System and method for producing printed matter - Patent application

Abstract

To provide a system and method for forming a product with different size particles.SOLUTION: A system for forming a product with different size particles includes at least one print head region and at least one processor. The at least one print head region is configured to retain: a first group of print heads 106 configurable to additively print at least a first portion of a product with a first material having a first average particle size; and a second group of print heads 106 configurable to additively print at least a second portion of the product with a second material having a second average particle size. The at least one processor is configured to receive information reflective of desired properties of the product and regulate the first group of print heads 106 and the second group of print heads 106 to unevenly distribute the first material and the second material in a layer-by-layer basis to impart differing structural characteristics to differing portions of the product based on the information reflective of the desired properties of the product.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS] This application is a continuation of U.S. Provisional Patent Application No. 62 / 487,670, filed April 20, 2017. No. 6,313,535, filed on Oct. 13, 2003, which claims the benefit of priority to US Pat. No. 6,313,535, filed on Oct. 13, 2003, which is incorporated herein by reference.

[0002] The present disclosure generally relates to a system for forming a product having particles of different sizes. In one embodiment, the system prints different sections or parts of the product in a sequential order. a print head region holding one or more print heads configured to print a The present disclosure also provides a method for adjusting the head of a system. The present invention relates to a method of manufacturing a product, such as by using a stem. [Background technology]

[0003] The three-dimensional (3D) inkjet printing process is a process similar to direct metal laser sintering or selective laser sintering. These are considered additive manufacturing processes such as DMLS and SLS (selective laser sintering, respectively). The inkjet printing process is used to print plastic, metal, or ceramic objects. Unlike DMLS and SLS, metals or In this case, the ceramic body is considered a "green" body that requires a final sintering step. Typically, metal or ceramic 3D inks are used because their mechanical properties are inferior to fully sintered parts. Jet printing requires the use of at least two materials: a model material and a support material. The model material and the support material are ink-jettable inks. The model material is The support material is used to form the desired object for at least a portion of the object. These are used to create support structures that can be used during printing or when the model is self-supporting. It is configured to support an object until it reaches an adequate mechanical strength to support the object. If the print contains channels or other voids, or needs to be printed at a negative angle, In some cases, the use of support materials is particularly desirable. Once the model has reached the free-standing stage, the support structure It will be deleted.

[0004] One of the fundamental challenges of 3D printing is to minimize cross-contamination of support materials within a model. This provides the necessary support for the printed model before it reaches the self-supporting stage, and The development of a support material that allows printing of support structures that can then be removed. Therefore, the support material must be compatible with the various properties of the model material. For example, according to one aspect of the present disclosure, as described in more detail below, the sintering temperature of the support structure It is important that the sintering temperature is higher than the sintering temperature of the model material.

[0005] The support material is removed in a post-printing process, either immediately after printing or after sintering. The removal of the support may be accomplished chemically, mechanically, or thermally. Regardless of the method used for removal, the printed model is transformed into a solid metal or ceramic piece. To convert it, some post-printing processing steps are required. After the printing stage, and after the model is automatically One problem associated with removing the support before it reaches the establishment stage is that the removal process At this stage, the printed part is The attached parts can easily be damaged.

[0006] Combinations of model and support materials for inkjet printing and the methods disclosed herein Such a method of combining materials addresses the shortcomings of the prior art. Such a method is intended to overcome one or more of the problems described above and / or other problems of the prior art. In particular, the present disclosure provides a novel and inventive method for producing such inks. Adjust the parameters between the ink and the ink to help manufacture products by inkjet printing? , improving the outcome of the final printed model, or both. Summary of the Invention [Means for solving the problem]

[0007] In part to address the aforementioned needs, the present disclosure relates to a system for forming a product. In one embodiment, the system comprises distributing at least a first portion of the product to a first average particle size. a first printhead group configurable to print with a first material; The first average particle size is a first average particle size. The system described herein is selected to provide a second sintering characteristic of the product. a second printing device that can be configured to print the portion of the second material having a second average particle size. The second average grain size is selected to impart a second sintering characteristic. do.

[0008] The systems described herein also include receiving information reflecting desired characteristics of the product, Adjusting the first printhead group and the second printhead group to obtain a desired printhead density for the product. To give different parts of the product different properties based on information reflecting the properties. at least one layer configured to dispense the first material and the second material in a layer-by-layer manner; Contains one processor.

[0009] The present disclosure also relates to inkjet printing, such as by using the disclosed system. In one embodiment, the method includes jetting an object material to forming a product structure having a first sintering temperature. Prior to that, the method further includes jetting a support material including particles to form a support structure. , where the support structure is jetted to support the product structure. In one embodiment, the support material The sintering temperature of the object material is higher than that of the object material. The bodies together constitute a green part. The method comprises heating the green part to above a first sintering temperature and By heating to a temperature below the second sintering temperature, the injection support is not substantially sintered. and at least partially sintering the injected object and removing substantially all of the at least partially sintered object. and removing the green support.

[0010] Apart from the above-mentioned subject matter, the present disclosure includes many other features as described below. Both the above and following descriptions are merely illustrative.

[0011] The accompanying drawings are incorporated in and constitute a part of this specification. [Brief description of the drawings]

[0012] [Figure 1] 1 illustrates an example of an additive manufacturing apparatus according to the present disclosure.

[0013] [Figure 2A-F]An example of an additive manufacturing process according to an embodiment of the present disclosure is shown, which includes the spraying of a layer of powder (FIG. 2A); the ink-jetting of nano-powder in a desired model area (FIG. 2B); and the consolidation of the model area (FIG. 2C). The steps of applying an additional layer of sprayed coarse powder are then repeated (FIG. 2E) and the ink-jetting of nano-powder (FIG. 2F).

[0014] [Diagram 3] 1 illustrates a printer head assembly according to an embodiment of the present disclosure that includes multiple printheads to enable printing of colored inorganics by inkjet printing.

[0015] [Figure 4A-C] FIG. 4A shows an ink dispersion according to one embodiment of the present disclosure that includes colorant particles such as pigments or pigments mixed with structural particles such as zirconia (FIG. 4B) or embedded in zirconia particles (FIG. 4C). FIG. 4C shows the structural particles removed.

[0016] [Diagram 5] 1 shows a colored cube having a white layer underneath the color layer made according to an embodiment of the present disclosure.

[0017] [Figure 6A] 1 is a graph showing sintering temperature versus grain size of materials. [Figure 6B] 1 is a graph showing relative density versus sintering temperature for four sintering stages associated with powder materials.

