate. In at least one embodiment, the method further includes a subsystem for synthesizing or receiving an article, a subsystem for treating a surface of the article, and a subsystem for applying a coating to a surface of the article. In at least one embodiment, the method further includes one or more of a common precursor delivery subsystem, a precursor delivery enhancement subsystem, or an effluent treatment or recycling subsystem.

[0127] The apparatus and methods described herein are suitable for synchronously processing a plurality of composite articles, such as discrete particles, powders, extrudates, granules, flowable articles and objects, or objects having suitable dimensions and characteristics, such as objects having a maximum dimension less than 125 mm in size, where at least 75% of the surface of said composite articles is coated or treated upon exiting the system. In at least one embodiment, the method further includes a machine learning algorithm that calculates sub-process deviations from modeled or empirical data using information derived from one or more of the direct in-situ signal, the indirect in-situ signal, the direct external signal, or the indirect external signal.

[0128] The apparatus and methods described herein are configured to produce materials suitable for use in batteries, fuel cells, catalysts, capacitors, pharmaceutical ingredients, passive electronic components, solar cells, 3D printers, semiconductor devices, integrated circuits, optoelectronic devices, thermoelectric devices, thermionic devices, electrochemical devices, biomedical devices, or electromechanical devices.

[0129] Precursors suitable for use in the apparatus and methods are described herein. In at least one embodiment, the apparatus and methods described herein are configured to utilize precursors that include one or more of phosphorus, sulfur, nitrogen, carbon, fluorine, chlorine, bromine, or iodine. In at least one embodiment, the apparatus and methods described herein are configured to utilize precursors that include one or more of phosphides, phosphates, sulfides, sulfates, nitrates, fluorides, chlorides, bromides, or iodides.

[0130] In another aspect, an atomic layer deposition apparatus for processing an article is disclosed, comprising: a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet; a second chamber having at least one each of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet; a first solid phase valve assembly or solid phase pump assembly in fluid communication with the first solid phase inlet of the first chamber, the first solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms; a first gas phase valve assembly adjacent to and in fluid communication with the first gas phase inlet of the first chamber; The system includes a first gas-phase valve assembly or gas-phase pump assembly having at least one actuation mechanism, a second solid-phase valve assembly or solid-phase pump assembly in fluid communication with the second solid-phase inlet of the second chamber, the second solid-phase valve assembly or solid-phase pump assembly having at least two actuation mechanisms, a second gas-phase valve assembly or gas-phase pump assembly adjacent to and in fluid communication with the second gas-phase inlet of the first chamber, the second gas-phase valve assembly or gas-phase pump assembly having at least one actuation mechanism, and a common signal hub.

[0131] In at least one embodiment, each actuation mechanism of the atomic layer deposition apparatus is configured in bidirectional signal communication with a common signal hub and is operable to control: i) instantaneous opening; ii) instantaneous closing; iii) controlled opening over a programmable time constant; iv) controlled closing over a programmable time constant; v) expansion of the subcomponent to reduce conductance through the assembly; vi) contraction of the subcomponent to increase conductance through the assembly; vii) concave or convex deflection of the subcomponent; viii) deflection of the subcomponent in a direction collinear with the direction of solid material flow; x) an instantaneous increase in conductance to a position less than fully open; xi) an instantaneous decrease in conductance to a position greater than fully closed; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to promote aeration, contraction or expansion of a primary phase unit volume; or xiv) an actuation mechanism initiated by electrical application of a sine wave, Dirac function, triangle wave or square wave over one or more programmable time constants.

[0132] In at least one embodiment, the first and second chambers of the atomic layer deposition apparatus are each configured to: a) receive a solid phase comprising the article having a definable specific surface area through a respective solid phase inlet; b) dispense a solid phase comprising the article having a treated surface with a definable specific surface area through a respective solid phase outlet; c) receive, create and / or contain a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through a respective gas phase inlet; and d) dispense a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through a respective gas phase outlet.

[0133] In at least one embodiment, the first chamber of the atomic layer deposition apparatus further includes a first sensor network including two or more sensors, each sensor in the first sensor network configured to deliver one or more signals to the common signal hub, and the first sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the article.

[0134] In at least one embodiment, the atomic layer deposition apparatus further includes at least one control system configured to simultaneously transmit a plurality of signals to and receive a plurality of signals from a common signal hub, the control system configured to provide a controllable unit for regulating material flow throughout the apparatus.

[0135] In at least one embodiment, the atomic layer deposition apparatus further includes: a) a third solid phase valve assembly or solid phase pump assembly in communication with a second solid phase outlet of the second chamber, the third solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms; and b) a first transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the article. In at least one embodiment, the first transport unit of the atomic layer deposition apparatus is in bidirectional control signal communication with a signal hub, and the one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the third solid phase valve assembly or solid phase pump assembly actuation mechanisms. In at least one embodiment, the outlet of the first transport unit is in fluid communication with a fourth solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms, and the one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the fourth solid phase valve assembly or solid phase pump assembly actuation mechanisms. In at least one embodiment, the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the third solid phase valve assembly or solid phase pump assembly and the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the fourth solid phase valve assembly or solid phase pump assembly are the same. In at least one embodiment, the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the third solid phase valve assembly or solid phase pump assembly and the actuation mechanism of the first transport unit configured to operate synchronously with the actuation mechanism of the fourth solid phase valve assembly or solid phase pump assembly are different.

[0136] In at least one embodiment, the atomic layer deposition apparatus further includes a second transport unit in fluid communication with the third solid phase valve assembly or solid phase pump assembly and in parallel with the first transport unit, the second transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the article. In at least one embodiment, the second transport unit of the atomic layer deposition apparatus is in bidirectional control signal communication with a signal hub, and the one or more actuation mechanisms of the second transport unit are configured to operate synchronously with the third solid phase valve assembly or solid phase pump assembly actuation mechanisms.

[0137] In at least one embodiment, the atomic layer deposition apparatus is further configured to adjust the flow rate of the solid phase including the article having the treated surface to each transport unit so that the specific surface area flowing through each transport unit can be defined. In at least one embodiment, the atomic layer deposition apparatus further includes a third gas phase valve assembly or gas phase pump assembly adjacent to, in fluid communication with, and interposed between a) the first gas phase outlet of the first chamber and b) the first exhaust return manifold. In at least one embodiment, the third gas phase valve assembly or gas phase pump assembly has at least one actuation mechanism in bidirectional signal communication with the common signal hub and is configured to control the pressure of the gas environment in the first chamber.

[0138] In at least one embodiment, the atomic layer deposition apparatus further comprises a fourth gas phase valve assembly or gas phase pump assembly adjacent to, in fluid communication with, and interposed between a) the second gas phase outlet of the second chamber and b) the second exhaust return manifold. In at least one embodiment, the fourth gas phase valve assembly or gas phase pump assembly has at least one actuation mechanism in bidirectional signal communication with the common signal hub and is configured to control a pressure of a gas environment in the second chamber. In at least one embodiment, at least one actuation mechanism of the fourth gas phase valve assembly or gas phase pump assembly is configured to operate synchronously with at least one actuation mechanism of the third gas phase valve assembly or gas phase pump assembly.

[0139] In at least one embodiment, the atomic layer deposition apparatus further comprises a first precursor delivery system having one or more actuation mechanisms and in fluid communication with the first gas-phase valve assembly or gas-phase pump assembly, the precursor delivery system including: i) an evaporator unit having an external heating mechanism; ii) an evaporator unit having an external cooling mechanism; iii) an evaporator unit having an internal heating mechanism; iv) an evaporator unit having an internal cooling mechanism; v) a precursor volume controller configurable for a particular article and process to be performed in the first chamber; vi) a liquid precursor injection pump system; vii) a solid precursor metering system; viii) one or more first capillary nozzles sized for a number of moles of precursor intended for delivery to the first chamber; ix) one or more first expansion tanks each having a definable total internal surface area, where the sum of the total surface areas of all first expansion tanks is greater than a total active surface area of ​​an article to be saturated in the first chamber; and x) a first evaporator unit having a rapid thermal processing system.

[0140] In at least one embodiment, the apparatus further includes a second precursor delivery system having one or more actuation mechanisms and in fluid communication with the second gas-phase valve assembly or gas-phase pump assembly, the precursor delivery system including: i) a second evaporator unit having an external heating mechanism; ii) a second evaporator unit having an external cooling mechanism; iii) a second evaporator unit having an internal heating mechanism; iv) a second evaporator unit having an internal cooling mechanism; v) a second precursor volume controller configurable for a particular article and process to be performed in the second chamber; vi) a second liquid precursor injection pump system; vii) a second solid precursor metering system; viii) one or more second capillary nozzles sized for the number of moles of precursor intended for delivery to the second chamber; ix) one or more second expansion tanks each having a definable total internal surface area, where the sum of the total surface areas of all second expansion tanks is greater than the total active surface area of ​​the article to be saturated in the second chamber; and x) a second evaporator unit having a rapid thermal processing system. In at least one embodiment, at least one actuation mechanism of a first precursor delivery system is synchronously actuated with at least one actuation mechanism of said second precursor delivery system.

[0141] The atomic layer deposition apparatus may be configured to perform one or more of batch, semi-batch, semi-continuous and continuous atomic layer deposition processes or sub-processes.

[0142] The positions or locations of the chambers, inlets, outlets and valves can be changed depending on the end use application. In at least one embodiment, the second chamber is below the first chamber. In at least one embodiment, at least a portion of the fourth solid valve assembly or pump assembly is disposed in the same horizontal plane as at least a portion of the first solid valve assembly or solid phase pump assembly. In at least one embodiment, the actuation mechanism of the fourth solid valve assembly or pump assembly is configured to operate synchronously with the actuation mechanism of the first solid phase valve assembly or solid phase pump assembly. In at least one embodiment, the outlet of the first transport unit is in fluid communication with the first solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms, and one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the actuation mechanism of the first solid phase valve assembly or solid phase pump assembly.

[0143] The systems and devices of the present technology can be configured to operate at a variety of pressure levels. For example, the devices can be configured to operate at a minimum pressure of about 0.1 Torr. Additionally, the devices can be configured to accommodate pressure drops of up to about 1500 Torr, for example.

[0144] FIG. 1 shows four of many possible configurations of the present technology. FIG. 1A shows a general embodiment of the present technology, a four-step method for producing encapsulated powders with optimized substructure and surface structure through post-synthesis and post-coating treatment steps. The embodiment shown in FIG. 1A provides an apparatus and method for producing synthesized and coated powders that benefit from post-synthesis and post-coating treatment steps without producing inferior composite powders. A more specific example of such a method is shown in FIG. 1B, where the synthesis process includes a flame-based or combustion synthesis type spray pyrolysis process, the pre-treatment step includes a rapid plasma annealing step, and the post-treatment step after the ALD coating step includes thermal annealing. In such a method, precursors are administered in or near a flame and particles can be synthesized in a continuous manner. In some applications, energy-providing steps (e.g., thermal treatment, plasma treatment, electromagnetic wave / field treatment, etc.) are beneficial to promote certain crystalline phases, reduce surface area, or reduce other attributes that would otherwise create an inferior product. Such combination of synthesis and treatment steps can be performed in one or more of the systems described herein, with each sub-step connected to a common signal hub that acts as a master controller that can have machine learning capabilities. Once conditions are optimized for the synthesis and treatment steps, surface modification sub-processes and subsystems can be integrated into comprehensive processes and systems. One such process, ALD, includes a specific set of steps and sequences that are performed over a specific space (spatial ALD) or time (temporal ALD). The specific number of steps and process conditions can be tailored for a specific product. Once a surface coating process is defined to produce a coated workpiece or powder, specific post-treatment sub-processes can be performed in subsystems to fully optimize the material for the end-use application.FIG. 1C shows an embodiment that includes multiple coating steps to produce a multifunctional, multi-layered and / or hybrid coating, or a first coating material is designed such that the components of the first coating material diffuse into a first synthesized powder to produce a first integrated substructure, and then a synthesis and coating step produces a multifunctional or hybrid superstructure, which can then optionally be followed by a post-processing step. This method incorporates a slurry spray method that includes particles or powders that are formulated into a slurry with other inert or active materials, which can be delivered, for example, through a flame spray, plasma spray, or spray drying system. This method is particularly useful for composite powders that benefit from being synthesized in two steps, where the composition produced in the two steps is unique and not easily achievable in a one-step method. This type of material can further benefit from a first ALD coating material that is uniformly applied to the substrate, which can then be processed in a second synthesis step to uniformly incorporate the uniformly dispersed first ALD coating material into the final composite particle. A second ALD coating material can then be applied to the outer surface of the composite material, followed by another processing step, if desired. Figure ID shows a simplified embodiment in which a powder is provided to the system and includes processing steps before and after the coating step. In this method, a pre-processing step is performed on the powder in one or more of the described subsystems and sub-processes, and once the powder is coated, it is processed in similar or different processing subsystems and sub-processes to produce an optimized composite substrate or powder.

[0145] FIG. 2 shows a process flow diagram of one embodiment of FIG. 1A, including a synthesis subsystem, a pre-treatment subsystem, a two-step ALD coating process in series, a post-treatment subsystem, unit operations to harvest optimized materials, and common computer control for all key process and operating parameters. The method is designed to produce composite powder products that are tailored and designed to achieve a value proposition for customers in an end-use environment. The synthesis subsystem 101 can represent one of an array of particle synthesis systems, where one or more precursor feedstocks are operatively delivered to the system through an inlet assembly 102 at known flow rates, concentrations, temperatures, pressures, and periodicities measured and controlled through control ports 103, and the system delivers synthesized materials through an outlet assembly 104. The control ports can include one or more of the following: i) valved ports designed for material or material flow into and out of the system, optionally with a filtration unit; ii) diagnostic ports for in-situ measurement capability for process material and / or product monitoring; iii) sampling ports for removing process material and / or product for external measurement capability; iv) optical ports for monitoring process material and / or product, such as plasma glow discharge, or FTIR spectroscopic monitoring of organic materials; v) injection or mechanical mixing ports for shearing and / or stirring / mixing powders, workpieces, extrudates, etc. throughout the process carried out in the synthesis subsystem. The control ports can be located at the top, near the top, in the middle, and / or at or near the bottom of the synthesis subsystem. In at least one embodiment, the same type or category of control ports are strategically placed in multiple locations throughout the system, sometimes including baffles or internals that can extend from the wall to the center of the synthesis subsystem or even to the other side of the synthesis subsystem. Upon completion, the synthesis powder exits the exit assembly in a controlled manner and is routed via transport units 105 and / or 106 to processing subsystems, one representing the primary pathway and the other representing a secondary pathway that enhances one or more characteristics of the primary pathway, including an inert flow booster system or a convective thermal modulation system.

[0146] The processing subsystem 201 represents a pre-treatment operation that performs a pre-treatment process. The control ports 202 are selected in type, location and frequency to perform specific sub-processes to improve the properties of the powder synthesized in the synthesis subsystem. An important feature of the processing subsystem is the computer-controlled processing assembly 203 that controls the overall material and mass transport of each phase involved in the process in the processing subsystem. The processing assembly includes material flow valves used to control the material flow through the subsystem and is configured to receive the powder directly from the transport unit or staged via a hopper as depicted above the processing assembly. The processing assembly is typically augmented by a processing enhancer 204 that can include one or more inert gases, reducing gases or gases, oxidizing gases or gases, etchants or other chemically reactive gases or gases, dopant gases, molecular grafting gases or other functionalization gases or gases. To maximize efficiency, the process enhancer is designed to be in electrical communication with the exit assembly 104 and the transport unit 106, so that the output parameters of the process enhancer are aligned with known quantified physical attributes of the synthesized material from the synthesis subsystem 101. One of the important characteristics that is monitored and passed through the control systems of each subsystem is the specific surface area of ​​the substrate, powder, extrudate or workpiece. The process subsystem can benefit from a process mixer 205, which can include material mixing or blending units (e.g., mechanical, acoustic, vibratory, etc.), such as stirrers, blenders, impellers, stators or tuning forks, and energy delivery and control means (e.g., conductive, convective or radiative heating, plasma exposure, etc.), which are fully controllable from a common signal hub. Additionally, the process control port 206, which is similar in form, classification and function to the control port 103, is useful for implementing certain types of sub-processes and operations in the process subsystem. Upon completion, the treated powder (and the synthesized and treated powders provided in FIG. 2) exits the treatment subsystem in a controlled manner and is sent via transport unit 207 to the coating subsystem.

[0147] Coating subsystem 301 is one embodiment of a broader category of coating subsystems that can be deployed to produce a wide range of optimized products using the processes, sub-processes, systems and / or subsystems of the present technology. The coating subsystem can represent a batch, semi-batch, semi-continuous or continuous coating subsystem. Exemplary systems include the batch system described by van Ommen et al. (U.S. Application Serial No. 11 / 955,184), the semi-batch or semi-continuous system described by King et al. (U.S. Application Serial No. 13 / 069,452), and the continuous system described by Elam et al. (U.S. Application Serial No. 14 / 339,058), all of which are incorporated herein by reference. Coating subsystem 301 is designed to be compatible with carrying out the process of King et al. (U.S. Application Serial No. 13 / 069,452), while the system and overall process incorporate important features that improve upon the systems described by Ommen et al., King et al. and Elam et al. The coating subsystem may include at least one chamber with an inlet, an outlet, and a controllable unit for simultaneously regulating material flow, controlling the conversion of precursors to functionalized products, and controlling nominal operating pressure and temperature. The coating subsystem may include at least one valve assembly 311 having an inlet and an outlet, where the inlet is in fluid communication with the outlet of an adjacent or above chamber, and the outlet is in fluid communication with the inlet of an adjacent or below chamber, and the valve assembly has at least two computer-controlled actuation mechanisms for maintaining a nominal pressure in the adjacent chamber. A first computer-controlled actuation mechanism provides a means for releasing a first phase of material without allowing other phases of material to flow from one chamber to the other, and a second, third, etc. computer-controlled actuation mechanism provides sequential means for allowing other phases of material to flow from one adjacent chamber to a different adjacent chamber. Each system or subsystem includes at least one computer-controlled actuation mechanism for each phase of material present in the system or subsystem.This goes beyond what is contemplated in any of the systems described by Ommen et al., King et al., and Elam et al. Each computer-controlled actuation mechanism is in electronic communication with a common signal hub and at least one computer-controlled actuation mechanism for the same phase of material of a separate subsystem for controlling a separate sub-process. This is conceptually illustrated by dashed rectangles connecting subsystems 104, 203, 302, etc., and for example, one or more subcomponents of a coating subsystem depicted as parallel (e.g., coating subsystems 302 and 402) may also be in the same horizontal plane when depicted in a horizontal plane, and nothing prevents the depicted subsystems or subcomponents from being in different horizontal planes. This material phase-based monitoring and control system is preferably designed for simultaneous feedback and feedforward control of reactant flows, product flows, operating conditions, and for continuous monitoring of mass or volumetric transport of material during production. The coating subsystem may further include at least one yield enhancing structural or functional design feature required for the production of a particular material combination suitable for use in a commercial or industrial product, including precursor delivery units, chamber geometries, analytical monitoring instrument connectivity, flow enhancers, stirrers, vibrators, agitators, heaters, filters, actuators, valves, control systems, control intelligence, or other unique design features determined to be essential for producing the product at high yields.

[0148] The coating subsystem of Fig. 2 includes at least two vertical transport operating means, each with an inlet, an outlet and a controllable unit for supplying and adjusting the material flow and for temporally controlling the surrounding environment. Suitably, at least one transport operating means faces downwards and deposits material into an underlying receiver, and at least one transport operating means (e.g., transport unit 303) faces upwards and deposits material into an underlying receiver (e.g., coating subsystem 401, processing system 501, stopping unit 601, or recirculation to synthesis system 101, processing system 201 or coating subsystem 301), and the supply operations of each vertical movement operating means are commonly controlled to maintain a substantially uniform hourly transport rate. The system is designed to provide a synchronized flow of material through the transport units 106, 207, 303, etc. from a common signal hub.