[0018] [Figure 7] FIG. 1 is a ternary phase diagram of components used to make a SiO2-supported ink according to the present disclosure.

[0019] [Figure 8] 1 shows a schematic of an in situ laser system with a model and supporting material.

[0020] [Figure 9A-B]9A and 9B are schematic diagrams showing particulate material before (FIG. 9A) and after (FIG. 9B) dispersant evaporation. FIG. 9A is a schematic diagram showing the particle wrapped with dispersant molecules at low temperature. FIG. 9B is a schematic diagram showing the particle remaining after loss of dispersant molecules at high temperature but below sintering.

[0021] [Figure 10A-D] 10A-10D are schematic diagrams showing the packing density of powders with various shapes and sizes, specifically, a mono-size dispersion (FIG. 10A), a multi-size dispersion (FIG. 10B), a mono-size and multi-size dispersion (FIG. 10C), and the mono-size and multi-size dispersion of FIG. 5C after heat treatment (FIG. 10D).

[0022] [Figure 11A-F] FIG. 13 is a schematic diagram illustrating separation and deformation of a model part associated with high stresses and strains due to differential shrinkage between support and model materials during sintering.

[0023] [Figure 12A-B] 12A and 12B show objects printed with different materials according to the present disclosure: Fig. 12A shows a coating on a bulk material, and Fig. 12B shows a coating on an impregnation layer on the bulk material.

[0024] [Figure 13A-B] 1 illustrates an object constructed of a mixture of materials according to the present disclosure.

[0025] [Figure 14] FIG. 1 is a flow diagram for producing a composite object according to the present disclosure by infiltrating a model material with a support material. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] This disclosure generally relates to a method for manufacturing a model inkjet printed product. The present invention relates to adjusting the parameters between the model ink and the supporting ink. Several integrated techniques and systems are disclosed for beneficially adjusting parameters between These include: i) The model is sintered before the support to facilitate removal of the support after sintering. Adjust the sintering temperature. As explained in more detail below, this can be achieved by adjusting the material selection, particle size, and , particle distribution, or a combination thereof. ii) Controlling shrinkage between the model and the support structure to reduce the time from printing to the green stage and brown stage This avoids distortion or cracking of the model during the temperature range throughout the molding process, sintering, and final sintering. iii) Selecting materials or using additives that will help achieve this result Reduce cross-contamination between the controller and supporting structures. iv) Control the particle size of both the model ink and the support ink to ensure uniform ink flow in both the model and support areas. It improves printing speed by covering the areas quickly and efficiently.

[0027] The following is a general description of the various embodiments described herein, and in particular, Printers, printing systems, inks and ink systems, and other related materials used to manufacture products Methods of using such systems and / or inks, and products made therefrom. Reference will now be made in detail to these foregoing embodiments, which are implemented in accordance with the present disclosure. Examples are illustrated in the accompanying drawings. Wherever possible, references to the same or like parts will be used throughout the drawings. The same reference numbers are used for each.

[0028] [printer] In one embodiment, an additive manufacturing device is disclosed. The term "material creation" refers to the process of creating a digital model by laying down successive layers of material until an object is created. FIG. 1 is a block diagram of a device or system for generating an object from a liquid. An example of an additive manufacturing device 100 in which various implementations as will be described may be implemented is shown in FIG. As such, the additive manufacturing device 100 includes a printing area 102, at least one print head 106, and The print head holder 104 supports the print head 106 and the ink reservoir 11. 0, at least one conduit 108 interconnecting the energy source 112, and the cooling fan 114. , a shield 116 , a leveling device 118 , and a controller 120 .

[0029] The print area 102 serves as a base to support an object to be built in an additive manufacturing process. The term “print area” may be used to refer to the area of ​​material dispensed from the additive manufacturing device 100. "Print tray" and "print tape" include areas with a rigid surface capable of holding multiple layers of The term "printable" may also be used interchangeably in this disclosure with respect to the printed area. In one embodiment, the print area 102 can include, for example, a thermally conductive material and The print area 102 may include a metal tray. 102 is a liquid ink for assisting in solidification of a recently printed layer or for removing at least one of the ink liquid components. To facilitate some evaporation, the object may be heated to a required object temperature. For example, the print area 102 may be made of wood, plastic, or other suitable material. In both embodiments, the print area 10 may include a dielectric material such as a plastic, or an insulating ceramic. 2. Maintain the temperature of the object and heat the recently printed layer with, for example, halogen lamps, IR lamps, Energy sources such as lamps, UV lamps, lasers, flash lamps, or microwave sources By using source 112, this is achieved by direct thermal radiation from above.

[0030] In one embodiment, the print zone 102 is attached to a tray holder (or "chuck"). The tray holder may be a print tray that can be heated as required. The tray holder may include any suitable device, including a vacuum or clipping jig. A rigid, flat, heat-conducting surface to which the tray can be attached by any means (including heating means under the cover). Alternatively, the holder may include an exposed heating element. It may include a holding frame surrounding the tray (e.g., radiant lamps that directly heat the tray). In one embodiment, the print tray is replaceable. For example, when printing is finished, the operator The printer will remove the tray with the prints from the printer and insert a clean tray into the printer. You can then attach the printer and start a new print session.

[0031] In one embodiment, the tray must be rigid. This is because the tray cannot be moved from the tray holder. This is necessary to prevent bending when removing the tray from the tray holder. It may be flat. This allows for good attachment between the tray holder surface and the tray. and is desirable to ensure good alignment between the print and a straight leveling device. The tray should be thermally conductive and not too heavy. According to one embodiment, the tray It is made of aluminum and has a thickness ranging from about 3 to 12 mm.

[0032] The term "printing area" should not be confused with the term "printing surface". At the beginning of the printing process, the print area 102 is the surface onto which the new layer is printed. This is possible because the first layer is printed directly on top of it. Every layer (e.g. second layer) is printed on top of the previously deposited layer. In the case of a 3-layer, the first layer is the printed surface, in the case of a 3-layer, the second layer is the printed surface, etc. In the example shown in Figure 1 In the figure, printing surface 122 is a previously deposited layer. A new layer 124 is deposited on top of printing surface 122. The new layer 124 is the layer currently being printed along the Z direction during every printing pass. This is also called the "upper layer" or "latest layer".

[0033] According to aspects of the disclosure described herein, the model is printed on a support, the support being a rigid stability of the part, a suitable interface with the supporting part material (model), and ease of separation from it According to another aspect, the support structure is also removable from the tray. According to one embodiment, a support structure is provided between the component and the tray. Please note that the tray is not fully assembled, so that the printed parts can be easily removed from the tray. Therefore, only a few of the support layers (e.g., 1 to 10) are deposited in a layer that is different from the layers that are subsequently deposited. In one embodiment, these few layers include only the support material.

[0034] In other embodiments, a few layers may be formed using a particular mixture or combination of support material and model material. In one embodiment, the model material may be added to the pillar structure. The mixture of a layer may differ from the mixture of the layer above, both of which are mixtures of support structures near the part. A more detailed description of this structure is incorporated herein by reference. No. 15 / 029,815 filed on Oct. 23, 2003.

[0035] Allows for even and consistent cooling of prints to aid in the integrity of the final print In one embodiment, this involves insulated cooling until the printed object reaches the desired temperature. By holding the print tray with the newly printed objects in a cool environment such as a box. This can be done.

[0036] Consistent with an embodiment of the present disclosure, reference is again made to FIG. 1. As shown in FIG. 00 maintains at least one printhead 106 spaced apart from the printing surface 122. The term "print head holder" may include a print head holder 104 for holding the print head. At least one print head 106 is positioned at a fixed distance or print area from the printing surface 122. Any structure suitable for holding the area 102 at a varying distance from the additive manufacturing process. involves laying down successive layers of material, so that the height of the object grows gradually. After each layer is laid down, the print area 102 is connected to at least one printhead 106. Shift slightly lower in the Z direction to maintain a fixed distance between the print surface 122. In an embodiment, after each layer is placed, the print head holder 104 is shifted slightly higher in the Z direction. 10 to maintain a fixed distance between the at least one printhead 106 and the printing surface 122. In one example, the fixed distance between the print head 106 and the printing surface 122 is 0.5 m. In another alternative embodiment, after each layer is laid down, the print area is 102 moves a little lower in the Z direction, and the print head holder 104 moves a little higher in the Z direction. 10 to maintain a fixed distance between the at least one printhead 106 and the printing surface 122. For simplicity, the following description assumes that the print head is rotated while the print tray is stationary. However, in an alternative embodiment, the print tray may be The actuator 104 may be configured to move under the steering head 106 .

[0037] According to some embodiments, the printhead holder 104 holds a single printhead. The printer may support a print head 106 or multiple print heads 106. The term refers to a device that is organized into a linear array or plate and generally manufactured together as a unit. When the print head 106 is connected to the additive manufacturing device 100, multiple nozzles are The nozzles are arranged to dispense ink from an ink reservoir 110 to build up the article layer by layer. At least one print head 106 is configured to dispense the first model material. a first group of nozzles for dispensing a second model material different from the first model material; The print head may include a plurality of nozzles, including a second group of nozzles. , characterized by the ability to contain and manage multiple sets of nozzles. However, the model Each printhead is supplied with one type of ink, regardless of the substrate. The term "object" is used to describe the combination of the model and the supporting structure. In one embodiment, a model is printed using a first material and a second material is used. A typical case for this embodiment is when the desired object is two In another embodiment, the first material is a material that produces the desired object. The first material is the object material used to print the object, and the second material is a support material used temporarily during printing. The print head 106 is a material that supports, for example, the "negative" sloping wall of an object. scans the new layer 124 in an X direction substantially perpendicular to the longitudinal axis Y of the new layer 124 Each object consists of thousands of printed layers, so thousands of cycles are usually required. If each cycle involves multiple prints from multiple printheads 106, the cycle The number of parts can be reduced from thousands to hundreds or even less. Multiple objects may be generated in the same run. In one embodiment, the nozzles may have different sizes. Different print heads 106 can be used for different print materials. For example, a first print head can be used to dispense the object material and a second print head can be used to dispense the object material. As another example, a first print head may be used to dispense the support material. The printhead has nozzles of a first size, and the second printhead has nozzles of a second size different from the first size. The nozzle may have a size of

[0038] In some embodiments, the additive manufacturing device 100 includes an inkjet printer 106. The at least one conduit 108 may be interconnected with a server 110. " generally refers to a body having a passage for the transport of a liquid or gas. At least one The conduit 108 allows relative motion between the print head 106 and the ink reservoir 110. In some embodiments, the at least one conduit 1 may be flexible. 08 interconnects the ink reservoir 110 to the printhead 106 to form a printhead A supply conduit that supplies ink to the printhead 106 and ink that has not been discharged from the printhead 106 The print head 106 is configured to circulate at least a portion of the ink to the ink reservoir 110. and a return conduit (not shown) interconnecting the ink reservoir 110 with the ink reservoir 110. The ink reservoir is configured to store ink before it is delivered to the print head 106. In some embodiments, the ink reservoir 110 includes one or more tank and delivers ultrasonic or shock waves to the ink to prevent agglomeration of solid particles in the ink. or, if agglomerates are already present in the ink, an ultrasonic vein configured to break up the agglomerates. In addition, the additive manufacturing device 100 may be controlled by the controller 120. and arranged along at least one conduit 108 to receive at least one printed Within the head 106, at least one conduit 108, and / or the ink reservoir 110 It may also include a number of valves (not shown) to control the pressure. A detailed description is provided in U.S. Patent Application Serial No. 15 / 921,279, which is incorporated herein by reference. It is written.

[0039] A single printhead dispensing a single ink, and multiple printers for a particular ink Typically, these printers use a print head, but they also use multi-nozzle arrays that dispense different inks. It is also possible to use a single inkjet head. Each nozzle array has a different nozzle number.

[0040] [Third printhead used in inkjet printing additives] In various embodiments, the properties of the final object, such as the color or mechanical properties of the print, may be modified. To improve the printability, one or more additive materials can be added to the ink during the final step, such as the printing or sintering step. It may aid in the processing of the final product or may be printed from a separate head. There is at least one separate head dedicated to the dispensing of additives, either alone or dissolved in a suitable solvent. As used herein, this refers to printing using two separate printheads. Used to deposit material other than the printed model or support, and is called a "third print head" These are called "additive heads" or "additive heads." For more information on the types of additives, see below. The additive is printed with a separate head, eliminating the need to worry about targets that may be incompatible with the additive. There is no problem with additives dissolving in the ink. In addition, the additive head allows for Different amounts of additive can be distributed in different zones.