[0149] The second coating subsystem of FIG. 2, i.e., coating subsystem 401, is similar to coating subsystem 301, however the sub-processes performed in each of these subsystems may be the same or different depending on the substrate or workpiece, the type and / or composition of the coating, whether the sub-process represents a first pass, second pass or nth pass through the subsystem, group of subsystems or entire system, the nature of the performance benefits resulting from the subject optimized composite material and its industrial applicability.

[0150] Processing subsystem 501 in FIG. 2 is similar to processing subsystem 201 and is designed to perform the fourth step shown in FIG. 1A. The sub-processes performed in each processing subsystem may be the same or different depending on the type of substrate or workpiece, the type of processing process, whether this sub-process represents a first, second or nth pass through a subsystem, a group of subsystems or the entire system, the nature of the performance benefits resulting from the targeted optimized composite material and its industrial applicability. For some materials and products, processing subsystem 501 is not required, making this step optional and simplifying each optional scheme shown in FIG. 1. For some other materials and products, processing subsystem 501 represents a thermal annealing sub-process designed to improve the performance of the material that optionally passes through subsystems 101, 201, 301 and / or 401 before reaching processing subsystem 501. For processing processes that benefit from residence times that exceed the time constants associated with the synchronized flow of material, this technique provides for converging or diverging flows in one or more parallel systems. These parallel systems are designed to maintain an overall uniform transport rate with appropriately sized transport units and chamber / vessel volumes, and to allow centralized management of at least one subsystem operating in a continuous mode and at least one subsystem operating in a semi-continuous or batch mode. For example, a single synthesis subsystem 101 can be a continuous process that is split into two or more parallel product streams using diverter valves or similar devices and then fed into a single semi-batch processing subsystem 201 that feeds into two or more parallel coating subsystems (an exemplary subsystem can be represented by the semi-continuous unit shown in FIG. 2). In such a system, the volume of each coating subsystem chamber can be smaller than the volume of the processing subsystem 201. Subsequent material handling systems are deployed to recombine the parallel product streams, feeding one common processing subsystem 501, which then flows into a bagging operation or similar operation as depicted by the stop unit 601.Alternatively, a surge tank can be used in which a batch, sub-batch or other unit volume of material can be collected or otherwise temporarily stored until a computer control signal causes the unit volume to re-enter the process for continued processing.

[0151] FIG. 3 shows one embodiment of the coating subsystem 302 of FIG. 2A, with a common signal hub (360) and a control scheme for machine learning with multi-sensor control by temperature, pressure, gas composition, pH, etc., with common dosing elements, common exhaust or filtration elements, and unit volume management of mass and material throughout both the subsystems and the complete system. In this configuration, the global transport vector of one phase of material is directed approximately vertically between the valve assemblies 311 and 315, and the second phase of material may be transported horizontally, for example, from an individual control port 330 or 331, for example, or alternatively, from the control port manifold 350. Alternatively, or in addition, one or more second phases of material may be dosed through the valve assemblies 311 and / or 315 before, during, or after the transport of the first phase. One or more control ports may be computer controlled and have actuation mechanisms that operate synchronously or asynchronously with other control ports (e.g., signal line 340) or valve assemblies (e.g., signal line 390). Additionally, the system includes signal lines 380 and common signal hub 360 as a means to operate the entire system in an infinite number of configurations and / or modes of operation, four of which are highlighted in Figure 1. Additionally, coating subsystem 302 may further include at least one yield improving structural or functional design feature required for the manufacture of a particular material combination suitable for use in a commercial or industrial product, including precursor delivery units, chamber geometries (e.g., the oversimplified geometry represented by 310), analytical monitoring instrumentation connectivity, flow enhancers (e.g., 320), stirrers, vibrators, agitators, heaters (e.g., 321), filters, actuators, valves, fluidization aids or phases, control systems, control intelligence, or other unique design features determined to be critical for manufacturing products with high yields.

[0152] For example, in a subsystem that performs a gas / solid sub-process, such as coating subsystem 302, it may be advantageous to utilize valve assembly 311 and valve assembly 315, each of which has at least two actuation mechanisms for controlling or metering the flow of substrates through coating subsystem 301. The two or more actuation mechanisms may control two or more separate sub-valves within valve assembly 311 or 315, or separate features of a common valve, with at least one actuation mechanism being predominantly driven by the properties of the solid phase and at least one other valve being predominantly driven by the properties of the gas phase. Each actuation mechanism may include one or more of: i) instantaneous opening of the valve; ii) instantaneous closing of the valve; iii) controlled opening of the valve over a programmable time constant; iv) controlled closing of the valve over a programmable time constant; v) expansion of a subcomponent of the valve assembly to reduce conductance through the valve assembly; vi) contraction of a subcomponent of the valve assembly to increase conductance through the valve assembly; vii) concave or convex deflection of a subcomponent of the valve assembly to change the volumetric capacity of the coating subsystem; viii) rotation of the subcomponent collinear with the direction of bulk material flow; or ix) rotation of the subcomponent tangential to the direction of bulk material flow.

[0153] In at least one embodiment, two or more of these mechanisms can be actuated synchronously, where two or more actuating mechanisms can be associated with a single valve assembly or two or more valve assemblies. In at least one embodiment, two or more actuating mechanisms can be associated in sequence with no time lapse between actuations. For some materials, time constants between actuating mechanisms can be useful and are typically associated with and scaled with key parameters such as the total surface area of ​​the material, total volume, particle size or size distribution, pore size, structure or size distribution, degradation phenomena, etching or deposition rates, temperature, pressure, etc. In any other embodiment, it can be useful to actuate one or more mechanisms intermittently throughout part or all of the duration of the sub-process performed by the coating subsystem 302, or randomly or stochastically while being controlled via the common signal hub 360. The actuating mechanisms (312, 313, 316, 317), as well as other valve assemblies of other subsystems and control ports of the coating subsystem 302, are preferably controlled and adjusted via the common signal hub 360 to accommodate different coating processes, substrate changes, among others.

[0154] FIG. 4 illustrates an embodiment of a chemical system 700 of precursor storage, delivery and recycling subsystem suitable for a single precursor as described herein. The storage unit 701 is configured for computer controlled delivery of chemical precursors through a pump station 702 to a distribution manifold 704, which can provide a particular chemical directly to the synthesis subsystem 101, the processing subsystem 201, the coating subsystem 301 or 401 or the processing subsystem 501, as applied to FIG. 2 for example, depending on the composition and applicability of the particular chemical. The pump station 702 preferably has the ability to maintain a constant precursor pressure using a secondary valve configuration with all components in electrical communication with a common signal hub. Again, the common signal hub 360 is represented as a means to provide an electrical communication path between a particular leg (with signal connector 705) of the distribution manifold 704 and, for example, the control port manifold 350 of FIG. 3. The chemical systems are in electrical communication with corresponding subsystems (e.g., 101, 201, 301, 401, 501, etc.) via a common signal hub 360, such that actuation of a particular mechanism of any one or more valve assemblies is fluidly communicated within or between one or more subsystems. Furthermore, actuation of the valve assemblies can be coordinated in any configuration, e.g., synchronously, continuously, intermittently, or offset by one or more time constants. The type of configuration depends on and is scaled by one or more common critical parameters, such as total surface area of ​​material, total volume, particle size or size distribution, degradation phenomena, etching or deposition rate, temperature, pressure, etc. The time constants can be further attenuated by the distance between the chemical system 700 and a particular delivery point (using signal connector 703), the flow rate from pump station 702, and the recycle introduction from return manifold 706.

[0155] The transport enhancer 800 shown in FIG. 4 is designed for two-phase (or three-phase) flow of precursors diluted in a secondary (tertiary) medium and can be particularly advantageous for the delivery of low vapor pressure liquid precursors, highly exothermic precursors, toxic or hazardous precursors, and solid precursors. The transport enhancer can be designed to vaporize the precursors by volume expansion, enhanced gas flow, larger precursor / container surface area to enhance the vaporization rate of the precursor when exposed to gas flow, improved heat transfer, or any combination thereof. In at least one embodiment, the precursor can be provided, stored, or placed in a precursor container 801 in fluid communication with a valved delivery assembly 805, which in turn can be operably connected to one or more subsystems of FIG. 2, e.g., 204, 302, 402, etc., and can optionally include an evaporator chamber 810, broadly representing an evaporation unit. The evaporator chamber can be externally heated or incorporate an internal heating mechanism. In other embodiments, the evaporator chamber can represent a capillary tube with appropriate characteristics related to the material to be vaporized. The transport enhancer is preferably configured to be sized based on one or more common critical parameters such as total surface area of ​​material, total volume, particle size or size distribution, degradation phenomenon, etching or deposition rate, reaction temperature, operating pressure, etc., specific to the method and material performed by the subsystem to which the transport enhancer is operably connected, and includes a precursor volume controller 804 that is further regulated using a common signal hub. The delivery nozzle 811 benefits from a pressure drop in the pressure of the chamber through which the precursor volume controller and the nozzle are configured to pass. In at least one embodiment, the transport enhancer is used to deliver a specific precursor to the coating subsystem. The common signal hub identifies the critical threshold amount of a specific precursor required to saturate the total surface area of ​​the material to be coated in the specific sub-process step corresponding to the coating subsystem, and loads that amount into the vacuum precursor volume controller. The pressure of the vaporizer chamber is simultaneously or sequentially brought to a pressure condition sufficiently lower than the pressure of the precursor volume controller when it is filled with the critical threshold amount of the specific precursor.The coating chambers 310 are simultaneously or sequentially brought to a pressure condition sufficiently lower than that of the vaporizer chamber. The condition is continuously monitored by a common signal hub via signal connectors 806 and 807. Alternatively, rather than using pressure differentials to control the delivery of the precursors, gravity transport may be sufficient for the delivery of some solid precursors, which may be dropped in whole or in part, directly or indirectly. In some cases, the vaporizer chamber 810 is filled with a fill medium 808, which is configured to have a surface area larger than the total surface area of ​​the material to be coated in a particular sub-process step corresponding to the coating subsystem 302. In at least one embodiment, the fill medium may have a smaller surface area. The vaporizer chamber may optionally be equipped with a rapid thermal processing system, which is designed to rapidly release the precursor from the fill medium at a specified time. Alternatively or in addition, reactive gases may be incorporated into such a system to enhance the ability to clean and switch the vaporizer chamber without removing the fill medium. The vaporizer chamber can be operably connected to additional secondary or tertiary media delivery systems via one or more purge ports 802a in fluid communication with the chamber when the valved delivery assembly 805 via valve 803 is so configured for operation, or optionally via purge port 802b in fluid communication with the chamber via distribution plate 809.

[0156] Each subsystem utilizing a particular low vapor pressure liquid or solid precursor may benefit from fluid communication with one or more dedicated transport enhancers 800 for each precursor inlet assembly versus a conventional centralized chemistry system 700 with a single distribution manifold 704, where the single distribution manifold 704 is operably connected to one or more subsystems, as disclosed, for example, in U.S. Patent Publication No. 2008 / 0202416 to Provencher et al. In at least one embodiment, one or more legs of the distribution manifold 704 are configured to be in fluid communication with a precursor container 801 to more precisely deliver and manage precursors that are not characterized as low vapor pressure liquid precursors, highly exothermic precursors, toxic or poisonous precursors, solid precursors, or other difficult or dangerous precursors. In such a configuration, the vaporizer chamber 810 may represent, for example, the coating chamber 310 of FIG. 3, and the delivery nozzle 811 may penetrate directly thereto for efficient precursor delivery. A transport enhancer may be utilized, for example, to increase the throughput of material produced in the subsystem by at least 10% or to increase the precursor consumption efficiency by at least 5% compared to a subsystem without the transport enhancer. For processes roughly determined by surface area (such as coating or grafting processes), the total surface area may be utilized as the critical parameter. For processes such as oxidation, reduction, and etching, both surface area and reaction penetration depth, which can define a volumetric value, may be utilized as the critical parameter. For processes such as thermal annealing, granulation, or agglomeration to achieve a particular secondary particle size, length scales such as average diameter may be utilized as the critical parameter. These process and potential critical parameters are not intended to be limiting of the invention, but are included as a representative subset of parameters that may be identified and monitored qualitatively or quantitatively at the inputs and outputs of each subsystem of interest, enabling machine learning for process and product optimization via a common signal hub.

[0157] FIG. 5 shows another embodiment of the present technology, which includes a pre-treatment subsystem 201 feeding a coating subsystem 301, each of which includes a two-stage rotation system electrically connected to a common signal hub 360. In this configuration, the batch or continuous rotating reactor subsystems for treatment and coating are connected to transport units 207 and 303, respectively, which each feed a separator system 901 before entering the subsequent unit operation. Particularly relevant to this system is the parameter monitoring required to achieve an efficient operating system. The process shown in FIG. 5 starts with powder as received from the bulk bag unloader or exit assembly 104, which is transported to the treatment assembly 203 and subjected to a first treatment step, e.g., mild reducing gas exposure, which is provided by the treatment enhancer 204, and is performed in a first rotating batch system. Process parameters such as exposure time, rotation speed, concentration, pressure and temperature can be determined primarily by the total surface area in this exemplary first treatment step. In the second process step, the material enters the process mixer 205 at a predetermined rate and the second process step can be carried out under computer controlled conditions through the process control port 206. If the function of this second process step is to uniformly preheat the material for hot flow to the subsequent coating step, the process parameters can be determined primarily by factors such as mass, thermal conductivity and / or heat capacity. The separator system 901 can represent a cyclone separator or other solid-gas classification system, in which case material density, particle size and flow rate through the transport units 207 and 303 are important parameters for the operation quality. Once the material passes through the first separator system 901 and enters the coating subsystem 302, which is represented by a batch rotating drum reactor, the exemplary coating process can be carried out in one or more unit operations in series or parallel. Figure 5 illustrates a configuration in which one precursor is sent from the chemical system (through one leg of the distribution manifold) to the coating subsystem 302a, while a different precursor benefits from delivery to the coating subsystem 302b with additional assistance from a transport enhancer.If desired, a separate transport enhancer can be operably connected to the coating subsystem 302a. In all cases, all coating subsystems (and all individual subcomponents that benefit from the transmission and reception of communication signals) are electrically connected to a common signal hub 360. Although the critical parameters of the process carried out in the coating subsystems may depend most heavily on the total surface area of ​​the material, further process refinements based on both material parameters and precursor properties may be required when using transport enhancers. Figure 5 further illustrates an embodiment in which material is staged from batch (201), continuous (901), batch (301), continuous (901) to a semi-batch stop unit 601, which includes at least two vertical transport operating means each having an inlet, an outlet, and controllable units for supplying and adjusting the material flow and temporarily controlling the surrounding environment. In such a system, at least one transport operating means faces downwards and deposits material into a receiver below, and at least one transport operating means faces upwards and deposits material into a receiver above. Additionally, the feed operation of the vertical transfer operation means is generally controlled to maintain a substantially uniform hourly transport rate. The system may include a control system designed for simultaneous feedback and feedforward control of the chemical reaction reactant flow, the chemical reaction product flow, the chemical reaction operating conditions, and continuous monitoring of the mass or volumetric transport of the material being produced. At least one subsystem operating in a continuous mode and at least one subsystem operating in a semi-continuous or batch mode may also be included. This serves to quantify and record all intrinsic and extrinsic properties and parameters of interest throughout the manufacturing system at a common signal hub as a means of maximizing the manufacturing efficiency of the composite product.

[0158] FIG. 6 shows a schematic diagram of a multi-stage spatially arranged continuous processing and / or coating system including computer-controlled individual synchronized unit operations with integrated machine learning to optimize process conditions and transport properties throughout the system. Initial batch and / or semi-batch operations are incorporated to monitor and control inputs, and material exits the entire system in a final batch or semi-batch unit operation. The exemplary process flow diagram shown in FIG. 6 includes unit operations of equal size, and transport rates through the individual subsystems should be the same, but in practice the size and number of parallel reactors performing each sub-process would be scaled based on key parameters related to precursors, materials, and products, and monitored and controlled by a common signal hub 360 (connections not shown). A representative continuous stirred reactor is shown throughout with flow enhancers, baffles, internals, stirrers / agitators, etc., represented as 320 and 321, resulting in good product uniformity. The advantage of this embodiment incorporating a series of separate continuous units, as opposed to a single continuous unit that does not include an internal separator system as taught by Elam et al. (U.S. Application Serial No. 14 / 339,058), is that each separator unit (901) allows for the release of gas phase reactants and products from the processing substrate, allows for the management of various effluent streams, and / or allows for the recycling of streams without mixing, overcoming potential issues with precursor mixing and precursor utilization. The separator system can be further improved by applying an additional inert purge to the dipleg that forms an inert curtain to minimize carryover of gas phase material to each subsequent continuously stirred vessel. Additional advantages of this system include the ability to operate at pressures greater than atmospheric pressure, which increases throughput capacity and facilitates the processing and coating of materials with large surface areas. In some embodiments, radial mixing predominates, while in other embodiments, axial mixing predominates.The reactor chamber can be mounted at an angle of 0°, 1°, 2°, 3°, 4°, 5°, 6°, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14° or 15° from the horizontal, with smaller angles being suitable for larger surface area materials that benefit from longer residence times.

[0159] FIG. 7 shows a schematic diagram of a multi-stage batch, semi-batch, semi-continuous or continuous processing and / or coating system including separate synchronized mechanical fluidization unit operations with computer control and integrated machine learning to optimize process conditions and transport properties throughout the system. In this configuration, powder or flowable articles or substrates are optionally synthesized using synthesis system 101 and conveyed to processing subsystem 205 or loaded manually or automatically. The processed substrates are dispensed into coating subsystem 302a through valve assembly 311 having an inlet and an outlet, where the inlet is in fluid communication with the outlet of an adjacent or overlying chamber and the outlet is in fluid communication with the inlet of an adjacent or underlying chamber. Valve assembly 311 has at least two computer-controlled actuation mechanisms for maintaining a nominal pressure in the adjacent chambers, where at least one computer-controlled actuation mechanism is available for each phase of material present in the subsystem. The first computer-controlled actuation mechanism provides a means for releasing one phase of material without allowing the other phase of material to flow from one chamber to the other. A second, third, etc. computer controlled actuation mechanism provides sequential means for flowing other phases of material from one adjacent chamber to a different adjacent chamber. The system of FIG. 7 also includes a common signal hub 360 designed for simultaneous feedback and feedforward control of chemical reaction reactant flows, chemical reaction product flows, chemical reaction operating conditions, and continuous monitoring of mass or volume transport of material during production. The system can include two parallel coating subsystems (e.g., as shown at 302 and 402 in FIG. 2), each having an inlet, an outlet, and a controllable unit for supplying and regulating material flow and temporarily controlling the surrounding environment, where at least one transfer operation means faces downward (e.g., valve assemblies 311 and 411) and deposits material into a receiver below, and at least one transfer operation means faces upward (e.g., transport unit 303) and deposits material into a receiver above.As the coating subsystems 302a and 302b are performing similar processes as the coating subsystems 402a and 402b, respectively, the feeding operations of the vertical transfer operating means are commonly controlled by a common signal hub to maintain a substantially uniform hourly transport rate. One or more mechanical fluidization systems (321) can be present in each subsystem chamber, such as rotors, ribbons, stators, or paddles, and the precursors can be configured to be injected into the reactor in gas, liquid, or solid phases under mechanical fluidization conditions. Continuous, intermittent, or periodic evacuation of reaction by-products can be performed, while the injection of precursors can be performed only initially, or simultaneously, sequentially, periodically, pulsed, or asynchronously to the evacuation process. The mechanical fluidization system 321 performs a dual function of supporting the substrate evacuation process. This system is useful for processing and coating particles and flowable substrates with a wide size distribution, and ranging from solid to highly porous. For example, about 0.01 m. 2 / g ~ approx. 1.5m 2 Materials with a specific surface area of ​​about 1.5 m / g can be processed without periodic discharge steps. 2 / g~about 50m 2 Materials with a specific surface area of ​​about 50 m / g can be processed using multiple discharge steps and one or several precursor dosage steps. 2 / g ~ approx. 2,000m 2Materials with specific surface areas of 10 ...