[0041] Printer Heat Source According to some embodiments, as shown in FIG. 1, the disclosed additive manufacturing apparatus 100 may include an energy source, such as energy source 112. The term "energy source" is configured to provide energy to an object printed by the additive manufacturing apparatus 100. For example, any device that applies energy in the form of radiation or heat to the new layer 124. to evaporate the dispersant material and other organic additives, and optionally to form at least In one example, the energy source 112 can initiate partial sintering of the new layer 12. 4. A small light source such as a lamp or laser configured to illuminate or scan a line along A spot-sized energy source is included to perform in-situ degassing of the newly formed layer 124. In another example, the energy The heat source 112 is adapted to initiate partial or complete in-situ debinding or sintering. 124, may include a flash lamp configured to cover the area of ​​the newly formed layer 124. According to this aspect of the disclosure, the energy source 112 is configured to: For this purpose, the ink may be selectively sintered only in the model ink. The method involves irradiating the new layer 124 with a wavelength that is more absorbed by the model ink than by the support ink. and / or by using pigments that increase the energy absorption at the irradiated wavelength. This can be achieved by adding

[0042] In a first embodiment, the energy source 112 is integrated into the print zone 102 to generate a warm tray. If the print is heated from below, the heat is constantly 24, and because of the heat flow resistance of the material, the bottom of the object (along the Z axis) becomes hotter and the A temperature gradient is created where the upper surface of the body is cooler. The temperature of the warm tray keeps the temperature of the upper layer constant. The height of the object being printed is controlled according to its virtual height to keep it constant. The disadvantages of such a procedure are However, heating the bottom layer to high temperatures can adversely affect organic molecules such as those found in dispersants and other additives. Another disadvantage is that it can be subjected to excessive heat, which can cause the organic matter to break down into carbon and other residues. Residual liquid remaining in the lower layer evaporates, creating high gas pressures that can cause the material to crumble or crack. Generally, creating a temperature difference between layers after drying can cause This is not recommended as cracks may occur due to different thermal expansion of the materials.

[0043] In a second embodiment shown in FIG. 1, a radiant energy source 112 is disposed above the object to be printed. Direct heating by the energy source 112 maintains a constant temperature of the new layer 124. The energy source 112 is located beside the print head 106. The porous layer below the temporary final layer can generate thermal radiation, e.g. electromagnetic radiation. The porous material absorbs some of the liquid carrier, making it difficult to dry the final layer layer by layer. Therefore, the intensity of the heat source must increase as a function of the intermediate height Z of the final layer. Alternatively, the heat source moves slowly along the X or Y direction as a function of the object height. It is necessary to.

[0044] In a third embodiment, the energy source 112 directs a stream of hot air at an angle to the new layer 124. The use of hot air can include an opening configured to blow hot air onto the new layer 124. Not only does it increase the temperature of the new layer, but it also reduces the partial pressure of the evaporated carrier liquid above the last layer, Evaporation of the liquid carrier (and possibly dispersants and other organic materials) from layer 124. Further, any combination of the first, second and third embodiments may be used to , heating and / or evaporation performance can be maximized.

[0045] cooling device As mentioned above, the heating of the new layer 124 can be part of an additive manufacturing process. In some embodiments, the remainder of the print is maintained at the same temperature as the new layer 124. Therefore, the additive manufacturing apparatus 100 should not store any data stored in the recently printed layer. A cooling fan 114 may be included to dissipate heat to the surrounding air. One reason for cooling the layer is that the ink droplets must be heated to a temperature (e.g., 30° C.) higher than the boiling point of the carrier liquid. When it reaches a surface at a temperature it may explode rather than attach to the surface (e.g. water (When the droplet reaches a surface at 120°C). The rest of the object is then coated with a new layer 1 It is not necessary to maintain the temperature at the same temperature as that of 24, but only to maintain a constant uniform temperature. For example, the previously printed layer may be maintained at a relatively low temperature using a cooling fan 114. In this case (e.g., about 230° C.), the new layer 124 is heated to a temperature above the boiling temperature of the carrier liquid. The new layer 124 may be heated to approximately 500° C. (eg, the new layer 124 may be heated to approximately 500° C.).

[0046] Heat shield In some embodiments, the additive manufacturing apparatus 100 also includes a thermal buffer, such as a shield 116. In the context of this disclosure, a heat shield may partially cover the nozzle array. This refers to a plate with an opening that allows easy printing from the nozzle to the printing area. Because the temperature is relatively high (e.g., about 230°C) compared to the The head 106 should be protected from heat and smoke emanating from the print area. In this case, the shield 116 is kept at a relatively low temperature (e.g., 10 to 200°C) compared to the temperature of the object being printed. 50° C.) to provide a thermal barrier between the printhead 106 and the print.

[0047] Leveling Device Due to variations in process conditions, including different jetting powers for different nozzles, the new layer 124 may be completely As a result of the surface tension of the liquid, the edges of the layers may not be perfectly sharp. Thus, the additive manufacturing apparatus 100 may planarize the new layer 124 and / or A leveling device 118 may also be included to level one or more edges of the thin layer 124. In some embodiments, the leveling device 118 may be a vertical or horizontal grinding roller or cutting roller. In another embodiment, the leveling device 118 may include a leveling device. The printhead may include a dust pump and dust filter 126 for sucking in the printhead output. During the process, the leveling device 118 moves the layer 124 over the new layer 124 while the layer is being dispensed and solidified. In one example, the leveling device 118 may operate at approximately 5% to 20% of the material of the top layer height. In some embodiments, the leveling device 118 may peel off the carrier. After the ink liquid has evaporated and the new layer 124 has at least partially dried and become solid, Contact with the

[0048] Control and Processing Unit The described additive manufacturing apparatus 100 is capable of generating any object from a digital model. To do so, the additive manufacturing apparatus 100 includes a controller for controlling the operation of the different printing components. In some embodiments, the controller 120 may include a processing device. In this case, the controller 120 is configured to determine how to operate the additive manufacturing device 100. The at least one processor may include a processor for performing a process for detecting an input. The physical device may comprise any physical device having electrical circuits that perform logical operations using at least one At least one processor may contain one or more integrated circuits, microchips, or microcontrollers. All or part of the controller, microprocessor, central processing unit (CPU), graphics Processing Unit (GPU), Digital Signal Processor (DSP), Field Programmable Gauge (FPGA), or other circuitry suitable for executing instructions or performing logical operations. The instructions executed by the at least one processor may be, for example, a control Preloaded into memory integrated with or embedded in the controller 120 The memory may be stored in a random access memory or in a separate memory. RAM, read-only memory (ROM), hard disk, optical disk, magnetic media memory, flash memory, other permanent memory, fixed memory, volatile memory, or instructions Other mechanisms for preservation may be included.

[0049] In some embodiments, the memory stores information representative of a product associated with the visual code. In some embodiments, the controller 120 is configured to store multiple processes. Each processor may have a similar structure and may be electrically For example, multiple processors may have different structures that are dynamically connected or disconnected. , which may be separate circuits or integrated into a single circuit. When performing the above steps, the processors may be configured to operate independently or in cooperation. The processors may be electrically, magnetically, optically, acoustically, mechanically, or otherwise capable of interacting with each other. The components may be coupled by other means that enable the

[0050] Printed Sensors The described additive manufacturing apparatus 100 performs a series of steps to ensure that the printing process proceeds as planned. For example, the additive manufacturing device 100 may include one or more sensors for detecting an image. An imager, such as sensor 128, may also be included. The term "sensor" refers to a device that detects optical signals in the near infrared, infrared, visible, and ultraviolet spectrum and converts them into electrical signals. The electrical signal is then converted into an image or video stream based on the detected signal. The term "image data" refers to a method for forming a ream (i.e., image data). is any form of data obtained from optical signals in the near infrared, infrared, visible, and ultraviolet spectrum. Examples of image sensors include semiconductor charge-coupled devices (CCDs), complementary metal oxide semiconductor (CMOS) Active metal oxide semiconductor (CMOS) or N-type metal oxide semiconductor (NMOS, live MOS) In some cases, the image sensor 128 may include a pixel sensor. 2.

[0051] The following are the sintering temperature, the shrinkage between the model and the support structure, and the interaction between the model and the support structure. The inventors will improve the final printed model by including compositions and methods for controlling contamination. Compositions and methods discovered to achieve this are described herein.

[0052] [Ink composition] The additive manufacturing device shown in FIG. 1 (100) is configured to print multiple types of inks. The term "ink" refers to the deposition of ink in a desired pattern on the printing surface 122. The term "ink" therefore includes any fluid intended to be a model, support, or or, if present, a third printhead, which contains material for printing additives from the third printhead. These different inks are called "model materials", "support materials", "additive manufacturing materials" and "printing materials". and "printing fluid." These terms are used interchangeably herein. Used for.

[0053] Printing multiple model inks on a given part is a different story than jet printing vs. selective laser printing. This combination is a unique and very important attribute of solid-state printing. Either as a homogenous mix (where you actually get a homogenous mix of the ingredients) or as a mixed mix. This is done on a macroscopic scale by creating different regions of a part that contain different materials. In composite printing, the printer uses multiple IDS (ink supply systems) and multiple heads. There is at least one head for each material to be jetted. This approach is incorporated herein by reference. Included in the literature [PCT_Friedman_3D Particle Printing g_4619 / 20_Chapter 17]. Consistent with this disclosure, Some examples of suitable inks may include the following attributes:

[0054] Particle size, material and shape The inks described herein can be used with any of a variety of metals (e.g., iron, stainless steel, copper, silver, gold, titanium, etc.). ), ceramic materials, metal oxides, oxides (e.g., SiO 2 , TiO 2 , ZrO 2 , BiO 2 ), metal carbonates, metal carbides, carbides (e.g., WC, Al 4 C 3 , TiC ), metal alloys (e.g., stainless steel, titanium, Ti64), nitrides, inorganic salts, polymers Any desired mixture of particles, including but not limited to, combinations thereof in a carrier liquid. In one embodiment, the solid particles may include a dispersion of silicon, aluminum, or other materials. nium, titanium, yttrium, cobalt, copper, iron, zinc, magnesium, zirconia, Includes metals and metalloids selected from combinations or alloys thereof.

[0055] In various embodiments, the particles maintain the required spatial resolution during printing or (after sintering) Micron size to maintain required material properties or meet dispensing head limitations (about 0.5 μm to about 50 μm) or nano-sized (about 5 to about 500 nm), e.g. For example, if the dispensing printhead contains a nozzle with a diameter of 30 μm, the particle size will be 2 μm. In the context of this disclosure, the term "model material" or "model illustration" is used. The term "ink" generally refers to the solid material or particles used to build a model. whereas "support material" or "support ink" generally refers to the material that is attached to the model, usually temporarily. This refers to the material or solid particles used to construct the support structure to which the material is attached.

[0056] Particle size is important for high print resolution. Generally, particle size is determined by the print image map. The size of the pixel should not exceed approximately 1 / 4 of the pixel size of the screen, but some clumping (approximately 10 particles) is permitted. Therefore, it is recommended that the particle size not exceed 1 / 10 pixel size. For example, if the pixel size is 15 microns, the particles need to be smaller than 1.5 microns. This ratio needs to be consistent with other pixel and grain sizes.

[0057] In one embodiment, the solid particles in the model typically have a continuous, multimodal particle size distribution. However, in special cases the distribution may be discrete, such as a bimodal distribution. In the case of a support material, the solid particles have a unimodal particle size distribution. Such a distribution is called a multimodal Better flow through the piping and head (less head clogging) compared to The only benefit is a reduced tendency to sinter. The average particle diameter is determined using standard measurement techniques. For example, in one embodiment, the average Particle size was determined by examination of dry model powders using a scanning electron microscope (SEM). The average particle diameter may be the average of the diameters of randomly selected particles, where particle diameter is the Feret diameter measured in a fixed direction.

[0058] Adjusting particle size to increase printing speed In one embodiment, we have developed a high speed printing block that covers both the model and support areas. The imaging technique is characterized by the printing of a volume, followed by the printing of small nanoparticles in a binder only in the model areas. To achieve this, large and inexpensive particles (1-5 μm) are used. As shown in Figure 2, smaller nano-sized ink is ejected (Figure 2B ) Using a combination of large micron-sized powders (Figure 2A) allows for faster and more cost-effective In this embodiment, we have found that it is possible to effectively print large, inexpensive 1 to 5 μm Using particles, both the model and support areas can be printed quickly, followed by the model area. Only small nanoparticles in a binder can be jetted.

[0059] Referring to FIG. 2A, the first step is to use, for example, a larger nozzle, air, fluid or via an inkjet printhead with electrospray or via a wire rod connector. A dispersion of 1-5 μm sized powder is sprayed onto the surface by coating or another method. At this stage, as shown in Figure 2B, In this method, the tray is coated with a dispersion of powder and then the dispersion is evaporated. After that, the nano-sized powder is inkjet printed onto the model, as shown in Figure 2C. This is followed by heat curing with a binder or partial sintering, which can be in situ. The deposition step is followed by a curing step as shown in FIG. 2D according to the process. Repeat as many times as necessary to obtain the desired thickness and profile, as shown in FIG. 2F. will be returned.