[0160] 8 shows a schematic diagram of the system, optionally including a common synthesis subsystem 101, a common first processing subsystem 201, distributed and / or parallel synchronized coating subsystems 302a and 302b including sub-chambers with computer control via a common signal hub 360 (connections to all sub-components labeled and unlabeled are not shown), with integrated machine learning to optimize process conditions and bidirectional transport characteristics across the individual subsystems, respectively, and then optimize the common second processing subsystem 501 and the re-centralized system of the stop unit 601. The system includes two parallel inlet valve assemblies 311a and 311b and outlet valve assemblies 315a and 315b for controlling or metering substrate flow through the coating subsystems 302a and 315b, respectively, each having at least two actuation mechanisms. The two or more actuation mechanisms can control two or more individual sub-valves in the valve assemblies 311 or 315, or individual features of the common valve, with at least one actuation mechanism being largely driven by the properties of the solid phase and at least one being largely driven by the properties of the gas phase. Each actuation mechanism may include one or more of: i) instantaneous opening of the valve, ii) instantaneous closing of the valve, iii) controlled opening of the valve over a programmable time constant, iv) controlled closing of the valve over a programmable time constant, v) expansion of a subcomponent of the valve assembly to reduce the conductance through the valve assembly, vi) contraction of a subcomponent of the valve assembly to increase the conductance through the valve assembly, vii) concave or convex deflection of a subcomponent of the valve assembly to change the volumetric capacity of the coating subsystem, viii) rotation of a subcomponent collinear with the direction of bulk material flow, or ix) rotation of a subcomponent tangential to the direction of bulk material flow. The mechanical fluidization system 321 serves the dual function of both mixing and supporting the substrate discharge process.In such a combined series and parallel subsystem approach, bidirectional flow or communication with each control port manifold 350 and / or with chemical subsystem 700 and / or transport enhancer 800, especially material and process information in steps and sub-steps that have different natural time constants based on particle size, surface area, size distribution, density, heat capacity, thermal conductivity, magnetic susceptibility, functional group and / or site density or similar properties must be carefully monitored and controlled, and the control system must provide simultaneous feedback and feedforward control of chemical reaction reactant flows, chemical reaction product flows, chemical reaction operating conditions, and continuous monitoring of mass or volumetric transport of materials during production. Typically there will be at least one subsystem operating in a continuous or pseudo-continuous mode, and at least one subsystem operating in a semi-continuous or batch mode, and the system is configured to quantify and record all intrinsic and extrinsic properties and parameters of interest throughout the manufacturing system at a common signal hub 360 as a means of coordinating and maximizing the manufacturing efficiency of the composite product.

[0161] FIG. 9 shows a schematic diagram of an asynchronous gas / solid coating or processing system including individual semi-continuous subchambers with external filtration and multiple actuation mechanisms that allow for computer control and machine learning, internal mixing assistance, gas distribution mechanisms, and / or solid flow control. The subsystems of FIG. 9 can emulate the coating subsystems 301 and 401 of FIG. 2, except for the addition of mixing internals 321 to each chamber specifically designed to further enhance powder mixing. The mixing internals are adjacent to and in fluid communication with one or more gas delivery inlets (such as those identified in the control port manifold 350 of FIG. 3). Precursor and powder mixing is enhanced by application of one or more of a gas distribution unit and a powder distribution unit, reducing gas-powder intermixing time by at least about 25%. The addition of reactor internals to enhance powder bulk mixing can reduce gas-powder intermixing time by at least about 50%. The gas distribution nozzles are preferentially designed and strategically positioned to mitigate powder bridging issues that may be present with certain types or classes of powders. Both coating subsystem 302 and coating subsystem 402 include an inlet, an outlet, and at least two vertical transport operation means each having a controllable unit for feeding and adjusting the material flow and temporally controlling the surrounding environment. In this depiction, coating subsystem N includes at least one transport operation means from chamber 302a, which faces downward and deposits the material into the receiver 302b below, and a transport unit 303, which faces upward and deposits the material into the receiver above in coating subsystem N+1, where the feeding operations are commonly controlled to maintain a substantially uniform hourly transport rate. Both the machine learning and the solid transport rate (e.g., in transport units 303 and 403) alleviate the maximum batch size restrictions that may exist in a comparable subsystem that does not incorporate the benefits of the mixing internal 321, and also allows the processing of materials with a large surface area to be performed at a higher material throughput. One or more standard valve operations can be used to control the solid transport and / or circulation rate throughout the system.

[0162] FIG. 10 shows a schematic diagram of a synchronized gas / solid coating or processing system including individual synchronized subchambers designed for co-flow / transport with external filtration, effluent management, solids flow control and transport management control using computer control and machine learning. In this configuration, for sequential step "a" and sequential step "b", valve assemblies 311 and 315 are replaced with pump assemblies 318 and 319, respectively. Similar to the actuation mechanisms present in each valve assembly described above, each of pump assemblies 318 and 319 has at least two actuation mechanisms to provide a means of controlling or metering the flow of both the gas and solid phases through coating subsystems 302a and 302b, respectively. The two or more actuation mechanisms may control separate features of two or more separate pump subassemblies or a common pump within pump assemblies 318 or 319, with at least one actuation mechanism being predominantly driven by the properties of the solid phase and at least one being predominantly driven by the properties of the gas phase. Each actuation mechanism includes one or more of: i) an instantaneous increase in pump feed rate; ii) an instantaneous decrease in pump feed rate; iii) electrical application of a sine, triangular or square wave to control variation of the pump feed rate over one or more programmable time constants; iv) expansion of a subcomponent of the pump assembly to reduce conductance through the pump assembly; v) contraction of a subcomponent of the pump assembly to increase conductance through the pump assembly; vi) concave or convex deflection of an in-line valved subcomponent within the pump assembly to vary the volumetric capacity of the pump assembly; vii) actuation of a piston or piston-like subcomponent within the pump assembly to provide a temporary process function increase or decrease in system pressure; vii) rotation of a subcomponent tangential to the direction of bulk material flow to change the transport vector of the delivered material; or viii) entrapment of a secondary phase to facilitate aeration, contraction or expansion of a primary phase unit volume during processing.

[0163] FIG. 10 shows a system in which each coating subsystem has its own dedicated external separator system 901 with filter assembly 902 selected based on the specific characteristics of the material, precursor, temperature, pressure and other process conditions. Many powders contain small particles resulting in Geldart Group C or Group A powders that are breathable and sometimes cohesive. In this configuration, the breathability and cohesiveness of these powders can be exploited in a continuous transport reactor, allowing operation at high pressures. The powders can be aerated using precursor gases diluted in an inert solvent or using jets, nozzles or similar known impingement devices known in the art. The co-currently fed and aerated powders and precursors are pumped or conveyed through the coating subsystem 302a at the specified operating temperature using pump assembly 318. Precursors can be appropriately added to the suction side of the pump when a particular type of pump is used such that pump cavitation is responsible for the completion of precursor-powder bulk mixing. In such a configuration, a significant length of pipe is installed on the discharge side of the pump, which determines the residence time of the resulting coating subsystem process. For example, in the case of an ALD process, the length of the pipe is constructed based on the specific surface area of ​​the material, the estimated saturation loading of the precursor, the target operating pressure and pump speed of the coating subsystem, and the throughput goal of the material for the particular end-use application. The length can be designed to allow the desired reaction to be completed before the residual unreacted precursor and by-product gases are separated from the powder in the separator system 901 of the filter assembly 902 (e.g., hot gas filter element). A purge step (typically inert) can also be performed in the dipleg of the hot gas filter to minimize carryover of precursors to the next stage or other materials that may be considered contamination of subsequent sub-processes. The embodiment of the system shown in FIG. 10 can be operated at slightly above ambient pressure by design.

[0164] FIG. 11 shows a schematic diagram of a synchronized gas / solid coating or treatment system including a continuous transport chamber with external filtration and separation, including multiple gas flow actuation mechanisms that enable computer control and machine learning to maximize gas / solid flow control and system pressure for efficient operation. As in the above embodiment, the coating subsystems 302a, 302b, 402a or 402b are in-line between similar or different processing subsystems for synthesis, treatment or coating, each with valve assemblies 311, 315, 411 and 415 separated by a separate separator system 901. In this embodiment, each valve assembly manages the continuous tangential flow of gas and solids transported through each reaction chamber. Each valve assembly is electrically connected to a common signal hub 360 as a means to tightly control each sub-process occurring in each different sub-reactor. Sub-reactors 302a and 302b can be used to perform different surface coating chemistries, requiring different (but known or predictable) parameters, including but not limited to temperature, pressure, flow rate, concentration, reactor diameter and pipe length. Without a common signal hub, materials and processes will intermix, leading to ineffective processing steps and material / product loss. Finally, this subsystem may favor larger particle size powders that fall into Geldart Group B or Group D. In embodiments where ALD in the coating subsystem 302 is applied to Group B or Group D powders, ALD can be accomplished in these sequential fluidized bed riser reactors, depicted here with a cyclone type separation unit. Both powder and diluted precursor are metered into chamber 302a using valve assembly 311 (which can be replaced with pump assembly 318) and fed to the bottom of the riser reactor. Precursors, typically diluted with inert gas, are used in the fluidization and / or elutriation media of the riser reactor. The good mixing and dispersive gas contact of the fluidized bed is responsible for the precursor-powder mix and product uniformity.Suitably, the reactor can be operated as a bubbling fluidized bed (e.g., with a superficial gas velocity of about 0.5 to about 2.0 ft / sec) and a large height-to-diameter ratio (e.g., greater than 2), although other operating regimes can be beneficial at certain operating times. Unreacted precursor and product gases are separated from the coated powder in a conventional cyclone. To minimize carryover of precursor to the next step, a N2 purge is provided to the cyclone dipleg. A purge step (typically inert) can also be performed on the hot gas filter dipleg to minimize precursor or other materials that could be considered as carryover to the next stage, contaminants of subsequent sub-processes. The embodiment of the system shown in FIG. 11 is preferentially operated at slightly above ambient pressure by design.

[0165] 10 and 11, some embodiments of the system may benefit from including subsystems 101, 201, 301, 401, or 501 that incorporate both valve and pump assemblies as a way to further regulate and control material flow within the subsystem. Other embodiments of the system may have at least one subsystem that operates in a continuous mode and at least one subsystem that operates in a semi-continuous or batch mode, where one or more of the subsystems may include one or more valve assemblies and one or more of the subsystems may include one or more pump assemblies.

[0166] FIG. 12 shows a schematic diagram of an asynchronous gas / solid coating or treatment system including individual synchronous subchambers with multiple actuation mechanisms enabling synchronous gas input, external filtration, gas recycle, computer control and machine learning, solid flow control and mechanical transport mechanisms in fluid communication with the top and bottom of each subchamber. In this configuration, coating subsystems 301 and 401 are configured to apply ALD or MLD coatings to particles, small flowable objects, catalyst pellets, extrudates, granules, or other mobile materials that are not easily characterized as particles or powders, such as Geldart Class D materials. When treating, coating or functionalizing porous objects, a common signal hub 360 (not shown) must configure and regulate flow rates and pressures to accommodate high surface area processes (the number of moles required for full surface saturation corresponds to the operating pressure of the system). When catalyst pellets or extrudates are intended to be used as substrates, the coating subsystem 301 provides multiple individual control ports 330a and 330b, where one or more of the individual control ports are located at or near the top of the reactor chamber, or at or near the bottom. The purpose of the multiple ports is to allow rapid adjustment of the pressure of the system, in some cases upwards to facilitate diffusion into a potentially tortuous pore network, in some cases downwards to exit the system uniformly and quickly, and in some cases to provide a gas blanket to prevent precursor mixing. One or more pressure regulation individual control ports can be co-located with the precursor delivery port 331, which can be connected to a precursor delivery system 700, a transport enhancer 800, or a similar useful subsystem designed for process enhancement. In this embodiment, the porous particles, pellets, or extrudates are fed into the top of the reactor pipe and continuously removed from the bottom of the reactor. The gas distributors and gas collectors are located at different heights within the reactor. The individual ALD half cycles are separated by valve assemblies 311, 315, 411 or 415, transport units 303, or by staged flush gas and gas collection.In some cases, the valve assembly (or pump assembly) may preferentially include an inert gas purge feature, which may assist with cleaning, flushing, purging, aeration, and the like.

[0167] FIG. 13 shows an exemplary flow chart for producing optimized Li-rich and Mn-rich lithium ion battery cathode powders with low capacity / voltage fade, high energy density, and suitable for 4.5-4.8V upper cutoff voltage operation. A first powder is synthesized in a first synthesis subsystem, where a powder 1001 having a specific size, size distribution, surface area, true density, tap density, and elemental composition is produced using one or more precursors referenced in the specification or text of this specification or any of the incorporated documents. The powder 1001 is then transported to a coating subsystem where a specific surface coating is applied to form powder 1002. The powder 1002 is directly compounded into a slurry 1003 in a third subsystem, where it is combined with precursors of specific elements in a ratio determined to produce an optimal second material phase when combined with the components of the powder 1001. The slurry is administered to a second synthesis subsystem to produce a composite powder 1004, which now comprises a first core of a first material, an inner coating of a second material, and another phase of a third material, the third another phase being primarily located on the surface of the powder 1002, except for preferential restructuring or rearrangement that occurs during the process performed in the second synthesis subsystem. The powder 1004 is transported to a second coating subsystem where a final surface coating is applied thereon to produce a powder 1005, which is then transported to a processing subsystem to produce a composite powder 1006. In another embodiment, additional processing steps can be performed after the first, second, third or fourth steps, in addition to after the fifth step. The final composite powder 1006 has superior properties compared to similar methods that do not include one or more steps described herein. Additionally, because lithium ion battery cathode materials tend to be moisture and / or air sensitive, the ability to perform all steps in an in-line process without exposing the materials to air, moisture or other deleterious environments results in optimal production of composite powders, flowable bodies or workpieces that can be transported through such systems in an automated fashion.

[0168] 14A-C are TEM (transmission electron microscope) images illustrating an embodiment of the method of FIG. 1D in which a substrate powder is pre-treated using any of the pre-treatment steps described herein (FIG. 14A), surface coated using an ALD process in coating subsystem 301 (FIG. 14B), and then subjected to a post-treatment process that provides diffusion of the surface coating species and creates through-coated regions of greater thickness than the starting coated material (FIG. 14C).

[0169] FIG. 15 illustrates an embodiment of the types of data streams, signal classifications and communication approaches that can be deployed by a common signal hub 360 and how the common signal hub monitors certain static and dynamic characteristics of a composite manufacturing system, which in turn controls each subsystem and subcomponent in both feedback and feedforward ways, enabling machine learning. Process data is collected through a programmable logic controller (PLC) and associated controller module. In one embodiment, a PLC can be used to regulate field instrumentation distributed throughout the manufacturing system and facility. Such a PLC can be used to establish an open database connection (ODBC) stream with a database server. In a preferred embodiment, the database server and the PLC are hosted on the same network, which allows for simple connection and monitoring access across the physical Ethernet layer.

[0170] In one embodiment, a PLC can be used to regulate field instrumentation to monitor and control one or more of temperature, heat, pressure, humidity, gas composition (e.g., reactants, catalysts, products, by-products, inert streams, humidity, etc.), safety detectors, interlocks, and countermeasures such as chemical extinguishers, substrate quantity levels (e.g., volume, height, weight, etc.), one or more valve assembly actuation levels, position, direction, conductance and / or contact, recipe and sub-process synchronization and / or sequence check steps, and periodically batch weight / control scales, such as the start and / or end of each subsystem process 361. In some embodiments, raw signal and / or instrumentation data can be streamed continuously at a particular frequency (e.g., about 0.1 to about 1 Hz or about 2 to 10 Hz for some subcomponents, about 30, 50, or 60 Hz for other subcomponents, etc.) to a database server via ODBC. In other embodiments, data can be streamed intermittently, synchronously, or asynchronously for certain critical signals sent to or received from certain subcomponents or subsystems throughout the system. In some embodiments, one or more bidirectional signals are sent between the valve assemblies 311 or 315 and the common signal hub 360, whereby one or more actuation mechanisms are triggered in the coating subsystem 301 (e.g., to initiate or continue operation of the transport unit 303), the coating subsystem 401 (e.g., to synchronously actuate the valve assemblies 411 or 415 with the valve assemblies 311 or 315, respectively), or the processing subsystem 501. The server data is preferentially generated with both a time and location stamp upon record entry to effectively index the database server and provide a comprehensive overview of all operations in progress. Another purpose of the common signal hub and its associated database server is to enable manufacturing facilities to rapidly comply with one or more governmental or non-governmental regulations and / or compliance metrics established by any tradecraft oversight agency or quality control and / or standards body, such as the International Organization for Standardization.A similar objective is for manufacturing facilities to track data for safety and to reduce the number of occurrences of process failures. In an exemplary embodiment, the server database is distributed across the facility network, allowing simple client access and server processing applications. The server processing applications enable dynamic feed-forward and feedback loops for ALD continuous manufacturing. Additionally, client connections to the electronic database server 363 and common signal hub 360 allow manual interaction with the process.

[0171] FIG. 16 illustrates a digital process flow that allows for feedback and feedforward (e.g., machine learning) process control for any particular process set point in any subsystem. In an embodiment where operating pressure is the target parameter and the subsystem is a coating subsystem 302, the critical inputs 364 can include the specific surface area of ​​the material, the estimated surface coverage of the coating material, and the average batch size processed per unit time. A critical signal setpoint calculation 365 incorporates the critical inputs 364 with subsystem related information from the server 362 to perform a signal setpoint calculation and initiates execution of a bidirectional signal monitoring hysteresis 366 baseline processing. In an embodiment where the coating subsystem 302 includes a valve assembly 311 (inlet) and / or 315 (outlet), the valve assembly has at least one actuation mechanism that is significantly dependent on the properties of the solid phase and at least one that is significantly dependent on the properties of the gas phase, each of which is stored in the server 362. Valve actuation mechanism X and valve actuation mechanism X+1 are triggered by signals Y and Y+1, respectively. Each actuation mechanism X or X+1 can represent one or more of: i) an instantaneous opening of a valve, ii) an instantaneous closing of a valve, iii) a controlled opening of a valve over a programmable time constant, iv) a controlled closing of a valve over a programmable time constant, v) an expansion of a subcomponent of the valve assembly to reduce the conductance through the valve assembly, vi) a contraction of a subcomponent of the valve assembly to increase the conductance through the valve assembly, vii) a concave or convex deflection of a subcomponent of the valve assembly to change the volumetric capacity of the coating subsystem, viii) a rotation of a subcomponent collinear with the direction of bulk material flow, or ix) a rotation of a subcomponent tangential to the direction of bulk material flow. In this embodiment, the valve actuation mechanisms X and XC+1 triggered by signals Y and Y+1, respectively, are represented diagrammatically by 367 and 368, respectively.Signals 367 and 368 are in a predefined state at the start of sub-process execution 369 and are then dynamically and independently controlled throughout sub-process execution 369 using monitored progress features 370 and 371 from ongoing execution steps, while monitored result features 372 and 373 represent historical processes, steps or trends of the same or similar sub-process. Sub-process model deviation calculator 374 uses all relevant information to determine deviations between inputs, outputs, expected values ​​and actual values, incorporating an interpolation step if gaps exist in the data set. Parameter records store all information in data warehouse 375 where, upon compilation of historical data and trends, machine learning algorithms 376 serve as a predictive mechanism to update critical signal setpoint calculation 365 and sub-process model deviation calculator 374.