[0060] According to one embodiment, a dispersion of powder having a size of 1 to 5 μm ... The dispersion of small nanoparticles may contain the same materials as small nanoparticle inks. A few non-limiting examples: As large and small particles, 316 stainless steel, silica, alloys, zirconia, and other It may be a metal or ceramic material. According to this embodiment, the debinding step During the pre-sintering step or the sintering step, small particles tend to generate necking, so the model Green or brown areas are created in the area to provide some hardening or other mechanical properties As a result, the model regions are free-standing, whereas the large particle-only supported regions are more detachable. According to another embodiment, the large size particles and the small size particles are They may be of different materials. One non-limiting example is large sized zirconia grains. According to another non-limiting example, a large sacrificial nanoparticle is The small size particles can be WC, and the small size particles can be stainless steel or copper. good.

[0061] Supporting Ink The support materials described herein remain an integral part of the finished product, even when forming a multi-component material. Alternatively, once an object has been printed, it can be subjected to post-printing processes, typically involving a heat treatment such as sintering. The support material is removed prior to printing. Alternatively, the support structure printed with the support ink may be removed prior to printing. In these cases, the support structure of the supporting ink may remain on the printed object during subsequent processing. The structure must remain soft and / or brittle enough to be removable after the sintering process. The metal composition of the final object should be the same or close to that of the initial ink, but with some In this embodiment, the starting composition may differ due to loss of some material during the printing process. be.

[0062] A detailed description of the support material is given in WO2015056232A1 (patent application no. PCT / IB2 No. 014 / 065402, which is incorporated herein by reference. The support ink according to the embodiments disclosed herein may be, for example, a carrier binder as described herein. It includes chemicals that include solid particles dispersed in a vehicle, dispersant and additives.

[0063] Solid particles for supporting inks In one embodiment, the support material comprises one or more types of material and / or particle sizes. For example, in one embodiment, one or more types of particles are mixed together. The particle size is given by diameter, but not specifically. , the particle diameters range from the nanometer scale, e.g., from about 10 nm to less than 500 nm, For example, 400 nm, 300 nm, submicron (about 0.5 μm to about 1 μm), It is up to 50 μm in diameter and serves the general function of support. The compound is miscible or at least partially soluble in water, basic, or acidic aqueous solutions.

[0064] In various embodiments, the solid particles of the support material have a particle size of at least 1.0 micron. at least 2.0 microns, at least 10.0 microns, at least 20.0 microns, In one embodiment, the solid particles of the support material have a particle size of 1.0 micron or less. The range is from 1.0 microns to 50 microns, such as from 1.0 microns to 5.0 microns. The particle size of the solid material in the model ink is 0.4 microns or less, 0.3 microns or less. Below 0.5 microns, such as below 0.2 microns, below 0.1 microns, 10 nm, etc. In one embodiment, the model particles have a particle size ranging from 10 nm to 0.5 microns.

[0065] In various embodiments, the solid particles may be one or more metal or ceramic materials, oxides, Such oxides and oxides which can be used as solid particles include carbides, nitrides, or carbonates. Non-limiting examples of carbonates include silicon oxide (silica -SiO 2 ), aluminum oxide ( Al 2 O 3 -alumina), titanium oxide (TiO 2 -titania), yttrium oxide (Y 2 O 3 -yttria), cobalt oxide (CoO), copper oxide (CuO), iron oxide ( Fe 2 O 3 ), zinc oxide (ZnO), magnesium oxide (MgO), zirconium oxide ( ZrO 2 -zirconia), iron carbonate (FeCO 3 ), and organic or inorganic salts.

[0066] In one embodiment, the support material is FeCO 3 Contains particles. FeCO 3 500~700℃ Iron oxide and CO at a temperature of 2 The support structure of the model ink containing iron. To provide FeCO 3 The powder is dispersed in a solution and then applied to an inkjet printhead. This allows the formation of a jettable ink that can be deposited onto a substrate from the FeCO 3 The particles are commercially available. It can be dispersed in a carrier liquid using a powder. 3 Other benefits associated with the use of The main advantage of iron oxide is that it is easily removed and becomes smaller during its chemical decomposition into iron. Iron oxide contaminants in the model are converted to metallic iron during sintering. It is possible to manufacture model pieces with mechanical properties that are not subject to stress.

[0067] Salt Support In another embodiment, the support may be made of other materials or particles that may interfere with the sintering of the support particles, such as sintered particles. The same model particles are mixed with alkali or organic or inorganic salts. Advantages of this support material The problem is that some of the residual support material that inadvertently contaminates the model contains the same model material. Salt-based support materials have a high water solubility for each salt, making them easy to wash off with water. In fact, if the removal of the support is done before sintering (green or brown), color stage), the parts are porous so water flows throughout the model material (not just on the outer surface) , flushing out contaminating salts within the bulk of the part, thus preventing contamination. In some cases, inorganic salts are preferred over organic salts to facilitate removal of the support in the green stage. This is possible because organic salts can be damaged at high temperatures.

[0068] In another embodiment, the support contains only salt. If the addition of model material is required, the addition is During printing, the blending is done based on the print map. In that case, the blending is done by injecting the model and support pixels. This can be done uniformly by interlacing the model pixels into the support matrix or This is done non-uniformly by printing islands of cells. This technique simplifies the production of support materials. Not only does it require multiple fabrications, but it also requires the manufacture of individual supports for each model material to be printed. Another advantage of this technique is that it allows you to control the ratio as a function of distance from the printed part. One advantage of this approach is the flexibility in determining the ratio of salt to model material in the support, including the possibility of using a 100% sol-gel support.

[0069] The salt support can be implemented as either a salt solution or a dispersion of salt particles in a liquid. In one embodiment, the salt is a mixture of particles, such as silicate nanoparticles, and inorganic or organic salt particles or may be a combination of the solutions.

[0070] In one embodiment, the support ink comprises insoluble salt particles, the salt being inorganic or organic. The particle size of these inorganic or organic salts is 10 to 800 nm, for example 50 to 600 nm. The insoluble salt particles may be in the range of 100 to 500 nm. This means that the salt does not dissolve in the solvent mixture (both the model and the support). The support ink is characterized by a first solvent in which the salt is insoluble. A second solvent in which the salt dissolves may be added either before or after sintering to remove The second solvent, the salt support removal solvent, is used, for example, by spraying, jetting, or spraying the printed part. Alternatively, the second solvent may be applied in a different form, such as by immersing the printed part in a bath of the aqueous solution. configured to increase the flow of the aqueous medium at the printed part. Supported by mechanical elements or by generating mechanical vibrations or pulses into the water medium According to another aspect, the printed parts are placed on a vibrating tray. may be applied to enhance removal of the support.

[0071] Carrier Fluid The aforementioned particles are dispersed in a carrier liquid, also called a "carrier" or "solvent." According to one embodiment, the carrier liquid evaporates immediately after printing, allowing subsequent layers to adhere to the underlying solid. The temperature of the upper layer of the object being printed is therefore It should be comparable to the boiling temperature of the liquid. The boiling point should not be too high to reduce heat output during printing. It is desirable to have inks that rely primarily on the viscosity of the carrier liquid to enable jetting ability. The viscosity of the liquid must not be too high, and the surface tension of the liquid must match the requirements of the jetting head. In one embodiment, a suitable carrier liquid has a boiling point of 100-250° C., It has a viscosity of 3 to 30°C and a surface tension of 20 to 70 millinewtons / m.

[0072] In another embodiment, the temperature of the upper layer is much higher than the boiling temperature of the liquid carrier, This facilitates the evaporation of other organic materials such as dispersants or various additives in the carrier liquid. can be.

[0073] Dissolving Model Materials of solid materials in the form of micro- or nano-sized particles used to build objects At least a portion of the dispersion of silver (Ag) particles can be dissolved in the carrier liquid. In addition to Ag particles, the liquid contains some Ag organic compounds dissolved in the carrier liquid. After printing and during firing, the organic portion of the Ag-based organic compound evaporates, leaving the metallic silver atoms fully dispersed. The ink containing dissolved silver is manufactured by Dyesol Inc. (USA) (California, USA). DYAG100 conductive silver print ink is available from 1001 West 5th Street, 3400 W., TX 95617 (#638). These are readily available.

[0074] Dispersants To keep the particles dispersed, a dispersant helps disperse the particles in the carrier liquid. Dispersants are known in the art and are often a type of polymer molecule. The molecules adhere to the surfaces of solid particles (i.e., they envelop the particles) and inhibit the aggregation of particles. When multiple solid particles are dispersed in a liquid, compatibility issues between different dispersant materials can be overcome. It is preferred to use the same dispersant for all solid particle types so that dispersion can be avoided. It must also be soluble in the carrier liquid so that a stable dispersion can be formed.

[0075] The dispersant must also be compatible with the liquid carrier for stability purposes. For example, In the case of water-based inks, the surface properties can be appropriately controlled by changing the pH of the dispersion liquid, etc. Stabilizers (i.e., dispersants) are agents that bind to particles by covalent bonding or physical adsorption. It should be noted that the cations are attached to the surface of the cations.

[0076] An additional role of the dispersant is realized during printing. During printing, after jetting and drying, the dispersant When particles are dispersed in a liquid carrier, this helps to disperse the particles. Note that this is the opposite of the powder. If more binding is required, a special binding agent may be used. An agent is added to the ink dispersion.

[0077] Non-limiting examples of dispersants that can be used herein include BykChemie's Dispersant rbyk 180, Disperbyk 190, Disperbyk 163;Lub Rizol's Solsperse 39000, Solsperse 33000, S olsperse 35000; Rheospers by Coatex (Arkema) e3020, 3450, 3620; BASF Efka 770 l, Efka 77 3l, Efka 7732. Ionic dispersants include, for example, SLS (sodium lauryl sulfate). sodium cetyl ammonium bromide), CTAB (cetyl tetraammonium bromide), AOT (dioctyl Sun Chemic Commercially available from als Ltd., 485 Berkshire Av, Slough, UK Conventional particle inks such as SunTronic Jet Silver U6503 are It is readily available.

[0078] The aforementioned dispersants can be found in amounts ranging from 1 to 10% by weight of the model particles. The exact amount of agent depends on the agent's dispersion power and the quality of the mixing tool, as well as the adhesion characteristics of the dry material. All of these can affect ink properties such as viscosity.

[0079] Dispersant removal The dispersant may also be added prior to or during any desired post-processing steps, such as pre-sintering or sintering. It must be such that it can be removed from the print during any thermal processing of the print. During printing in the high temperature environment of the printer, partial removal of the dispersant may occur. Partial sintering occurs, replacing the bonding power of the dispersant. A more detailed explanation is provided below.

[0080] Surface Modifiers Surface modifiers affect properties such as surface tension, scratch resistance, and interface properties with printed matter. Exemplary surface modifiers include ethyl cellulose, carboxymethyl cellulose, Cellulosic polymers such as cellulose acetate, hydroxypropyl methylcellulose, and cellulose acetate Other surface modifiers may include polybutyral (Butvar) As explained in more detail below, surface modifiers can provide a complete solution, such as adding color or abrasion resistance. The surface modifiers facilitate the separation of the support from the model. or handling the print, such as providing a barrier between the support and the model to reduce cross-contamination. It may also improve.

[0081] When present in the support ink, the surface modifier may be: The carrier may comprise from about 0.1 to about 5% by weight of the ink.

[0082] Additives used as modifiers As used herein, an "additive" refers to a material that is added to an ink to support the printing of target particles. Materials that support the printing and sintering process, harden the green part, or prevent harmful phenomena during the printing and sintering process. In various embodiments, the processing of the final product, such as a printing or sintering step, or One or more additives to aid in the properties of the final object, such as the color or mechanical properties of the print. In one embodiment, the additives alone or dissolved in a suitable solvent may be added to the ink. There is at least one separate print head dedicated to dispensing the dissolved additive. As used herein, it refers to the deposition of material other than a model or support. The head is called an "additive head." In this case, it may not be compatible with the additive. There is no problem with dissolving the additive in the target ink. Furthermore, using the additive head, Different amounts of additive can be dispensed to different zones of the object.

[0083] Additives used to color the surface of a model In various embodiments, one or more additives may be added to the surface of the print to impart a desired color. For example, there may be additives added or overused. One zone that can be used is the perimeter area of ​​the model. The additive is a specific color that is only needed at the perimeter. It is possible.

[0084] [System for forming products with particles of different sizes] In one embodiment, a system for forming a product containing particles of different sizes is described. The system comprises coating at least a first portion of the article with a first material having a first average particle size. a small number of printheads configured to hold a first group of printheads that can be configured to print by adding at least one print head region, wherein the first average grain size is a first structure upon sintering In one embodiment, the first portion is selected to provide a core or For example, when printing artificial teeth, the printed layer, as opposed to the outer layer, The core or a substantial part of the tooth constitutes the tooth core.