[0172] FIG. 17 shows an embodiment of the control scheme behind the temperature signal and control loop, which includes a primary method of increasing temperature by delivering additional heat, and a secondary method from a secondary service programmed to correlate as an indirect effect driver with a critical application rate. In one embodiment where the sub-process is a flame spray synthesis process performed in the synthesis subsystem 101, multiple thermocouples are placed along the critical range of the subsystem reactor. Each has a control set point, signal monitor, and value response, which are continuously adjusted based on data from both the data warehouse 375 and the server 362. An important feature is how the machine learning algorithm 376 (not shown) evolves over time, allowing background identification of secondary services that can be activated or modulated to reduce the delay time required for the tuning algorithm to achieve a particular process parameter set point. The machine learning algorithm generates a dynamic list of available secondary services associated with the primary control system, and can assign a weighted percentage to each secondary service, which is updated over time. This matrix of weighted effects enables the machine learning algorithm to activate one or more secondary services to thereby improve process efficiency, reduce process costs, increase subsystem uptime, reduce maintenance intervals, reduce raw material waste, shorten process times, or any combination thereof. The machine learning algorithm monitors the causes and consequences of process failures and safety incidents to maximize process and facility safety integrity.

[0173] The systems, devices and methods described herein encompass any reactor configuration in which particles, powders, small objects or other flowable materials or substrates are conveyed from a system inlet to a system outlet, passing through one or more subsystems, typically two or more subsystems, to perform or execute a specific process that may vary over the execution of a series of applied sub-processes, but that is critically related to the physicochemical properties of the substrate, which can be modeled, monitored or otherwise tracked throughout the system. The system includes a sequence of predetermined steps, where the coordinated sub-processes are executed from a comprehensive database and controlled via a common signal hub for feedback, feedforward and / or machine learning control. The one or more subsystem configurations can include one or more towers with one or more primarily vertical transfer or transport mechanisms, one or more units with one or more primarily horizontal transfer or transport mechanisms, one or more general transport units that transport or move the substrates in sequence from one subsystem to the next. In some cases, the subsystem configuration may include one or more units suitable for diverting and / or separating material between two or more identical subsystems operating in a synchronous manner, which may include, among other benefits, the ability to match hourly transport rates while performing continuous, semi-continuous, semi-batch or a series of batch processing steps, where each step has a similar or different substrate flux or residence time through each subsystem performing a designated processing step.

[0174] For further versatility, the substrate can be optionally recycled or recirculated to one or more subsystems to increase the overall residence time through the sub-process, the hourly transport rate can be matched with other sub-processes that may or may not require a recycle or recycle process, or preferentially, the effectiveness of the application of a given sub-process or series of sub-processes can be multiplied if the recycle or recycle step transports the material in reverse order through multiple subsystems or sub-processes. The type, value, production costs and / or volume of composite materials can justify the inclusion of the installation costs of a second series of subsystems in a particular system, rather than recycling or recirculating the substrate through a subsystem previously used in the manufacturing process.

[0175] The apparatus or reactor in any of the above-mentioned subsystems of the present technology can include many additional components or features that may be necessary or useful to carry out the desired reaction. For example, one or more inlet ports can be in fluid communication with an external source of reactive precursors. Various types of valves, pumps, metering and / or sensing devices can be provided to ensure accurate dosing of reactive precursors. One or more inlet ports can be in fluid communication with a source of purge or sweep gas, again optionally combined with various types of valves, pumps, and metering and / or sensing devices. The outlet ports can be in fluid communication with various valves, vacuum pumps, metering devices and / or sensing devices. Various sensors and gauges or other measurement devices can be present as needed or desired. There can be analytical devices to detect the presence and / or concentration of reactive precursors (e.g., in the precursor delivery system 700 and interconnection points, the transport enhancer 800 and interconnection points, etc.), to detect the purge gas and / or various reaction products, and to measure the presence and / or degree of coating on the particle surfaces. Heating and / or cooling devices can be present to provide temperature control to the powder reservoir, the reactive precursor reservoir, or both. A computerized control and operating device can be used to operate one or more valves, pumps, heating and / or cooling devices, or other devices. A porous valve or similar device can be present between the powder reservoir and the reactive precursor reservoir. When closed, this porous valve or similar device acts as a support for the powder bed, allowing the reactor to function as a conventional fluidized bed reactor.

[0176] As described herein, the apparatus according to the present technology may include a subsystem suitable for synthesizing a powder, article, or flowable object, configured to perform one or more of flame spray, combustion spray, plasma spray, spray drying, or a combination thereof. Alternatively or additionally, one or more of the subsystems described herein may be suitable for performing gas processing and / or gas phase deposition techniques on the powder or flowable substrate or article. The systems, apparatus, and methods described herein may be configured to perform chemical or physical reactions including one or more steps of atomic layer deposition, molecular layer deposition, chemical vapor deposition, physical vapor deposition, molecular layering, atomic layer chemical vapor deposition, epitaxial deposition, chemical grafting, atomic layer etching, atomic layer etching, atomic layer combustion, or any combination thereof. In at least one embodiment, the systems, apparatus, and methods described herein are configured to perform a method including atomic layer deposition (ALD), molecular layer deposition (MLD), or a combination thereof. ALD techniques are particularly suited for applying a variety of inorganic coatings to substrates, including, for example, oxide coatings such as aluminum oxide, silicon oxide, zinc oxide, zirconium oxide, titanium oxide, transition metal oxides, boron oxide, yttria, zinc oxide, magnesium oxide, etc., nitride coatings such as silicon nitride, boron nitride, and aluminum nitride, sulfide coatings such as gallium sulfide, tungsten sulfide, and molybdenum sulfide, as well as inorganic phosphides. Additionally, a variety of metal coatings can be applied using ALD techniques, including cobalt, palladium, platinum, zinc, rhenium, molybdenum, antimony, selenium, thallium, chromium, platinum, ruthenium, iridium, germanium, and tungsten. Optionally, when including a transport enhancer, one or more precursors described herein can be delivered to a surface of a plurality of articles to treat the articles or deposit one or more cations and / or anions on the articles, where the cations or anions are assigned to Groups 1a, 2a, 3a, 4a, 5a, 6a, 7a, 8, 1b, 2b, 3b, 4b, 5b, 6b, or 7b of the Periodic Table of the Elements.In some cases, one or more of the subsystems are configured to utilize precursors and / or deposit materials that include phosphorus, sulfur, nitrogen, carbon, fluorine, chlorine, bromine, or iodine, where the precursors include phosphides, phosphates, sulfides, sulfates, nitrates, fluorides, chlorides, bromides, or iodides.

[0177] The systems, apparatus, and methods described herein can include one or more subsystems, including a processing subsystem, that can be configured to control nominal values ​​and rates of change of one or more of: i) process pressure, ii) process temperature, iii) gas phase composition or flow rate, iv) liquid phase composition or flow rate, v) solute or solvent composition or flow rate, and vi) solid phase composition or flow rate.

[0178] In ALD processes, the coating-forming reaction is carried out as a series of two or more (typically two) half-reactions. In each of these half-reactions, a single reagent is introduced into contact with the substrate surface. Conditions are typically such that the reagent is in gaseous form, although it is understood that liquid-phase and supercritical-phase ALD and MLD processes are also known and may be applied to one or more of the systems described herein. The reagent is deposited on the surface of the substrate. In most cases, the reagent reacts with functional groups on the surface of the substrate and becomes bonded to the substrate. Because the reagent only reacts with functional groups on the substrate, it penetrates the pores of the substrate and deposits on the interior surfaces of the pores and on the exterior surfaces of the substrate. Any excess amount of reagent is then removed. This helps to prevent the growth of undesirable large inclusions of the coating material. Each remaining half-reaction is then carried out in sequence, each time introducing a single reagent, allowing it to react on the surface of the particle, and removing the excess reactant before introducing the next reagent, all in the same chamber or reaction vessel. A carrier gas can be used to introduce the reagents, and the powder can be swept with the carrier gas to aid in the removal of excess reagents and gaseous reaction products. In a preferred embodiment, at least one subsystem is configured to perform a surface treatment process, and at least one subsystem is configured to perform an atomic layer deposition process, and the surface treatment process is part of a sequence that includes one or more steps, and occurs before the atomic layer deposition process, after the atomic layer deposition process, or both.

[0179] In one aspect of the present technology, the system can be described as a composite article manufacturing system including a control system in communication with two or more subsystems configured to synthesize, treat and / or coat an article using a continuous, semi-continuous, semi-batch or batch process, where a first subsystem includes one or more chambers having at least one inlet or outlet in fluid communication with at least one valve or pump assembly having one or more actuation mechanisms, and at least one of the first or second subsystems is configured to deliver one or more precursors to a surface of the article to cause a chemical or physical reaction, thereby forming a composite article. In general, the control system, which may represent a master control system when multiple control systems exist, electronically communicates with all the actuation mechanisms through a common signal hub and provides a commonly controllable unit for regulating material flow. In many cases, it is beneficial when at least one actuation mechanism from one subsystem can be configured to operate in synchronization with at least one actuation mechanism from a different subsystem, and in other cases, it is beneficial when at least one actuation mechanism from one subsystem can be configured to operate sequentially at a synchronous or asynchronous speed with at least one actuation mechanism from a different subsystem. Additionally, it is often beneficial for one or more of the systems or subsystems to further include one or more of a common precursor delivery subsystem, a precursor delivery enhancement subsystem, or an exhaust treatment or recycling subsystem.

[0180] The device of the present technology can be suitable for synchronously processing multiple composite articles, where the composite articles include one or more separate particles, powders, extrudates, granules, flowable objects, or any objects of a size with a maximum dimension less than about 125 millimeters, and at least about 75% of the surface of the composite articles is coated or treated when exiting the system. Even if at least about 10% of the surface of one or more composite articles is inside the structure of the article, efficient processing of the interior and exterior surfaces can be performed. In some cases, one or more parameters, including but not limited to pressure, temperature, molar flux, or residence time, are scaled as a function of the total surface area, or one or more parameters are scaled as a function of the interior surface area. In either case, efficiency can be realized when each subsystem is connected by a transport unit with a controllable environment, and one or more transport units are controlled synchronously.

[0181] The systems, devices and methods described herein may be used to produce materials such as lithium ion battery materials, fluorescent materials, high surface area metals, solid electrolytes, particularly those containing sulfides, phosphides, etc., and catalysts, which are known to ingest, react, or otherwise interact with chemical, mechanical, electrical, or physical mechanisms. Minimizing, or ideally eliminating, unwanted interactions provides substantial cost savings, performance benefits, or both. For example, while cement powders can be kiln dried in very high energy intensity clinker processes to minimize moisture uptake from the environment, the inventive method of treating, surface coating (e.g., with a hydrophobic coating), and optionally post-treating one or more cement component powders in an all-in-line system as taught herein substantially reduces the operational costs of cementitious material production and adds value to low-cost commodity materials in the form of high performance cement products.

[0182] In some embodiments, the systems, apparatus, and methods described herein can be used to produce coated fine or ultrafine particles for cathodes, anodes, dielectrics, metals, polymers, semiconductors, and other ceramics for integration into power system devices, including, but not limited to, batteries, capacitors, varistors, thyristors, inverters, transistors, light emitting diodes and phosphors, photovoltaic devices, and thermoelectric devices.

[0183] In some embodiments, the systems, apparatus, and methods described herein can be used to produce particles ALD produced powders for batteries, fuel cells, catalysts, capacitors, pharmaceutical ingredients, passive electronic components, solar cells, 3D printers, semiconductor devices, integrated circuits, optoelectronic devices, thermoelectric devices, thermionic devices, electrochemical devices, biomedical devices, or electromechanical devices, paints, pigments, and materials suitable for use in the power systems industry.

[0184] The systems, devices, and methods described herein can be used for the synthesis and post-synthesis modification of many well-defined catalysts known in the art, such as those described in PCT / US2010 / 001689 and PCT / US2012 / 039343, which are incorporated by reference in their entirety. Nanoparticles or films of nearly any catalytic material can be synthesized using the systems, devices, and methods described herein. For example, the systems, devices, and methods described can be used to apply ALD techniques to the synthesis of catalysts, including catalytic coatings on the surface of metal or metal oxide substrates (e.g., using catalytically active metals and / or metal oxides as precursors). Such catalyst-coated substrates can include, for example, cathodes including carbon materials having a thin layer of inert material on the surface, and thin layer-coated catalysts that can be used in zinc-air and lithium-air batteries. Catalysts can include metal or metal oxide nanoparticles that can be coated on inert materials such as metal oxides, non-metal oxides, metal halides, metal phosphates, metal sulfates, or metal oxyfluorides. The systems, devices and methods described herein can provide catalytic materials with improved stability, selectivity and activity due to uniform surfaces with high conformability, improved controllability and thickness accuracy and reproducibility.

[0185] The flowable article can move along a conveyor or the flowable substrate can be extruded through a die to form an extrudate. In at least one embodiment, the flowable article comprises one or more discrete particles, powders, extrudates, granules, flowable objects or objects having a maximum dimension less than 125 millimeters in size.

[0186] Aspects of the present technology are to establish a modular process to synthesize and upgrade materials without breaking the process chain, i) eliminating additional handling steps, ii) minimizing or eliminating product and manufacturing environment interactions, iii) automating two or more separate processes operating under different conditions, and iv) providing a means to aid in vertical integration, cost reduction and overall efficiency, which collectively contribute to improved safety, higher profit margins, better end-user products and experiences, etc. The present technology is advantageous in that it overcomes unforeseen challenges that arise when combining two process steps, modules or other distinct linkages between dissimilar unit operations, and can provide a holistic approach to producing upgraded materials designed for use in specific applications.

[0187] A significant percentage of particles, powders and flowable objects used across all industries can be enhanced by upgrading or post-treatment processes that modify the surface properties of the bulk material without adversely affecting the properties of the bulk material itself. The upgrading process can result in discrete shells, layers, films or other coatings, ranging from sub-nanometers to hundreds of micrometers thick, or interdiffusion layers that are homogenized regions incorporating materials, functions, structures or physical or chemical properties derived from both bulk and surface composition. In the absence of a coating, adjacent particles may fuse, sinter, age or undergo other similar processes when exposed to a particular post-treatment or set of treatment conditions, and the coating acts as a barrier to inhibit, delay, prevent or otherwise reduce the tendency of such processes to occur. Alternatively, a post-treatment process can be used to remove the native surface by physical or chemical etching, reaction, conversion or other removal methods. In most cases, if one post-treatment process can enhance the value of a particular product, multiple post-treatment processes can also be expected to synergistically enhance performance, either by similar processes with dissimilar materials, similar materials applied using dissimilar processes, or dissimilar materials applied using dissimilar processes. Sometimes, in certain market segment applications, one, two, three or even four post-processing processes can be useful, while other, particularly high value applications, can further benefit from five, six, seven, eight, nine, ten or more post-processing processes. Additionally, several synthetic processes can be performed in sequence (using similar or dissimilar process conditions or materials or synthetic processes) to enhance the starting powder and result in a core-shell material, where the core and shell can be distinguished by composition, crystal structure, geometry, density, physicochemical properties or other pairings, to produce a single workpiece that is known to have superior functionality, utility or advantage in one or more applications when used in combination with one or more similarly processed workpieces.

[0188] Gas phase deposition techniques are sometimes used to deposit coatings and can be augmented by incorporating plasma, pulsed or non-pulsed lasers, RF energy, and electric arc or similar discharge techniques. Sometimes liquid phase techniques are used to synthesize materials and / or deposit coatings. Examples of liquid phase techniques include, but are not limited to, sol-gel, co-precipitation, self-assembly, layer-by-layer, or other techniques. In producing powders, liquid phase techniques have at least one thing in common. Due to the energy intensiveness and cost of mixing, separating, and drying materials synthesized or coated using liquid phase techniques, greater efficiency and uniformity can be obtained by utilizing gas / solid unit operations. An additional advantage of utilizing gas / solid unit operations is the ability to perform solid phase reaction techniques (e.g., annealing, calcination, or other heat treatments in various controlled gas environments) following the synthesis or coating steps. The present technology provides a manufacturing system and strategy that fully controls all aspects of the production of target materials in one comprehensive scheme.

[0189] One commonality of gas phase processing systems for producing or encapsulating powders is that the chemical reactant precursor must be volatile or otherwise capable of vaporization. However, chemical precursors can be in many different physical phases, states and reactivities depending on the surrounding environment as well as temperature and pressure. Possible precursor states include binary dilutions or mixtures of reactive or toxic gases and inert gases, gases or gas mixtures including binary, ternary, quaternary, etc. mixtures of one or more reactive elements such as air, binary dilutions or mixtures of non-reactive solvents and reactive liquids, liquids or liquid mixtures including binary, ternary, quaternary, etc. mixtures of one or more reactive elements such as formalin, subliming solids, solids dissolved in one or more liquids, solvents or other miscible media, vaporizable elements such as sulfur or gallium, plasmas or ionized gases of single elements or gases such as Ar, plasmas or ionized gas mixtures such as argon or oxygen in argon, reaction products such as hydrogen reacting with sulfur to form hydrogen sulfide, fugitive reaction products (e.g., chemical radicals or ions), decomposition or combustion products such as CO or CO2, and electrons.

[0190] Apart from precursors already in the gas phase (e.g., BCl3, NF3, NO2, O3, etc.), the volatility of each liquid or solid precursor or class of precursors can vary substantially, ranging from high vapor pressure alkylmetal precursors (such as trimethylaluminum and diethylzinc) to solid precursors that require sublimation at >200°C (such as zinc chloride and zirconium chloride).

[0191] Vapor deposition processes are typically operated in batch mode in reaction vessels such as fluidized bed reactors, rotating reactors, and V-blenders, among others. Batch processing is very inefficient when operated on a large scale for several reasons. Synthesis processes tend to be continuous in nature, but require separation and processing steps that can be operated batchwise, semi-continuously, or continuously, and / or benefit from subsequent processing and / or coating steps that can be performed in any of the methods described herein. The throughput of each reactor is a function of the total particle mass or volume that is loaded into a vessel of a particular size for a particular process, the total process time (on-time), and the total time to load, unload, clean, prepare, etc. (downtime). Batch processing incurs significant downtime because the reaction products must be removed from the reactor at the end of each batch and fresh starting materials must be added to the equipment before the next batch is made. Equipment breakdowns and maintenance add to this downtime. Process equipment tends to be very large and expensive for batch processes. The additional requirement to operate these processes under vacuum adds significantly to the cost of the equipment, especially as the size of the equipment increases. Because of all this, equipment costs for batch processes tend to grow faster than operational capabilities, but several approaches to incorporating typical batch unit operations into highly efficient systems, as described herein, can allow such subsystems to remain of sufficient value to certain industries. Another problem that arises as process equipment becomes larger is that it becomes more difficult to maintain uniform reaction conditions throughout the vessel. For example, temperatures can vary considerably in large reaction vessels. It is also difficult to adequately fluidize large amounts of particles, especially nanoparticles. Such problems can lead to inconsistencies and defects in the coated product.

[0192] In gas phase deposition methods such as ALD and MLD, the particles are contacted with two or more different reactants sequentially. This represents yet another problem of batch operations. In traditional batch processes, all cycles are performed sequentially in a single reaction vessel. Batch particle ALD processes require more frequent periodic cleaning, creating additional downtime and not allowing the reaction vessel to be used for multi-layer film types when cross contamination can be an issue. Furthermore, the two sequential self-limiting reactions may take place at different temperatures, requiring the reactor to be heated or cooled between cycle steps to accommodate each step. The throughput of batch processes can be increased by building larger reaction vessels and / or operating identical reaction vessels in parallel. A capital cost-effective trend to counter this downtime from a throughput perspective is to build larger reaction vessels. In larger vessels, it becomes more difficult to control local process conditions including internal bed heating, pressure gradients, mechanical agitation to break up nanoparticle agglomerates, and diffusion limitations, among others. When performing ALD processes on fine and ultrafine particles, there is a practical maximum reactor size that limits the annual throughput of a single batch reactor operating continuously, where the process time to produce a given amount of coated material is the on-time plus downtime. There is a practical maximum allowable capital cost to manufacture particle ALD production equipment, effectively limiting the number of batch reactors operating the same process in parallel. These constraints create practical throughput limitations that prevent the integration of some particle ALD processes at industrial scale. Thus, to meet the demands of industrial scale, high-throughput semi-continuous or continuous-flow ALD processes must be developed, and the present technology is designed to meet these demands.

[0193] In gas phase deposition processes such as CVD, particles can be contacted with two or more different reactants simultaneously, or with one or more reactants that do not exhibit the self-limiting behavior characteristic of ALD and MLD processes. In traditional batch CVD processes, the primary method of controlling the reaction is limited to the exposure time of the reactants and the operating conditions, such as the process temperature and pressure. Batch particle CVD processes have limited opportunities to prevent undesirable gas phase side reactions. When implementing batch particle CVD processes, there is also a practical maximum reaction vessel size, since small variations in process conditions can lead to large variations in product quality across the batch of particles produced. Therefore, there is a need to develop high throughput continuous, semi-batch or semi-continuous particle CVD processes to meet the demands of industrial scale without sacrificing product quality, and the present technology is designed to meet these demands.

[0194] In any of the above mentioned vapor deposition techniques, the need and ability to control the flow of gaseous precursors, reactants, contacting agents, products and carrier gases is paramount to be able to effectively control the specific process intended to be applied to a specific surface area of ​​a solid substrate. The incompatibility of many precursor types, chemistries, conditions and materials necessitates various schemes for the delivery of precursors to the reaction chamber. Several methods and equipment configurations have been developed to transport one or more precursors from a separate state into chemical contact with one or more deposition substrates and simultaneously in a reactive form or to a location where they will subsequently become reactive.

[0195] The simplest method of precursor delivery is direct exposure to the precursor gas using pressure and / or concentration differentials and diffusion, thereby moving the precursor to and through the reaction zone. The gas precursor has sufficient vapor pressure under storage conditions, or the gas phase precursor can be created by heating the storage vessel, reducing the pressure in the vessel, or otherwise introducing the precursor into a larger vacuum volume. The storage vessel is separated from the substrate via a controllable separation mechanism. This includes physical and mechanical barriers that separate the precursor gas from fluid contact with the substrate. Alternatively, separation can be achieved by applying localized temperature or pressure to reduce the presence of gas phase precursor, or by the introduction and subsequent actuation of a countercurrent gas flow that provides a non-diffusive gas barrier between the precursor source and the substrate. The separation of the precursors and exposure to the substrate (or lack thereof) is controlled by controlling the actuation of the isolation valve and the length of time between actuation steps of the isolation valve, a mass flow controller such as a thermal mass flow controller or a Coriolis flow controller, a pressure control meter or orifice to regulate the precursor flow to the reaction vessel, a temperature ramp, stepping or initiation of a heating element to promote and increase or decrease gas production, a gas diversion or bypass element such as a valve, orifice, mass flow controller or pressure controller, and by regulating the countercurrent flow of gas into or around the reaction vessel.

[0196] Low vapor pressure precursors that diffuse slowly or have a high degree of van der Waals interactions with other materials and surfaces that stabilize the interactions, making them less likely to remain or transition to the gas phase, can be pushed into the reaction chamber and accessory manifolds by adding a carrier stream. Carrier fluids can be gases or liquids, inert or otherwise non-reactive at the reaction conditions in use, and can be driven or drawn through the reactor and subcomponents using pumps, pressure and temperature differentials, and can be regulated or controlled by mass flow controllers such as thermal mass flow controllers or Coriolis flow controllers, pressure control meters or orifices, temperature ramps, stepping or initiation of heating elements to promote and increase or decrease gas generation, gas diversion or bypass elements such as valves, orifices, mass flow controllers or pressure controllers to regulate gas counterflow to or around the reaction and / or precursor containment vessels. Some examples of carrier fluids include dry air, nitrogen, argon, helium, methane, and carbon dioxide. Entrainment of the precursor into the carrier stream is achieved by the intersection of the precursor gas stream with the carrier stream. The carrier gas may be redirected through the precursor containment vessel through an inlet, either concentric or separate from the outlet port. To maximize contact between the carrier stream and the precursor, in one embodiment, the inlet of the precursor vessel can be submerged in the precursor and equipped with one or more spargers or nozzles to reduce the size and increase the number of bubbles as the carrier stream moves through the liquid phase precursor. In another embodiment, the inlet redirects the carrier stream across only the surface of the liquid or solid precursor. To allow the carrier stream to contact the largest possible surface area of ​​the precursor, the size and shape of the precursor containment vessel can be modified to a long tube, a large diameter vessel, or a serpentine path between the inlet and outlet ports inside the containment vessel. Alternatively, the precursor can be introduced by spraying, atomizing, or spraying the liquid precursor or liquid precursor mixture into the gas stream via a pump, spray nozzle, injection nozzle, or piezoelectric actuator.

[0197] Materials with very low vapor pressure, highly reactive precursors, precursors that contaminate the surfaces of the reactor and reactor subcomponents, precursors that are not stable in the gas phase, precursors that are short-lived or transient species, or precursors that decompose in the presence of temperature or vacuum, may be introduced into the reaction vessel beneath, adjacent to, above, or within the substrate or substrate bed in the gas or non-gaseous phase. In one embodiment, the precursor is introduced into the reactor through one or more valves, nozzles, or tubes in liquid or solid state, and a change in pressure or volume expansion causes a change in the phase of the precursor. In another embodiment, the precursor is introduced into the reactor through one or more valves, nozzles, or tubes in liquid or solid state, and a temperature difference between the reactor and the precursor containment vessel causes a change in the state of the precursor. In another embodiment, the precursor is introduced into the reactor through one or more valves, nozzles, or tubes, and dispersion on the reactor walls or substrate media provides heat transfer and a larger surface area to facilitate vaporization. In another embodiment, the precursor is ionized or energized into a plasma. In another embodiment, the precursors can be distributed to the space inside the reactor by using a showerhead or distribution plate. A specific amount of precursor can be metered using a mass or liquid flow controller, regulator, orifice, a single valve, or a series of valves, pumps, or syringes working together in series or in a specific order. Alternatively, the precursors can be metered by filling a container content of known volume, mass, or density, and then draining or replacing it. Filling or draining can be accomplished by gravity, mechanical motion, applied vibration or shock, pressure difference due to an applied pressurized gas push or vacuum pull, or a siphon initiated by a passing fluid flow and / or the Venturi effect. During the introduction of the precursor, the substrate can be stationary, moving, fluidized, or semi-fluidized. Immediately after the introduction of the precursor, the substrate can be stationary, moving, fluidized, or semi-fluidized. The environment within the reactor may be an active vacuum, a passive vacuum, gas-filled, pressurized, fluidized gas, liquid-filled, flowing liquid, or dissolved, dispersed or mixed in or with a supercritical fluid, or a combination of these processes or pulse sequences may be performed.

[0198] Alternatively, materials with very low vapor pressure, highly reactive precursors, precursors that contaminate the surfaces of the reactor and reactor subcomponents, precursors that are not stable in the gas phase, precursors that are short-lived or transient species, or precursors that decompose in the presence of temperature or vacuum can be introduced into a secondary vessel that is neither a precursor containment vessel nor a reactor. This secondary vessel outlet can also be connected to a reactor inlet that is directly / below, adjacent to, above / on or inside the unit volume containing the substrate or substrate bed. In one embodiment, the precursor is introduced into the secondary vessel in liquid or solid state through one or more valves, nozzles or tubes, and a change in pressure or volume expansion causes a change in the phase of the precursor. In another embodiment, the precursor is introduced into the secondary vessel in liquid or solid state through one or more valves, nozzles or tubes, and a temperature difference between the secondary vessel and the precursor containment vessel and / or the secondary vessel and the reactor causes a change in the state of the precursor. In another embodiment, the precursor is introduced into the secondary vessel through one or more valves, nozzles or tubes, and a distribution on the vessel wall or packing medium provides heat transfer and a larger surface area to facilitate vaporization. The packing media may be comprised of metals such as titanium, aluminum, molybdenum, tungsten, nickel, silver or silicon, alloys such as stainless steel, Inconel, Monel, ceramics or metal oxides (e.g., Al2O3, ZnO, SiO2, ZrO2, TiO2, etc.), mixed metal oxides such as silicates, aluminates, titanates, zirconates, nitrides such as TiN, Si3N4, BN, AlN, carbides such as SiC, WC, ZrC, TiC, carbons such as graphite, graphene, carbon black, activated carbon, charcoal, polymers or plastics such as PTFE, PEEK, PET, PEN, PP, LDPE, HDPE, PS, PS-DVB, PI, PEI, coblock polymers, or may be comprised of the same, similar or different substrate materials or powders currently used in the reactor, or distillation packing in the form of balls, beads, extrudates, fine or coarse milling media or cut tubes, distillation packing materials generally found to be useful, vacuum distillation packing materials.Ideally, the packing medium has a high surface area / volume ratio, is configured in a non-close packed configuration or a high free space ratio, or is fluidized to reduce pressure loss. In another embodiment, the packing medium can be arranged on multiple distribution plates to maximize contact between the liquid precursor and the packing medium and the gaseous fluid stream and the medium, and to contain the packing within a specific area of ​​the secondary vessel. The distribution plate can be porous metal, metal screen, laminated metal screen, porous ceramic, conical screen, porous polymer, polymer mesh, secondary packing medium, glass wool, metal wool, or ceramic wool. In another embodiment, a showerhead or distribution plate can be used to distribute the precursor to the space in the secondary vessel. A specific volume of precursor can be metered using a mass or liquid flow controller, regulator, orifice, a single valve or a series of valves, pumps, or syringes working together in series or in a specific order. Alternatively, the precursor can be metered by filling the contents of a vessel of known volume, mass, or density, and then draining or replacing it. Filling or emptying the vessel and / or secondary vessel of known volume can be accomplished by gravity, mechanical motion, applied vibration or shock, pressure differentials due to applied pressurized gas push or aspirating vacuum, or a passing fluid flow and siphoning initiated by the Venturi effect. During introduction of the precursor, the filler can be stationary, moving, fluidized or semi-fluidized. Immediately after introduction of the precursor, the filler can be stationary, moving, fluidized or semi-fluidized. The environment in the secondary vessel can be active vacuum, passive vacuum, gas-filled, pressurized, fluidized gas, liquid-filled, flowing liquid, or dissolved, dispersed or mixed in or with a supercritical fluid, or a combination of these processes or pulse sequences can be performed. Additionally, in-situ characterization tools such as mass spectrometry, optical spectroscopy, electrical conductivity, thermal conductivity, and ultrasonic or other acoustic probes of the contents of the secondary vessel can be implemented.

[0199] Atomization or spraying assemblies can also be implemented to disperse the precursor into small droplets in the form of a mist or fog to increase the interfacial area between the precursor and a carrier gas or fluid. Liquid precursor, solvated precursor or precursor dilution or molten precursor is metered through a rapidly acting valve or series of valves via a liquid flow meter, syringe pump or peristaltic pump to generate a small volume of separate liquid that is drawn into the reaction chamber by a pressure differential or pushed into the reaction chamber by a flowing gas that can be pulsed alternately with the precursor through the same rapidly acting valve or series of valves. The spraying valve assembly can be integrated into the manifold, the reactor itself, or a secondary container in fluid contact with the manifold or reactor. In one embodiment, the evaporator and dilution of liquid precursor in anhydrous solvent were performed. The system uses a piezoelectric actuator to pulse a microvalve to mix small pulses of liquid with gas and spray into the hotbox at each step. The output of the hotbox is entrained in the secondary gas flow. In another embodiment, the atomizing element is not a valve, but a piezoelectric or fast vibration element integrated into the bottom or side of the precursor containment vessel and in contact with the precursor solution in the vessel or in contact with a flexible membrane that is in contact with the precursor solution. The rapid vibrations caused by the piezoelectric actuation agitate the liquid, expelling small droplets from the top surface of the liquid.

[0200] In addition to transporting reactive precursors from outside the reactor to inside the reactor, reactive secondary precursors can be generated in situ from one or more primary precursors. Many formation methods are possible, including decomposition initiated by temperature or pressure inside the reactor or in the gas phase before the reactor, at the substrate, at the reactor or manifold surface, or by passing an incorporated decomposition element such as a hot filament or wire, or by reaction with other gas phase precursors, reaction with a surface inside the reactor or before the reactor, reaction with charged species, radicals or plasma, passing through or near a plasma source, electron beam or ion beam.

[0201] Precursor delivery and utilization are two of the most important aspects of ALD. Unreacted precursors can be recycled from the exhaust of a system or subsystem back through the system or downstream to another subsystem to increase precursor utilization or increase exposure / residence time. In one embodiment, the exhaust or select elements of the exhaust from one chamber can be used as precursor feed for the next chamber. The amount of precursor introduced to the first reaction step can be excessive and / or additional precursor can be added in a later step. In another embodiment, reactive precursors can be collected from the exhaust from one or more process chambers by condensation or membrane separation and later used as precursors in the same or different reactors. In one embodiment, the chamber size can be manipulated to carry the precursor downstream. Compressors or pumps can be implemented to move the precursor and effluent to the next chamber or back through the chamber. Alternatively, the flow direction can be reversed through the same chamber.

[0202] The method of the present technology is also useful for producing core-shell catalyst particles with high specific mass activity, of the type described in US Patent Application Publication No. 2010 / 0092841, or for producing size-selected metal nanoclusters, as described in US Patent No. 7,713,907. In some examples, the systems and methods are configured to produce materials suitable for use in batteries, fuel cells, capacitors, passive electronic components, solar cells, 3D printers, semiconductor devices, integrated circuits, optoelectronic devices, thermoelectric devices, thermoelectronic devices, electrochemical devices, or electromechanical devices. The method of the present technology can be used to perform plasma-based methods, such as those described in US Patent Nos. 7,758,928 and 6,428,861, in which particles are functionalized. In some cases, an advantage of such plasma-based methods is that they reduce the operating temperature of the deposition process. The plasma methods described in these two patents can be performed in some or all of the individual chambers in which the method of the present technology is performed. The method of the present technology can be used to produce high volume products such as titanium dioxide coated particles as described in US Patent Application Publication No. 2010 / 0326322 or coated lithium metal oxide particles for use as high performance cathodes in lithium ion batteries as described in US Patent Application No. 9,570,734. The advantage of this continuous, semi-continuous or semi-batch invention over conventional batch fluidized bed reactors is that high annual throughput can be achieved using reasonably sized equipment and therefore reasonable capital costs. Furthermore, the rate limiting step of batch gas phase deposition processes in fluidized bed reactors is the rate at which gas can enter the reactor without elutriating the article. In some embodiments, the present technology allows the article to be transported in a rate limiting step through a semi-continuous or continuous process when the gas phase reactants are preloaded into the chamber independently of the solid article. In other cases, a batch method or system may be preferred when a high degree of process precision is required and spatial separation and / or high throughput transport may adversely affect one or more properties of the substrate, treatment layer, coating process, synthesis process, delivery mechanism, emission reduction, etc.

[0203] The present technology can also be used in-line directly after a titanium dioxide manufacturing process, such as described in U.S. Pat. No. 7,476,378, to produce titanium dioxide coated particles. Lithium oxide particles can be produced by flame spraying, such as described in U.S. Pat. No. 7,211,236, or plasma spraying, such as described in U.S. Pat. No. 7,081,267, or similar methods, and the coating process of the present technology can be carried out directly in-line after such lithium oxide particles are produced. More generally, the particles coated by the present technology can be of any type produced using known particle production processes. The coating process of the present technology can be carried out as part of an integrated manufacturing process that includes a manufacturing process that produces particles that are directly or indirectly followed by the coating process of the present technology. Another example of such a particle manufacturing process that can be integrated with the coating process of the present technology is the manufacturing process of ultrafine metal particles, such as described in U.S. Pat. No. 6,689,191. Air and moisture sensitive powder materials can be safely transported in-line from the manufacturing process of the present technology to the semi-continuous coating process. The method of the present technology can be integrated into a manufacturing process for producing moisture-resistant phosphors, such as the ZnS phosphor particle manufacturing process described in U.S. Pat. No. 7,833,437. Using the method of the present technology, a first subset of chambers can be used to dope rare earth elements onto or into ZnS carrier particles to make them phosphorescent, or to adjust the refractive index of the composite article. Subsequent subsets of chambers can be used to perform atomic layer deposition cycles for a desired number of chambers (equal to twice the number of desired ALD cycles), or ALD and CVD can be alternated along the reactor chain to produce more precise ALD / CVD multilayers in a semi-continuous manner.

[0204] Molecular layer deposition is performed in a similar manner and is useful for applying organic or inorganic-organic hybrid coatings. Examples of molecular layer deposition are described, for example, in U.S. Pat. No. 8,124,179. The key is to incorporate one or more processing subsystems before or after the MLD coating process to condition or preferentially modify the starting surface, the finished coating, or both. Sometimes, one or more subsystems of the present technology may convert the precursor, feedstock, or coated article into a composite article containing inorganic or graphitic carbon.

[0205] Atomic and molecular layer deposition techniques allow the deposition of coatings approximately 0.1-5 angstroms thick per reaction cycle, thus providing a means of very fine control over coating thickness. Thicker coatings can be prepared by repeating the reaction sequence to sequentially deposit additional layers of coating material until the desired coating thickness is achieved.

[0206] The reaction conditions in gas phase deposition processes such as ALD and MLD are selected to satisfy three main criteria. The first criterion is that the reagents are gaseous or have sufficient vapor pressure under the reaction conditions. Thus, the temperature and pressure conditions are selected so that the reactants volatilize when they contact the powder at each reaction step. The second criterion is one reactivity. The conditions, especially the temperature, are selected so that the desired reaction between the reactive precursor and the particle surface occurs at a commercially reasonable rate. The third criterion is that the substrate is thermally stable from a chemical and physical point of view. The substrate should generally not decompose or react at the process temperature other than possible reaction with one reactive precursor on the surface functional groups at the early stage of the process. However, some surface treatment processes do apparently undergo a controlled corrosion or etching process, in which case this phenomenon is preferred. Similarly, the substrate should not melt or soften significantly at the process temperature so that the physical geometry of the substrate, especially the pore structure, is largely maintained. However, in some cases, controlled disintegration or release of the substrate is an objective of the coating process itself (either during the coating process or in the end-use environment), so such phenomena are not expressly prohibited in such systems. Similarly, the precursors diffuse into or within the substrate, allowing for expansion of the substrate at least by the volume occupied by the precursors. The reaction is generally carried out at a temperature of about 270-1000 K, preferably 290-600 K, more preferably 370-500 K, and often 370-460 K. By incorporating a plasma, the reaction temperature can be reduced by 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100 (K) or more.

[0207] Between successive doses of reactive precursors, the particles can be exposed to conditions sufficient to remove reaction products and unreacted reagents. This can be done, for example, by subjecting the particles to about 10 -5This can be accomplished by subjecting the particles to a high vacuum, such as 1000 torr or higher. Another way to achieve this, which is more readily applicable to industrial applications, is to sweep the particles with an inert purge gas between reaction steps. This sweep with inert gas can be performed while the particles are being transported from one reactor to the next in the apparatus. Dense and dilute phase techniques, whether under vacuum or not, are known to be suitable for pneumatic transport of a wide variety of industrially relevant particles that are well served by the functionalization processes described herein.

[0208] In the CVD process, two or more reactive precursors are simultaneously brought into contact with the powder particles. The reactive precursors typically react in the gas phase to produce a reaction product that deposits on the particle surface to form a coating. All the precursors in this case are introduced into a reactive precursor reservoir and collected in a powder reservoir. Alternatively, it is possible to introduce one of the reactive precursors in gaseous form together with the powder into the powder reservoir. A second reactive precursor is introduced into the reactive precursor reservoir as described above at a pressure higher than the pressure established in the powder reservoir. The valve unit separating the reservoirs is opened as before, allowing the second reactive precursor to escape into the powder reservoir, at least partially fluidizing the particles and reacting with the first reactive precursor to produce a reaction product that deposits on the powder particles to form a coating thereon.

[0209] The applied coating can be as thin as about 1 Angstrom (corresponding to about one ALD cycle) and as thick as 100 nm or more, with preferred thicknesses ranging from 0.5 Angstroms to about 25 nm, which varies widely depending on the end use application.

[0210] Particles made in a preliminary particle manufacturing step can be produced directly in the particle manufacturing process using a convenient continuous flow process and can be fed into a metered batch system with a metering valve (rotary airlock or similar) and then into the process described in the present technology. In general, when combining processes and / or subsystems having different residence times, precursor usage, pressures, temperatures or other parameters, it is advantageous to configure the control system to perform machine learning. In such cases, one way to incorporate machine learning into a composite article manufacturing system is by one or more algorithms that calculate sub-process deviations from modeled data or empirical data that includes information derived from one or more of direct in-situ signals, indirect in-situ signals, direct external signals or indirect external signals. Over time, one or more machine learning algorithms can be optimized to increase relative efficiency or reduce operating costs by about 1%, 5%, 10%, 15%, 20%, or ideally 30-50% or more, depending on the type of process and the importance, measurability and / or repeatability of the endpoint determination.

[0211] For clarity and conciseness of description, features may be described herein as part of the same or separate aspects or embodiments of the technology. Those skilled in the art will appreciate that the scope of the technology may include embodiments having all or some combination of the features described herein as part of the same or separate embodiments.

[0212] The present invention will be described in more detail in the following non-limiting examples.The examples are provided to describe the coating methods applicable to the production of particles of the present technology.These examples are not intended to limit the scope of the present technology.All parts and percentages are by weight unless otherwise specified. EXAMPLES

[0213] example Example 1 - Preparation of superior Li-rich, Mn-rich and / or Ni-rich materials for high energy low voltage fade cathode powders

[0214] Li x Mn y O z Five batches of Li were synthesized by flame spray pyrolysis. x Mn y O z Five additional batches of were synthesized by plasma spray pyrolysis, using a solution of lithium and manganese mixed in the appropriate ratio. Using SEM, primary particle sizes ranging from 50 nm to 500 nm are observed. Prior to synthesizing the batches, an initial screening was performed using various stoichiometric ratios of Li:Mn (x:y) in salt solutions to directly control the Li:Mn ratio of the final powder. Exemplary useful target ratios of x:y can be 2:1 or higher. In some applications, excess lithium is used, for example, 1%, 2%, 5% for powders that do not undergo subsequent synthesis steps, and sometimes 10%-15%-25% for powders that undergo subsequent synthesis steps to make a composite powder. The Li:Mn ratio is highly tunable on an atomic basis to an accuracy of 0.1%, which can be important for the performance of the final product. The average specific surface area of ​​the powders can range from 2 m2 depending on the flame vs. plasma spray technique and subsequent processing steps. 2 / g~50m 2 / g range. For fast charging battery materials, higher surface areas are desirable but require additional interface preparation using one or more pretreatments, surface coatings, or post-treatments described herein. Flame sprayed materials tend to form powders with lower tap densities (0.2g / cc to 1.5g / cc) and plasma sprayed materials tend to form powders with higher tap densities (0.5g / cc to 2.5g / cc). Although various examples are described herein in the context of Li2MnO3, it is understood that materials can advantageously have different element ratios that enhance subsequent processing steps or produce final materials.

[0215] Some of the Li2MnO3 powders are subjected to pretreatments, including, for example, annealing steps or exposure to molecular species that improve the intrinsic properties (e.g., crystallinity, purity, homogeneity, atomic ratios) of the starting core powder, or extrinsic properties (e.g., metal:oxygen ratio) of the surface, or treatments to form atomic gradients, morphologies, secondary aggregates throughout the outer layer of the powder. These treatments can be performed in an inert environment (N2, Ar, He, etc.), advantageously containing reducing species such as H2, CO, alkylaluminum, alkyllithium, alkylboron, NaBF4, formic acid, thiosulfate, oxalic acid, etc., and can be performed in gaseous or liquid state. In some batches, solid-phase reactions have been developed by blending Li2MnO3 powder with solid inorganic or polymeric powders (Li2S, Na2S, PVDF, PTFE, ULTEM, PEI, etc.) at high temperatures and in a suitable gas environment to allow for beneficial transfer of elements from one species to another.

[0216] The synthesized and pretreated Li x Mn y O z The powder is introduced into a suitable surface modification chamber designed to apply a coating onto the powder using gas / solid reactions. Fully continuous, semi-continuous and batch fluidized bed atomic layer deposition systems are deployed to deposit nanoscale inorganic coatings. Any suitable precursor described herein can be used to deposit the metal centers, which can be further converted to oxides, nitrides, sulfides / sulfates, phosphides / phosphates, halides, or simply reduced to the metal species. In this example, ZnO, Al2O3, TiO2, Nb2O5 and WO3 are applied to five batches synthesized from each production method. These materials are selected for their unique properties, known utility for use in combination with battery materials, and the range of atomic radii and oxidation states of the materials (e.g., ranging from +2 to +6).

[0217] Specific surface area is 25±5m 2 / g Li 2.25MnO3 nanopowder was synthesized and annealed at a temperature of 375 °C for 4 hours in a dry air environment. The powder was then transported to a semi-continuous ALD reactor equipped for TiO2 deposition. Alternating exposures of TiCl4 and H2O2 were used to deposit 200-5,000 ppm of TiO2 directly onto the surface of the primary nanoparticles. The material was then transported to another system configured to synthesize the material and mixed with salts containing Ni, Mn, and Co in the appropriate metal ratios to produce a material commonly referred to as Lithium Manganese Rich NMC (LMR-NMC). The material of the appropriate stoichiometry (30-50 atomic percent Li2MnO3 / NMC) was used to synthesize a composite material that exhibits both substantial voltage fade with cycling (i.e., intrinsic properties) and capacity fade with cycling (i.e., extrinsic properties) when fabricated using conventional co-precipitation techniques. It has been found that an ALD layer that is uniformly and effectively fixed "inside" the powder is sufficient to reduce the inherent degradation of the composite (about 10% decrease, about 50% decrease, or about 100% decrease). The actual or predicted voltage decay trends can be reduced to 20% after 50 cycles, after 250 cycles, and in some tuned configurations, after 1,000-3,000 cycles.

[0218] The powder is then transported to an atomic layer deposition reactor designed to apply an Al2O3 coating on the surface of the internally modified LMR-NMC powder. Depending on the final free lithium content, 2-20 ALD cycles can be used to apply a highly uniform coating of 0.1 nm to 20 nm. Thicker coatings are observed when there is substantial free lithium with which the ALD precursors can react beyond the traditional surface site limited model. In ALD post-treatment, we have found that an ALD layer that effectively pins the surface layer uniformly is sufficient to reduce the intrinsic and extrinsic combined degradation of the composite (about 10% decrease, about 50% decrease, or about 100% decrease). The actual or predicted voltage decay trend can be reduced to 20% after 50 cycles, after 250 cycles, and after 1,000-3,000 cycles for some tailored configurations. The pinned surface layer can be the outermost atomic surface or a shell containing 10-100 atoms that infiltrates inward into the secondary agglomerated particle species. Initial capacities are 300 mAh / g, sometimes 275 mAh / g, usually greater than 250 mAh / g, and typically always greater than 235 mAh / g.

[0219] The synthesized composite particles can be produced in separate unit operations or directly connected to in-line processing for efficient and streamlined production. Some powders are subjected to post-processing steps such as humidification, annealing (oxygen, dry air, or 20% oxygen with the balance being nitrogen), post-lithiation (exposure to lithium-containing precursors to produce lithiated ALD coatings) or exposure to precursor sources designed to apply capping layers of fluoride, phosphate or sulfate species (effectively preventing moisture migration during operation).

[0220] Different "internal" ALD cations can be used to further tune (5%, 10%, 20% or 35%) the initial capacity, crystallite size, power density, conductivity or resistivity (as measured in powder or electrode form), decay rate or other important measurable aspects of the powder that govern the applicability of the material to various types of batteries, applications or markets. The "internal" ALD layers can be used to completely and uniformly deliver beneficial inorganic dopants to the powder, while or to directly tune the inherent properties of the battery materials (e.g., anode, cathode, electrolyte, conductive additives, separators, binders, etc.) or to modify the powder with unique decomposition mechanisms that can be deployed in any application. This method can be used to produce engineered composite particles designed for high energy, maximum operational efficiency and ultra-low cost. This method can be used to synthesize similar battery materials including starting materials of Li2S, elemental sulfur, lithium, silicon and other materials to produce powders for superior lithium-sulfur batteries. Similar materials when using Na or K instead of lithium-based precursors or materials can produce high performance powders for sodium-ion and potassium-ion batteries. Using this sequential method, high performance air / moisture stable solid electrolyte materials (e.g., LPS, LXPS (X is a group 14 metal), garnet, LLTO, LLZO, LiPON, etc.) can also be synthesized, enabling the fabrication of new cost-effective solid-state batteries.

[0221] Example 2: Manufacturing of high performance oxidation-resistant metal powders

[0222] Three batches of copper nanoparticles and three batches of nickel nanopowder were synthesized using a plasma spray process to produce spherical metal powders with d50 in the 50-80 nm range. Each batch of synthesized powder was transported to an ALD system in an inert environment without exposing the metal powder to ambient conditions. 5-50 ALD layers of TiO2 (or ZrO2) were applied to each powder using precursors selected from the list above. In one embodiment, to avoid sintering issues, the initial process cycle included alternating exposures of TiCl4 and H2O (or H2O2 or O3) at temperatures ranging from 60-120 °C. After five or sometimes ten of these TiO2 cycles, the temperature was increased to allow a transition from the oxide coating to a nitride coating. This was performed using TiCl4, TEMAT, TDMAT or TDEAT, alternating with either NH3, N2H4 or nitrogen-containing plasma. Typically, however, when TiCl4 and NH3 are used as precursors, the presence of residual chlorine can approach 1-2 wt% depending on the processing conditions. Instead of TiN, ZrO2 or Zr3N4 were also produced to test the effect of various coatings on end-use systems such as co-fired internal electrodes in multilayer ceramic capacitors. After production of each "core-shell-shell" powder (i.e., comprising a TiN shell coated on a TiO2 shell coated on Ni or Cu), a post-treatment step was found to be beneficial to minimize the presence of residual halide species in the coating (or carbon by-products if alkylamine precursors are used). One post-treatment option was to heat treat the powder in an inert or weakly or strongly reducing environment. Annealing temperatures of 300-500°C for 1-10 hours helped to reduce the residual chlorine content to less than 1%, sometimes less than 0.5%, typically less than 0.25%, and occasionally to undetectable levels. Depending on the time and temperature used, the powder began to sinter slightly and the d50 particle size increased to 100nm, 200nm, and sometimes up to 500nm. This may become undesirable for end-use functionality.Rather than traditional annealing, some powders were subjected to a hypervelocity plasma spray process operating with a material flux capable of purifying and cleaning the shell without sufficient energy flux to melt or otherwise decompose the core substrate material. The resulting materials were produced with undetectable amounts of impurities present in the coating. Performance was further verified using thermogravimetric analysis, which demonstrated that the materials were resistant to oxidation in air at least 400°C, typically 500°C, sometimes 600°C, occasionally 850°C, and in certain combinations with relatively thick conductive shells, up to 1,000°C.

[0223] Example 3A: Effective delivery of challenge precursors to powder surfaces in the saturation regime

[0224] Approximately 5.0m 2 TiO2 particles (10 kg) with a surface area of ​​1 / g were coated with atomic layer deposition to produce a coating of approximately 50,000 m 2The palladium is transported to the reservoir of the coating subsystem 301 after a pretreatment process in the processing subsystem 201 that prepares the surface area of ​​the palladium. The intended coating process is palladium, including exposure to palladium hexafluoroacetylacetonate (Pd-HFAC) and formalin. The Pd-HFAC is loaded into the chamber 810 of one embodiment of the transport enhancer 800. Extruded 0.16 inch packing, previously pretreated with an atomic layer deposition coating cycle, is used as the packing medium 808. The large surface area is effective for improved wettability and / or increased adsorption capacity with the ALD coating, which allows for efficient mass transfer between the liquid and gas phases. The surface area is approximately 576 ft2 / ft3 for the 0.16 inch size (possibly replaced with 372 ft2 / ft3 for the 0.24 inch size packing material in subsequent experiments). The packing factor is 693 for the 0.16 inch size (and 420 for the 0.24 inch size). High free space is especially important in vacuum distillation (to reduce pressure drop) and in extractive distillation and absorption (high liquid or gas loadings are common), which is the system emulated by this particular embodiment of the transport enhancer 800. This particular packing material is chosen to result in high free space (94% for the 0.16 inch size (96% for the 24 inch size). To achieve efficient precursor delivery, the coating chamber 302a is evacuated to rough vacuum conditions (<10 Torr) in synchronization with the automatic filling of the precursor container 801 with a solution containing a sufficient amount of Pd-HFAC to saturate the surface of the powder to be coated in the coating subsystem 301. To this end, characteristics are distributed from the electronic database server 363 through the common signal hub 360 to the control port 315 and the process enhancer 800. The vaporizer chamber 810 is then evacuated and purged by passing an inert gas through the valve 802b and the distribution plate 809, while the valved delivery assembly 805 is configured to accommodate the appropriate level of flow.The valved delivery assembly 805 is then configured to create the appropriate void space in the precursor volume controller 804, for which the common signal hub 360 sets a target point based on the contents and properties (e.g., saturation levels, among other considerations) of the coating subsystem 801 and the transport enhancer 800. Once the common signal hub 360 identifies that the conditions and criteria are suitable to achieve the objective via one or more signal connectors 806 and 807, the valved delivery assembly 805 is configured to allow an appropriate volume of precursor to flow from 804 to the vaporizer chamber 810, which allows the precursor to be adsorbed onto a portion of the surface of the packing medium 808. The common signal hub 360 then operates a first actuation mechanism for the coating subsystem 301 (or 302, 302a, 302b, 401, 402, 402a, 402b, etc.) in synchronization with one or more actuation mechanisms of 802a, 802b, 803 and 812, which together can be configured to be used as either a valve assembly or a pump assembly controlled by the common signal hub 360 to efficiently deliver the 50,000 m of Pd-HFAC loaded to the coating subsystem 301. 2 A given percentage of the powder surface area (100% in this example) can be saturated.

[0225] Example 3B: Effective delivery of precursors to the surface of a flowable object at sub-saturated conditions

[0226] In another series of trials, the TiO2 powder from Example 3A was 2The aluminum oxide catalyst pellets (or extrudates) having a surface area of ​​1000 μg / g are replaced. The volumes of the chambers in the coating subsystem 301, precursor container 801, precursor volume controller 804, and vaporizer chamber 810 are appropriately configured based on information stored in database 363. The packing medium 808 is replaced for a larger surface area substrate, increasing the total surface area in this example. In these tests, target loadings of 200, 400, 600, 800, and 1,000 ppm Pd are desirable to achieve the end-use properties of the composite material being manufactured and narrow and / or optimize the selection range. The synchronization procedure of Example 3A is again followed, allowing for adjustment of the time constant based on the differences in volume and surface area contained throughout the system. During each subsaturation exposure, the appropriate amount of Pd-HFAC is again delivered to the surface of the substrate in the coating subsystem 302 via synchronized actuation of the valve mechanisms of both the coating subsystem 301 and the transport enhancer 800. After each trial, the material is removed and evaluated for Pd ppm content using an inductively coupled plasma system, which is then entered into an electronic database server 363 to define a trial series. Five trials of trial series 1 are completed with concurrent evaluation of loading. Experimental results of actual Pd deposited for each target loading are shown in Table 1 below. Sub-processes (369) performed in trial series 1 resulted in loadings higher than the target loadings for these materials, as shown in Table 1. Table 1 shows one of many potential direct external signal monitoring sub-process results 372, which are introduced into a sub-process model deviation calculator 374. These results are fed to a critical signal setpoint calculator 365 via a machine learning algorithm 376, selecting and adjusting one or more critical setpoints (typically further benefiting from additional historical processes for different materials). Trial series 2, which includes sub-processes with different critical setpoints, is then performed based in part on the results of trial series 1. The results of Trial Series 2 are also shown in Table 1 below and result in loadings within the target range falling into the low loading range, but with the measured loadings gradually increasing as the target loadings increase.This illustrates the unexpected challenges associated with delivering difficult precursors to the surface of high surface area powders or flowable materials. Clearly, there are nonlinear adjustments required when designing a process for less than saturated conditions. This can include modulation of two or more of the following: volume, mass, total surface area, pressure, temperature, actuation mechanism speed, and exposure / residence time. Fortunately, it has been determined that machine learning, although complex, can effectively predict methods and mechanisms for overcoming this unexpected nonlinear behavior, leading to minimization of processing time (or maximization of production rate) of composites that achieve functional end-use properties. To demonstrate this, Trial Series 3 is performed in which critical signal set points are nonlinearly adjusted to allow higher loading samples to fall within specified loading targets, thereby achieving the overall system objective. [Table 1]

[0227] Example 3C: Effective Delivery of Precursor Exposure to the Surface of a Flowable Object

[0228] In another series of trials, the TiO2 powder from Example 3A was added to about 0.7 ml 2A lithium ion battery cathode powder containing lithium, nickel, cobalt, aluminum, and oxygen with a surface area of ​​1000 ppm / g was substituted. The desired coating was an aluminum phosphate (AlPO) material, where the ratio of aluminum and phosphorus (Al:P) was measurable and controllable, and one or more precursors contained alkoxide-like ligands. The coating subsystem 301, precursor container 801, precursor volume controller 804, and chamber volumes in the vaporizer chamber 810 were appropriately configured based on information stored in database 363. The loading medium 808 was selected to match the total surface area in this example. Approximately 2,200 grams of powder was loaded into the coating subsystem 301, loaded with trimethylaluminum (TMA) and trimethylphosphate (TMPO). In these trials, a target loading of approximately 50-300 ppm aluminum was added to achieve, narrow the selection range, and / or optimize the end-use properties of the composite being manufactured, and an Al:P ratio of 1:1 to 4:1 was desired. The synchronization procedure of Example 3A was performed again, allowing the time constant to be adjusted based on differences in the volumes and surface areas involved throughout the systems. During each exposure, an appropriate amount of TMA was delivered to the surface of the substrate in coating subsystem 302 by synchronous actuation of the valve mechanisms for both coating subsystem 301 and transport enhancer 800, both maintained at a delivery temperature of 30° C. Then, in a synchronized fashion, an appropriate amount of TMPO was delivered to the surface of the substrate in coating subsystem 402 by synchronous actuation of the valve mechanisms for both coating subsystem 401 and transport enhancer 800, both maintained at a delivery temperature of 90° C. After each run, the material was removed and evaluated for Al and P ppm content using the inductively coupled plasma system and entered into electronic database server 363 to define the trial series. Four runs in trial series 1 were completed with simultaneous evaluation of loading using four cycle numbers (2, 4, 6, and 8) and an operating pressure of approximately 15 Torr. Four runs of Trial Series 2 were completed and loading evaluations were performed simultaneously using the same four cycle numbers (2, 4, 6, and 8), but at an operating pressure of approximately 20 Torr. The experimental results of the actual deposited Al and P for each target loading are shown in Table 2 below.The sub-processes (369) implemented in Trial Series 1 resulted in aluminum loadings that achieved linear target loadings for these materials (Table 2), with the sub-process model deviation calculator 374 showing that it can function properly even when the difference between the target loading and the actual loading is very close. These results were fed back to the critical signal setpoint calculator 365, via a machine learning algorithm 376, selecting and adjusting one or more critical setpoints (typically residence time and / or one or more actuation mechanism parameters). Trial Series 2, including sub-processes with various critical setpoints, was implemented based in part on the results of Trial Series 1. The results of Trial Series 2, also shown in Table 2 below, demonstrate the ability of the system to maintain the aluminum loadings from Trial Series 1 while decreasing the Al:P ratio, which illustrates the use of machine learning to overcome the challenges associated with delivering one difficult precursor to the surface of a high surface area powder or flowable material without disrupting or adversely affecting the delivery of one or more less difficult precursors to the surface. Although complex, it was determined that machine learning can effectively predict methods and mechanisms to overcome this unexpected nonlinear behavior, leading to minimization of processing time (or maximization of production rate) of composites that achieve functional end-use properties. To evaluate electrochemical performance, materials were prepared into coin cell cells. In some cases, materials with Al:P ratios between 1.1 and 1.3 showed greater than 20% increases in cycle life, rate capability, and / or calendar life. In other cases, Al:P ratios between 1.5 and 2.2 showed greater than 20% increases in cycle life, rate capability, and / or calendar life at least 10° C. above room temperature, 0.1 V above standard operating potential (typically 4.2 volts), or both. In some cases, increasing the number of ALD cycles (6, 8, 10, 12, 14, or 16 cycles) and lower Al:P ratios (0.9:1 to 1.2:1) of aluminum phosphate provided at least 30% improvement, often 50% improvement, and sometimes 80% improvement.Each of these results are stored in an electronic data server 363 so that future materials engineered for superior rate capability, temperature performance, cycle life, calendar life, etc. can begin the design process in an advanced parameter space as determined by machine learning algorithms 376. [Table 2]

[0229] Example 3D: Effective Delivery of Precursors to the Surface of a Flowable Object Using Liquid Injection

[0230] In another trial series, the same lithium ion battery cathode powder containing lithium, nickel, cobalt, aluminum, and oxygen of Example 3C was used to produce a cathode having a surface area of ​​about 0.7 m 2A powder with a concentration of 0.01 ppm / g was used. The desired coating was a titanium dioxide material using the alkylamide precursor tetrakis-dimethylamido titanium (TDMAT). The coating subsystem 301, precursor container 801, precursor volume controller 804, and chamber volumes in the vaporizer chamber 810 were appropriately configured based on information stored in the database 363, which was pre-optimized based on the results of Example 3C. The loading medium 808 was also the same as that used in Example 3C. The transport enhancer 800 was also modified to accommodate delivery of liquid to the coating subsystem 302 that can accommodate a phase change of the liquid to a gas, and to utilize it as an alternative to the vaporizer chamber 810. Two trial sets, each consisting of four runs (1-4 TDMAT+H2O cycles each), were conducted using two different precursor delivery strategies. After each run, the material was removed and evaluated for Tippm content using an inductively coupled plasma system, which was then entered into the electronic database server 363. In the direct liquid injection approach, 2 feet of heating tape was attached to the delivery line of the transport enhancer 800, which was further equipped with a syringe pump to deliver a controlled amount of material to the coating subsystem 302. The precursor system was preheated to the desired set point temperature for at least 1 hour. The set point temperature, tubing size, syringe parameters and precursor tare weight were entered into the machine learning algorithm 376. The system was fully evacuated before injecting the liquid into the transport enhancer 800. A predetermined amount of liquid was dosed to the coating subsystem 302 using one or more injection times to correspond to the total surface area to be coated in the process. Synchronized actuation of the delivery pump and control valves was required to maintain proper control of the molar amount delivered to the coating subsystem 302. The actual pressure of the coating subsystem 302 was monitored in real time to provide a visualization of the effect of liquid evaporating within the coating subsystem. Once the pressure equilibrated, the process proceeded as normal.Overall loading results from the two different approaches were similar (approximately 90-100 ppm Ti per cycle), although the overall process time per cycle was typically shorter with the direct liquid injection process approach. Overall process times were similar when the coating system 301 chamber volume was 10-20% filled, but additional benefits were observed when the chamber was 30% or more full. Process time reductions of 10-36% were achieved with various combinations of total surface area and chamber volume.

[0231] Example 3E: Effective Delivery of Nitrogen-Containing Precursors to the Surface of a Flowable Object

[0232] In another series of trials, the same lithium ion battery cathode powder containing lithium, nickel, cobalt, aluminum, and oxygen of Example 3C, but having a surface area of ​​about 0.7 m 2Powders with a 100% Cr / g content were used. The desired coatings are an array of various metal oxide and nitride materials derived from alkylamine precursors, among the non-limiting list of precursors described herein, and the coatings or substrate / surrogate particles used herein. Precursors that could be effectively delivered in the gas phase were delivered using either the gas phase or direct liquid injection approach, and precursors that could not be effectively delivered in the gas phase were delivered using the direct liquid injection approach only in these tests. Tris(diethylamido)aluminum and anhydrous ammonia were used to deposit the AlN coatings. antimony trioxide coatings are deposited using tris(dimethylamido)antimony(III) and H2O (or O3), gallium nitride and gallium sulfide are deposited using tris(dimethylamido)gallium and ammonia or H2S, respectively, hafnium oxide coatings are deposited using tetrakis(diethylamido)hafnium(IV) and water, and boron doped TiO2 coatings (B:Ti ratios of 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1 and 1:1 are deposited using TDMAT, H2O and either triethylboron ("TEB") or triisopropylborate in sequence, by varying the number of moles controllably dosed into coating systems 301 and 401. ), lithium trimethylsilylamide is alternated with a series of precursors including TMPO, TDMAT, TMA, niobium isopropoxide, and TEB to produce lithium phosphate, titanate, aluminate, niobate, and borate, respectively, and combinations thereof; tris(ethylmethylamido)tert-butylimido)tantalum(V), TDMAT, and HO / O to produce tantalum doped titanium oxide coatings; tetrakis(dimethylamino)tin(IV) and HO or HS to deposit tin oxide and tin sulfide, respectively; and tetrakis(dimethylamido)zirconium(IV) and HO to deposit zirconium oxide coatings on battery materials.

[0233] Example 4: Composite synthesis in the system of Figure 5

[0234] Composite powders are produced at a target capacity of 5 kilotons per year using a system similar to that shown in FIG. 5. Micron-sized metal powder substrate with a tap density of 2 kg / L is continuously fed to a hopper 104, which then feeds the powder first to a pretreatment subsystem 201 where heat treatment is performed in a reducing environment (here 4% H2 in N2), followed by a coating subsystem 301 performing a sequential gas phase molecular grafting process to apply a two-member block copolymer coating. A production rate of 694 kg / hr is proposed via a common signal hub 360 with a stream time of 300 days per year and a residence time per chamber of 15 minutes. In this particular process, a 36 inch internal diameter 2,170 L tube filled to a 4.0% V / V fill ratio is used, configured to process the equivalent of 0.8 supersacks per hour. In the first pretreatment subsystem 201, reducing gas is continuously dosed to a moving rotating bed at an average rate of 10 kg / hr for a processing time of about 2.0 hours, which has been found sufficient in previous runs to minimize and / or remove native oxides from the surface of similar metal powders with similar surface areas. The material is then transferred to the coating subsystem 301, where a first precursor is grafted to the surface of the metal powder in the coating subsystem 302a, followed by a second precursor grafted to the first polymer by a chemical process. In this example, a cyclic olefin copolymer (COC) is produced as a moisture barrier, making the surface of the metal particles biocompatible, with low extractable content and high purity. Not shown in FIG. 5 is an additional coating subsystem that applies an additional coating layer, resulting in coated particles with a COC shell with adjustable coating thickness. COC coating thicknesses of 1.0, 2.0, 3.0, 5.0, 7.5 and 10.0 nm have been applied to metal particles to produce chemically resistant metal powders that do not affect optical properties, however, the system allows alternative substrates to be easily coated with one or more COC, alternating polymeric or non-polymeric coatings. Additionally, a subsequent processing subsystem 501 can be deployed to tailor the properties of one or more deposited coating layers.

[0235] Example 5A: Composite synthesis in the system of FIG. 7

[0236] Flowable composite materials are produced using a system similar to that shown in FIG. 7, where mixed metal oxide nanopowder is synthesized in synthesis subsystem 101, followed by pretreatment subsystem 205, where it is coated with a first ALD coating (302) and then a second ALD coating (402). In this system, sized at a capacity of 5 kilotons per year, the continuously synthesized substrate is pretreated with hot silane-based molecules in a metered batch system before entering coating subsystem 302a via valve assembly 311. A first actuation mechanism of valve assembly 311 is in electrical communication with at least one pressure sensor of pretreatment subsystem 205, which indicates when the pretreatment sub-process is complete. A common signal hub 360 controls the first release of the gas phase and then the transport of the solid phase to the coating subsystem. A pretreatment time of 20 minutes is used for this material, followed by a 20 minute purge and / or drying step. The flowable material is loaded into chamber 302a, where mixing internals 321 are used to manage the mechanical fluidization process. The chamber of this particular embodiment can be operated in batch / static, semi-continuous / intermittent or pulsed, or fully continuous mode. In this case, the static option is selected with a direct liquid injection precursor dosing system based on the specific physicochemical properties of the substrate and coating material. Upon flash evaporation of the precursor, the powder and reactive precursor are mixed with constant mechanical fluidization for 20 minutes under aeration conditions. The nanopowder is then subjected to a second precursor in subsystem 302b for a static exposure time of 55 minutes after a 10 minute evacuation and 5 minute powder transport step. The coated powder is then conveyed to a holding / surge tank at the top of the coating subsystem 401. At this point, this sub-batch of material is positioned and prepared for loading into the coating subsystem 402a via the valve assembly 411, and a second identically sized sub-batch of material is prepared for loading into the coating subsystem 302a via the valve assembly 311, defining two consecutive subsystems of the present technology.The first actuation mechanism of valve assembly 411 is actuated in synchronization with the first actuation mechanism of valve assembly 311 to dispense precursors to subsystems 302a and 402a via 704a and 704b, respectively. The common signal hub 360 can simultaneously monitor and control each step of each sub-process taking place within each subsystem, while continuously monitoring all field signals and predicting sub-process model deviations accordingly.

[0237] Example 5B: Scaled-up composite synthesis in the system of FIG.

[0238] With a demonstrated process capability of 5 kilotons per year capacity as described in Example 5A, this process is emulated at a 50 kilotons per year capacity with a similar layout and configuration using model predictive control associated with machine learning algorithm 376. 50 kilotons of powder is simulated with a system configured to compound and coat materials to produce composite articles at a production rate of 6,944 kg / hr in a 4,416 gallon reactor size. Machine learning algorithm 376 receives critical inputs 364 for this material set and sets the scheduling / frequency and speeds of valve actuation mechanism X (367) and valve actuation mechanism X+1 (368) of subsystem 301 and subsystem 401. Based on the critical parameters, a powder loading time of 60 min was emulated, with the following sequence (calculated process times): evacuation / preheat (45 min), drying (20 min), first precursor exposure (20 min), first precursor purge (20 min), transport (30 min), second precursor exposure (100 min), second precursor purge (20 min) and final pressurization and transport to subsequent subsystems (75 min).

[0239] Comparative Example 1: Composite synthesis in the system described by King et al. (U.S. Pat. No. 9,284,643, "the '243 patent")

[0240] Using a semi-continuous gas phase coating system similar to that taught by the '243 patent, a coating volume of approximately 3.0 to 3.4 m was obtained at various sub-batch volumes. 2An aluminum oxide coating was applied onto boron nitride particles having a surface area of ​​1000 nm / g. In such a system, a valve unit having only one actuation mechanism was inserted between a powder reservoir and a reactive precursor reservoir, the valve unit being operable between an open position and a closed position, such that when the valve unit was in the open position, the powder reservoir was isolated from the reactive precursor reservoir, but when the valve unit was in the closed position, the powder reservoir was in communication with the reactive precursor reservoir, so that the reactive precursor contained in the reactive precursor reservoir could flow into the powder reservoir and the powder contained in the powder reservoir could fall into the reactive precursor reservoir. The valve unit also established a constricted flow path of the reactive precursor from the reactive precursor reservoir to the powder reservoir, creating an eruptive fluidized bed for a time period based on the geometry of the system, the physicochemical properties of the substrate material, and the properties of the reactive precursor. With boron nitride, a solid lubricant, the ability to create and maintain an eruptive fluidized bed can be challenging, as pockets of reactive precursor can slip through pockets of boron nitride powder without fully exposing all of the surface. This limited the amount of material that could be processed, reducing overall throughput. One way to overcome this problem was to incorporate mixing internals 321 into chambers 302a and 302b. This enhanced solid-gas mixing in the constricted flow passages, such as those incorporated in the subsystem of FIG. 9. However, it was discovered that a second actuation mechanism could be incorporated at each valve assembly, where a first actuation mechanism that largely controls the transport of the gas phase and a second actuation mechanism that largely controls the transport of the solid phase could be actuated separately to maximize mixing in each region of the subsystem. Not only is this beneficial in maximizing process efficiency within a particular subsystem, but unexpectedly, there are certain efficiencies (such as one or more precursor feeds, effluent capture, separation or regeneration, pump / vacuum throughput, reduced process time, etc.) that can be exploited when at least one actuation mechanism from one subsystem is operated in synchrony with at least one actuation mechanism from a different subsystem. This benefits from a control system that electronically communicates with all the actuation mechanisms via a common signal hub to ensure synchronous operation.Table 3 below shows the ICP data for the measured aluminum content. Based on these results, the loadings from the two systems fell within standard error of each other when processing 2-10 kilograms of material. However, when the sub-batch size was increased to 50 kilograms and 100 kilograms, the measured loadings decreased with increasing batch size. This shows that having multiple actuation mechanisms can improve processing efficiency. Using this process, additional data points are generated. [Table 3]

[0241] Comparative Example 2: Composite synthesis in the system described by Liebsch et al. (WO2018019627, "the '627 application")

[0242] A semi-continuous gas-phase ALD coating system is constructed based on the teachings of the '627 application. Such a system is identical to that taught by the '243 patent, except for the requirement to have at least one buffer device disposed between the first and second reactors. It is believed that the operation of such a system without the use of a buffer device would be sufficiently similar to the apparatus and process described in Comparative Example 1. The '627 application system is a 0.7 m2 surface area ALD coating system. 2The '627 application was used to apply aluminum oxide coatings in various sub-batch quantities onto lithium metal oxide battery material having a powder density of 10000000000000 / g. The '627 application also teaches that particles are conveyed from a first reactor to a second reactor via a first valve assembly, where the valve assembly includes a first valve unit (gas lock) having only one actuation mechanism, and a second valve unit (gas lock) having only one actuation mechanism is inserted between the first and second reactors. The '627 application and the '243 patent teach that particles can be recirculated through a semi-continuous ALD coating apparatus to increase the number of ALD cycles that can be provided in a given tool footprint. The only difference is the buffer device, where the valve assembly of the '243 patent was modified to include the buffer device and diverter valve of the '627 application. The apparatus was operated according to the methods of the '243 patent (without diverting the powder to the buffer device) and the '627 application (with diverting the powder to the buffer device). It was found that both the '243 and '627 apparatuses had practical limitations in the percentage of the coating chamber volume that could be filled with powder. This was due to reduced mixing efficiency with valve assemblies having first and second valves (or gas locks) with only one actuation mechanism. The larger valve assembly of the '627 application, requiring a similarly sized diverter valve and buffer device, was able to achieve a slightly higher volumetric fill factor only because of the expanded mixing area of ​​the larger valve assembly. However, the capital cost of such a larger valve assembly with the additional diverter valve and buffer device was approximately three times greater than the '243 apparatus. Furthermore, although the fill factor was greater in the '627 apparatus, the additional time required to fill and empty the buffer device resulted in a substantial reduction in the net particles coated per hour.As production weights increased, the single actuation mechanism of the diverter valve was insufficient to divert 100% of the material to the buffer device, so that 5-20% of the material bypassed the buffer device and was delivered early to the subsequent chamber (although this fraction continued to effectively follow the method of the '243 patent, but not the '627 application). Two further shortcomings of the '627 application's apparatus are a) inefficient purging of material from the buffer device when the process was restarted, and b) loss of spouted fluidized bed action (due to the presence of the additional diverter valve and buffer device in or adjacent to the flow path) as material was transported through the valve assembly of the '243 patent. The inefficient purging became evident after 20 passes of particles to apply 20 ALD cycles. Typically, 2-15% of the material in process was retained in the buffer device after each ALD cycle. Because ALD is a sequential process, material held in such a buffer device does not receive subsequent coating treatments, and effective growth rates are adversely affected. Furthermore, subsequent equipment adjustments are required to remove the final material from the buffer device, reducing uptime and overall production rates. Loss of the erupting fluidized bed action reduces mixing efficiency, which is exacerbated when the '627 application's apparatus is filled to less than 50% volume. This was overcome to some extent by increasing the amount of reactive precursor delivered to the powder in the first reactor, but this increased precursor costs by 100-150%. Compared to materials produced using the '627 application's apparatus, materials produced using the '243 patent's apparatus exhibited i) less variability in aluminum loading, ii) higher precursor efficiency, iii) reduced maintenance and downtime, and iv) substantially lower operating and capital costs.

[0243] However, the shortcomings of the '243 and '627 patents have been overcome with respect to the present technology's apparatus having valve or pump assemblies with two or more actuation mechanisms (without substantially increasing capital costs compared to valve assemblies with one actuation mechanism). Materials produced with the present technology's apparatus are superior in production rate, quality and cost, and the present technology's apparatus has higher uptime, lower maintenance costs and higher achievable throughput. Furthermore, the present technology's apparatus can be configured to operate in semi-continuous or continuous mode as desired and / or recommended by the machine learning algorithm 376. Furthermore, batch recirculation strategies can be deployed more uniformly without risking the reduced production rate and quality observed with the '627 technology's apparatus.

Claims

1. 1. An apparatus for treating a surface of a plurality of flowable articles with a gaseous precursor, comprising: a) a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet; b) a first solid phase valve or pump assembly in fluid communication with the first solid phase inlet of the first chamber; c) a first gas phase valve or pump assembly adjacent to and in fluid communication with the first gas phase inlet of the first chamber; d) a common signal hub; e) at least one control system; Including, the at least one first solid phase inlet and the at least one first solid phase outlet include a solid phase valve assembly or a solid phase pump assembly having at least two actuation mechanisms configured for bidirectional control signal communication with a signal hub; the at least one first gas phase inlet and the at least one first gas phase outlet include a gas phase valve assembly or a gas phase pump assembly having at least one actuation mechanism configured for bidirectional control signal communication with a signal hub; the first chamber further includes a first sensor network including two or more sensors, each sensor in the first sensor network configured to deliver one or more signals to a signal hub, the first sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the item; At least one control system is configured to simultaneously transmit signals to and receive signals from one or more signal hubs, providing a controllable unit for regulating material flow.

2. The first chamber comprises: a) receiving a solid phase comprising a flowable article having a definable specific surface area through one or more first solid phase inlets; b) dispensing through one or more first solid phase outlets a solid phase comprising a flowable article having a treated surface with a definable specific surface area; c) receiving, creating and / or containing a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux through one or more first gas phase inlets; and d) distributing a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through one or more first gas phase outlets. The apparatus of claim 1 , configured to:

3. at least one transport unit having one or more actuation mechanisms and configured to control a temperature, pressure, and composition of the gaseous environment while regulating a material flow rate of the plurality of flowable articles; the inlet of the transport unit i) in fluid communication with at least one first solid phase outlet valve assembly or solid phase pump assembly; ii) in bidirectional control signal communication with a signal hub; and The apparatus of claim 1 , wherein the one or more transport unit actuation mechanisms are configured to operate synchronously with one or more of the first solid phase outlet valve assembly or solid phase pump assembly actuation mechanisms.

4. The second chamber further comprises: a) at least one each of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet; b) a second solid phase valve or pump assembly in fluid communication with the second solid phase inlet of the second chamber; c) a second gas phase valve or pump assembly adjacent to and in fluid communication with the second gas phase inlet of the second chamber; and d) a common signal hub; Including, the at least one second solid phase inlet and the at least one second solid phase outlet include a solid phase valve assembly or a solid phase pump assembly having at least two actuation mechanisms configured in bidirectional control signal communication with the signal hub; the at least one second gas phase inlet and the at least one second gas phase outlet include a gas phase valve assembly or a gas phase pump assembly having at least one actuation mechanism configured for bidirectional control signal communication with the signal hub; the second chamber further includes a second sensor network including two or more sensors, each sensor in the second sensor network configured to deliver one or more signals to a signal hub, the second sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the item; and At least one control system is configured to simultaneously transmit and receive a plurality of signals to and from one or more signal hubs to provide a controllable unit for regulating material flow; 2. The apparatus of claim 1.

5. The second chamber comprises: a) receiving a solid phase comprising a flowable article having a definable specific surface area through one or more second solid phase inlets; b) dispensing through one or more second solid phase outlets a solid phase comprising a flowable article having a treated surface with a definable specific surface area; c) receiving, creating and / or containing a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar fluidity through one or more second gas phase inlets; and d) distributing a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux through one or more second gas phase outlets; 5. The apparatus of claim 4, wherein the apparatus is configured to:

6. at least one transport unit having one or more actuation mechanisms and configured to control a temperature, pressure, and composition of the gaseous environment while regulating a material flow rate of the plurality of flowable articles; The inlet of the transport unit i) is in fluid communication with at least one first solid phase outlet valve assembly or solid phase pump assembly, and ii) is in bidirectional control signal communication with a signal hub, and the one or more transport unit actuation mechanisms are synchronously actuated with the one or more first solid phase outlet valve assembly or solid phase pump assembly actuation mechanisms; an outlet of the transport unit i) in fluid communication with at least one second solid phase inlet valve assembly or a solid phase pump assembly; and ii) in bidirectional control signal communication with a signal hub; 5. The apparatus of claim 4, wherein the one or more transport unit actuation mechanisms are synchronously actuated with one or more second solid phase inlet valve assemblies or solid phase pump assembly actuation mechanisms.

7. The apparatus of claim 6, wherein the one or more transport unit actuation mechanisms are synchronously actuated with the one or more first solid phase outlet valve assemblies or solid phase pump assembly actuation mechanisms and the one or more second solid phase inlet valve assemblies or solid phase pump assembly actuation mechanisms.

8. The apparatus of claim 1 , further comprising: a plurality of control systems; and a master control system configured to simultaneously control the plurality of control systems.

9. The apparatus of claim 1 , further comprising: a plurality of signal hubs; and a common signal hub configured to aggregate signals to and from the plurality of signal hubs.

10. Each actuation mechanism of the valve assembly or pump assembly is i) Instantaneous release; ii) instantaneous closure; iii) controlled release over a programmable time constant; iv) controlled closure over a programmable time constant; v) Enlarging the subcomponents to reduce the conductance through the assembly; vi) contraction of subcomponents to increase conductance through the assembly; vii) Concave or convex deflection of the subcomponent; viii) rotation of the subcomponent collinear with the direction of solid material flow; ix) rotation of the subcomponent tangential to the direction of solid material flow; x) an instantaneous increase in conductance to a position less than the fully open position; xi) an instantaneous decrease in conductance to a position greater than the fully closed position; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to facilitate aeration, contraction or expansion of the primary phase unit volume; and xiv) actuation mechanisms initiated by electrical application of sine waves, Dirac functions, triangle waves or square waves over one or more programmable time constants; The apparatus of claim 1 , comprising:

11. 2. The apparatus of claim 1, wherein at least one actuation mechanism of any one or more of the solid phase valve assemblies or solid phase pump assemblies is configured to be initiated synchronously with any one or more actuation mechanisms of any one or more of the gas valve or pump assemblies.

12. at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the first chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve assemblies or gas phase pump assemblies of the first chamber; at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the second chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more gas phase valve or pump assemblies of the second chamber; at least one actuation mechanism of any one or more solid phase valve assemblies or solid phase pump assemblies of the second chamber can be configured to be initiated synchronously with any one or more actuation mechanisms of any one or more solid phase valve assemblies or solid phase pump assemblies of the first chamber; 5. The apparatus according to claim 4.

13. The apparatus of claim 1 , wherein the at least one control system is configured to perform machine learning.

14. 1. A method for performing a first surface treatment process on a plurality of fluent articles, comprising: a) providing a plurality of flowable articles having provided, estimated, measured or known specific surface areas in a first chamber and inputting said specific surface areas into at least one control system; b) inputting into a control system of the surface treatment system a nominal target value for the amount, mass or unit volume of flowable articles to be treated, thereby defining a first total surface area target; c) providing a reactive precursor for treating surfaces of the plurality of flowable articles, and inputting into the control system a provided, estimated, measured or known number of moles of reactive precursor required to saturate, react or treat the entire first total surface area target using empirical or estimated process conditions to define a full saturation amount; and d) selecting a target saturation ratio to obtain a process recipe for a batch, semi-batch, semi-continuous or continuous surface treatment process, wherein said process recipe includes at least one target pressure level associated with said target saturation ratio; A method comprising:

15. e) dispensing a target amount, mass or unit volume of flowable article and gas phase environment into the first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where the first actuation mechanism effects delivery of a gas-solid composition comprising primarily a gas phase and the second actuation mechanism effects delivery of a gas-solid composition comprising primarily a solid phase; and f) subsequently dispensing a gas phase comprising a target number of moles of one or more reactive or non-reactive gases or precursors into said first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the first actuation mechanisms effect the transport of said gas phase under conditions suitable for carrying out a surface treatment reaction while preventing said solid phase from exiting said first chamber; The method of claim 14, further comprising:

16. g) dispensing a gas phase comprising a target number of moles of one or more reactive or non-reactive gases or precursors into the first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the first actuation mechanisms effect delivery of the gas phase under conditions suitable for effecting a surface treatment reaction; and h) subsequently dispensing a target amount, mass or unit volume of flowable article and gas phase environment into said first chamber through one or more first solid phase inlets having two or more actuation mechanisms, wherein a first actuation mechanism effects delivery of a gas-solid composition comprising primarily or entirely a gas phase and a second actuation mechanism effects delivery of a gas-solid composition comprising primarily a solid phase; The method of claim 14, further comprising:

17. i) dispensing a target amount, mass or unit volume of flowable article and gas phase environment into a first chamber through one or more first solid phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects delivery of a gas-solid composition comprising primarily a gas phase and a second actuation mechanism effects delivery of a gas-solid composition comprising primarily a solid phase; and j) synchronously dispensing a gas phase comprising a target number of moles of one or more reactive or non-reactive gases or precursors into said first chamber through one or more first gas phase inlets having one or more actuation mechanisms, where the first actuation mechanisms effect the transport of said gas phase under conditions suitable for carrying out a surface treatment reaction while preventing a solid phase from exiting said first chamber; The method of claim 14, further comprising:

18. k) incorporating a unit for monitoring the signal from one or more pressure measurement sensors and increasing the residence time, the allowable mixing time and / or the interdiffusion rate of the gas and solid phases until a target pressure level is achieved; l) synchronously, asynchronously, sequentially and / or cyclically discharging gas and solid materials through one or more outlets to the transport unit in relation to the main operating mechanism due to each phase; m) characterizing the treated solid material for one or more of surface treatment loading, specific surface area after treatment, or particle size or size distribution after treatment and inputting these into a control system to incorporate machine learning; 18. The method of claim 15, 16 or 17, further comprising one or more of:

19. n) synchronously, asynchronously, sequentially and / or cyclically discharging gas and solid materials through one or more outlets to a transport unit in relation to the main operating mechanism due to each phase; and o) initiating a second surface treatment process by dispensing a target amount, mass or unit volume of flowable article and gas-phase environment into the second chamber through one or more second solid-phase inlets having two or more actuation mechanisms, where a first actuation mechanism effects delivery of a gas-solid composition comprising primarily a gas phase and a second actuation mechanism effects delivery of a gas-solid composition comprising primarily a solid phase; wherein the second surface treatment process in the second reactor chamber utilizes one or more of a different reactive precursor, a different operating pressure, a different operating temperature, a different residence time, or different other process parameters than those used in the first surface treatment process.

18. The method of claim 15, 16 or 17, further comprising:

20. 18. The method of claim 15, 16 or 17, wherein the first surface treatment process comprises one or more of atomic layer deposition, molecular layer deposition, chemical vapor deposition, physical vapor deposition, molecular layering, atomic layer chemical vapor deposition, epitaxial deposition, chemical grafting, atomic layer etching, atomic layer etching, atomic layer combustion or combinations thereof.

21. 18. The method of claim 15, 16 or 17, further comprising a subsystem configured to perform one or more of a flame spray process, a combustion spray process, a plasma spray process, a spray drying process, or a combination thereof.

22. 18. The method of claim 15, 16 or 17, further comprising a subsystem configured to control nominal values ​​and rates of change of one or more of: i) process pressure, ii) process temperature, iii) gas phase composition or flow rate, iv) liquid phase composition or flow rate, v) solute or solvent composition or flow rate, and vi) solid phase composition or flow rate.

23. 18. The method of claim 15, 16 or 17, comprising a subsystem for synthesizing or receiving the article, a subsystem for treating a surface of the article, and a subsystem for applying a coating to the surface of the article.

24. 18. The method of claim 15, 16 or 17 adapted for synchronously processing multiple composite articles, the flowable articles comprising one or more individual particles, powders, extrudates, granules, flowable objects or objects having a maximum dimension less than 125 millimeters in size, and at least 75% of the surface of the composite article is coated or treated upon exiting the system.

25. 18. The method of claim 15, 16 or 17 configured to produce a material suitable for use in a battery, a fuel cell, a catalyst, a capacitor, a pharmaceutical ingredient, a passive electronic component, a solar cell, a 3D printer, a semiconductor device, an integrated circuit, an optoelectronic device, a thermoelectric device, a thermionic device, an electrochemical device, a biomedical device or an electromechanical device.

26. 18. The method of claim 15, 16 or 17 configured to utilise a precursor comprising phosphorus, sulfur, nitrogen, carbon, fluorine, chlorine, bromine or iodine.

27. 27. The method of claim 26, wherein the precursor comprises a phosphide, phosphate, sulfide, sulfate, nitrate, fluoride, chloride, bromide, or iodide.

28. 18. The method of claim 15, 16 or 17, further comprising one or more of a common precursor delivery subsystem, a precursor delivery enhancement subsystem or an effluent treatment or recycling subsystem.

29. 18. The method of claim 15, 16 or 17, wherein the machine learning algorithm calculates the sub-process deviations from modeled data or empirical data using information derived from one or more of direct in-situ signals, indirect in-situ signals, direct external signals, or indirect external signals.

30. a) a first chamber having at least one each of a first solid phase inlet, a first solid phase outlet, a first gas phase inlet, and a first gas phase outlet; b) a second chamber having at least one each of a second solid phase inlet, a second solid phase outlet, a second gas phase inlet, and a second gas phase outlet; c) a first solid phase valve assembly or a solid phase pump assembly in fluid communication with the first solid phase inlet of the first chamber, the first solid phase valve assembly or the solid phase pump assembly having at least two actuation mechanisms; d) a first gas-phase valve assembly or gas-phase pump assembly adjacent to and in fluid communication with the first gas-phase inlet of the first chamber, the first gas-phase valve assembly or gas-phase pump assembly having at least one actuation mechanism; e) a second solid phase valve assembly or solid phase pump assembly in fluid communication with the second solid phase inlet of the second chamber, the second solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms; f) a second gas-phase valve assembly or gas-phase pump assembly adjacent to and in fluid communication with the second gas-phase inlet of the first chamber, the second gas-phase valve assembly or gas-phase pump assembly having at least one actuation mechanism; and g) a common signal hub; 1. An atomic layer deposition apparatus for processing an article, comprising:

31. Each actuation mechanism is configured for bidirectional signal communication with a common signal hub; and i) Instantaneous release; ii) instantaneous closure; iii) controlled release over a programmable time constant; iv) controlled closure over a programmable time constant; v) Enlarging the subcomponents to reduce the conductance through the assembly; vi) contraction of subcomponents to increase conductance through the assembly; vii) Concave or convex deflection of the subcomponent; viii) rotation of the subcomponent collinear with the direction of solid material flow; ix) rotation of the subcomponent tangential to the direction of solid material flow; x) an instantaneous increase in conductance to a position less than the fully open position; xi) an instantaneous decrease in conductance to a position greater than the fully closed position; xii) actuation of a piston or piston-like subcomponent; xiii) actuation to deliver a secondary phase to facilitate aeration, contraction or expansion of the primary phase unit volume; or xiv) actuation mechanisms initiated by electrical application of sine waves, Dirac functions, triangle waves or square waves over one or more programmable time constants; 31. The apparatus of claim 30, comprising:

32. The first chamber and the second chamber each include: a) receiving through each solid phase inlet a solid phase comprising said article having a definable specific surface area; b) distributing through each solid phase outlet a solid phase comprising said article having a treated surface with a definable specific surface area; c) receiving, creating and / or containing, through each gas phase inlet, a gas phase comprising one or more reactive or non-reactive gases or precursors having a definable number of moles or molar flux; and d) distributing through each gas phase outlet a gas phase comprising one or more reactive or non-reactive gases or by-products having a definable number of moles or molar flux; 31. The apparatus of claim 30, configured to:

33. 31. The apparatus of claim 30, wherein the first chamber further comprises a first sensor network including two or more sensors, each sensor in the first sensor network configured to deliver one or more signals to the common signal hub, and the first sensor network configured to monitor a temperature, pressure, and / or composition of a gaseous environment surrounding the item.

34. 31. The apparatus of claim 30, further comprising at least one control system configured to simultaneously send a plurality of signals to and receive a plurality of signals from a common signal hub, said control system configured to provide a controllable unit for regulating material flow throughout the apparatus.

35. a third solid phase valve assembly or solid phase pump assembly in fluid communication with: a) a second solid phase outlet of said second chamber, wherein said third solid phase valve assembly or solid phase pump assembly has at least two actuation mechanisms; and b) a first transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of said article; The apparatus of claim 30, wherein the first transport unit is in bidirectional control signal communication with a signal hub, and one or more actuation mechanisms of the first transport unit are configured to operate synchronously with an actuation mechanism of the third solid phase valve assembly or solid phase pump assembly.

36. 36. The apparatus of claim 35, wherein the outlet of the first transport unit is fluidly connected to a fourth solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms, and one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the fourth solid phase valve assembly or solid phase pump assembly actuation mechanism.

37. The apparatus of claim 35, wherein an actuation mechanism of the first transport unit configured to operate synchronously with an actuation mechanism of the third solid phase valve assembly or solid phase pump assembly and an actuation mechanism of the first transport unit configured to operate synchronously with an actuation mechanism of the fourth solid phase valve assembly or solid phase pump assembly are the same.

38. The apparatus of claim 35, wherein an actuation mechanism of the first transport unit configured to operate synchronously with an actuation mechanism of the third solid phase valve assembly or solid phase pump assembly is different from an actuation mechanism of the first transport unit configured to operate synchronously with an actuation mechanism of the fourth solid phase valve assembly or solid phase pump assembly.

39. a second transport unit in fluid communication with the third solid phase valve assembly or solid phase pump assembly and in parallel with the first transport unit, the second transport unit having one or more actuation mechanisms and configured to control the temperature, pressure and composition of the gaseous environment while regulating the material flow rate of the article; and 36. The apparatus of claim 35, wherein the second transport unit is in bidirectional control signal communication with a signal hub, and one or more actuation mechanisms of the second transport unit are configured to operate synchronously with an actuation mechanism of the third solid phase valve assembly or solid phase pump assembly.

40. 40. The apparatus of claim 39, further configured to adjust the flow rate of the solid phase comprising the article having a treated surface to each transport unit such that a specific surface area flows through each transport unit.

41. a) the first gas phase outlet of the first chamber; and b) a first exhaust return manifold; a third gas-phase valve assembly or gas-phase pump assembly adjacent to, in fluid communication with, and interposed therebetween; 34. The apparatus of claim 33, wherein the third gas phase valve assembly or gas phase pump assembly has at least one actuation mechanism in bidirectional signal communication with the common signal hub and is configured to control the pressure of the gas environment in the first chamber.

42. a) the second gas phase outlet of the second chamber; and b) a second exhaust return manifold; a fourth gas-phase valve assembly or gas-phase pump assembly adjacent to, in fluid communication with, and interposed therebetween; the fourth gas phase valve assembly or gas phase pump assembly having at least one actuation mechanism in bidirectional signal communication with the common signal hub and configured to control a pressure of a gaseous environment in the second chamber; 42. The apparatus of claim 41, wherein at least one actuation mechanism of a fourth gas phase valve assembly or gas phase pump assembly is configured to operate synchronously with at least one actuation mechanism of the third gas phase valve assembly or gas phase pump assembly.

43. and a first precursor delivery system having one or more actuation mechanisms and in fluid communication with the first gas-phase valve assembly or the gas-phase pump assembly, the precursor delivery system comprising: i) an evaporator unit having an external heating mechanism; ii) an evaporator unit having an external cooling mechanism; iii) an evaporator unit having an internal heating mechanism; iv) an evaporator unit having an internal cooling mechanism; v) a precursor volume controller configurable to the particular article and process being performed in said first chamber; vi) a liquid precursor injection pump system; vii) a solid precursor metering system; viii) one or more first capillary nozzles sized for the number of moles of precursor intended for delivery to said first chamber; ix) one or more first expansion tanks each having a definable total internal surface area, where the combined total surface areas of all said first expansion tanks is greater than the total active surface area of ​​the article to be saturated in said first chamber; and x) a first evaporator unit having a rapid thermal processing system; 34. The apparatus of claim 33, comprising:

44. a second precursor delivery system having one or more actuation mechanisms and in fluid communication with the second gas-phase valve assembly or gas-phase pump assembly, the precursor delivery system comprising: i) a second evaporator unit having an external heating mechanism; ii) a second evaporator unit having an external cooling mechanism; iii) a second evaporator unit having an internal heating mechanism; iv) a second evaporator unit having an internal cooling mechanism; v) a second precursor volume controller configurable for a particular article and process to be performed in the second chamber; vi) a second liquid precursor injection pump system; vii) a second solid precursor metering system; viii) one or more second capillary nozzles sized for the number of moles of precursor intended for delivery to the second chamber; ix) one or more second expansion tanks each having a definable total internal surface area, where the combined total surface areas of all the second expansion tanks is greater than a total active surface area of ​​an article to be saturated in the second chamber; x) a second evaporator unit having a rapid thermal processing system; 44. The apparatus of claim 43, wherein at least one actuation mechanism of a first precursor delivery system is synchronously actuated with at least one actuation mechanism of the second precursor delivery system.

45. 31. The apparatus of claim 30, configured to perform one or more of batch, semi-batch, semi-continuous, and continuous atomic layer deposition processes or sub-processes.

46. 31. The apparatus of claim 30, wherein the second chamber is below the first chamber.

47. 37. The apparatus of claim 36, wherein at least a portion of the fourth solid valve assembly or pump assembly is disposed in the same horizontal plane as at least a portion of the first solid valve assembly or solid phase pump assembly.

48. 48. The apparatus of claim 47, wherein an actuation mechanism of the fourth solid phase valve assembly or pump assembly is configured to operate synchronously with an actuation mechanism of the first solid phase valve assembly or solid phase pump assembly.

49. The apparatus of claim 35, wherein the outlet of the first transport unit is fluidly connected to the first solid phase valve assembly or solid phase pump assembly having at least two actuation mechanisms, and one or more actuation mechanisms of the first transport unit are configured to operate synchronously with the first solid phase valve assembly or solid phase pump assembly actuation mechanism.

50. 31. The apparatus of claim 30, wherein the article is selected from the group consisting of particles, powders, and porous supports.

51. 31. The apparatus of claim 30, wherein the apparatus is configured to operate at a minimum pressure of about 0.1 Torr.

52. 31. The apparatus of claim 30, wherein the apparatus is configured to accommodate a pressure drop of up to about 1,500 Torr.

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