[0085] The system further comprises dissolving at least a second portion of the product in a second material having a second average particle size. and at least a second printhead group configurable to print in a multi-colored manner, The second average grain size is adapted to impart a second structural characteristic upon sintering that is different from the first structural characteristic. In one embodiment, the second portion includes a peripheral portion of the printed product. When a tooth is printed, the peripheral portion of the printed tooth is the outer layer of the tooth, as opposed to the core structure. Configure.

[0086] In one embodiment, the first material and the second material have different average grain sizes and different sintering properties. They are substantially the same, such as having the same chemical or crystal structure, except for having a sintering temperature. In another embodiment, the first material and the second material have different chemical structures and / or or have substantially different crystal structures, but have substantially the same sintering temperature.

[0087] The system receives information reflecting a desired characteristic of the product and prints the first printhead and adjusting the first and second printhead groups to print the first and second materials layer by layer. uniform distribution, thereby allowing different parts of the product to be differentiated based on information that reflects the desired properties of the product. at least one processor configured to impart different structural properties to the components; In one embodiment, the at least one processor may perform a process to achieve a desired characteristic of the product. The method is configured to determine a distribution of the first and second materials to achieve the desired effect.

[0088] As used herein, "interlace" refers to the separation of different parts of a product. The first and second materials mix together during deposition to form a single structure, rather than separating over time. A unitary structure means that the first material and the second material are interspersed with each other so that they are interspersed with each other. It may include different amounts in terms of quantity or volume, e.g., between different materials across the interlace. The ratio of is different in different parts of the product depending on the desired characteristics of the product. The lint head does not randomly interweave the first and second materials and deposits such materials. For example, at least one processor may be configured to In order to achieve a printing product, a first print head group and a second print head group are However, the first and second materials may be configured to be digitally interlaced with each other. .

[0089] In one embodiment, the system described herein comprises at least one of the two materials A material is deposited so that it permeates into another material. In this embodiment, a first material is deposited on a second material. The web of strings formed into a printed product by wicking the material or vice versa. One or more strings of are formed.

[0090] The desired properties can be achieved by varying the amount and / or distribution of the first and second materials in each layer. For example, the at least one processor may include a first layer of a second material. and the second layer comprises more of the second material than the first material. The method may be configured to determine a distribution of the first and second materials in each layer. a first portion comprising a core of the object by varying the amount and / or distribution of a second material; and enables printing of at least a second portion including the periphery of the object.

[0091] Typical desirable properties of a product that can be modified or imparted include thermal, mechanical, chemical or Non-limiting examples of thermal properties include sintering temperature, coefficient of thermal expansion, coefficient of contraction, Non-limiting examples of desirable mechanical properties include thermal conductivity, thermal diffusivity, and wear resistance. Non-limiting examples of physical properties include toughness, brittleness, ductility, elasticity, stiffness, toughness, and yield strength. Non-limiting examples of chemical properties include stability, corrosion resistance, and hardness. As used herein, chemical "stability" refers to the ability to withstand environmental or mechanical stresses. This means that the material is not particularly reactive during normal use. For example, the material is A substance is considered stable if it is inert to air, water, moisture, heat, solvents, etc. under certain conditions. Similarly, the product will not corrode, decompose, polymerize, burn, or undergo any other damage under expected conditions of use or normal environmental conditions. A material may be considered unstable if it is likely to explode or explode. any combination of the foregoing by alternating the second material, as well as the amounts of each It can be applied to a printed product.

[0092] As mentioned above, the desired properties of the product may vary depending on various chemical or mechanical properties, particularly the product or The shrinkage coefficient of only a particular portion of the product may be included. In one embodiment, the sintering temperature and shrinkage coefficient By adjusting at least one of the printed model part and the printed support, It may be desirable to reduce or eliminate dimensional shrinkage during printing. The difference in dimensional shrinkage between the printed model and the printed substrate is less than 10%, or even less than 5%. etc., less than 15%.

[0093] In one embodiment, at least one of the support ink or the model ink is printed. The model part is sintered at a lower temperature than the support material. For example, in one embodiment, the printed model includes solid particles having a combination thereof. The components are heated to a temperature at least 100°C lower than the temperature of the support structure, e.g. The sintering temperature is at least 150° C. lower, or even at least 200° C. lower.

[0094] The size, size distribution, or combination of solid particles in the support ink and model ink The alignment can be modified to allow the printed model to sinter at a lower temperature than the support material. For example, the particle size of the solid material in the support ink may be In one embodiment, the particle size of the solid material in the support ink is greater than 1.0 microns. and the particle size of the solid material in the model ink is 0.5 microns or less. In this embodiment, the support ink comprises solid particles having a monomodal particle size distribution, and the model ink comprises The support ink contains solid particles having a multimodal particle size distribution. The solid particles may include solid particles having a packing density lower than the packing density of the solid particles of the granules.

[0095] As previously mentioned, inks that can be used in accordance with the present disclosure include those containing silicone, aluminum, titanium, Ni, yttrium, cobalt, copper, iron, zinc, magnesium, zirconia, and combinations thereof A composite or alloy of one or more solid particles of a metal or semi-metal oxide or carbonate. One or more support inks for inkjet printing support structures including model parts and and a model ink for inkjet printing. At least one of the inks is used to reduce the dimensional shrinkage between the printed model and the printed support. In one embodiment, the oxide or carbonate of the supporting ink One or more solid particles of SiO 2 , Al 2 O 3 , TiO 2 , Y 2 O 3 , CoO, CuO , ZnO, MgO, ZrO 2 , FeCO 3 and combinations thereof.

[0096] In one embodiment, the model ink is selected from iron, copper, silver, gold, and titanium. metal, SiO2 , TiO 2 , BiO 2 Metal oxide selected from WC, Al 4 C 3 , T iC is selected from metal carbides, stainless steel and titanium based composites. The solid particles are made of an alloy of the metals to be mixed.

[0097] In one embodiment, at least one of the support ink or the model ink contains a dispersant, a rheological agent, The composition further comprises an additive selected from a binder, a binder, or a combination thereof. The additive is present in an amount sufficient to control the gap between the solid particles contained in the ink. .

[0098] In one embodiment, the print head area of ​​the described system includes a third print head. The third printhead group is configured to hold the first and second printhead groups. Can be configured to print with removable support material to temporarily support objects As described above, the one or more additive materials may be added by a printing or sintering step, etc. They are added to inks to aid in the processing of the final product, or to improve the color or mechanical properties of the print. It is printed from a separate head to improve the properties of the final object.

[0099] [Method of forming products with particles of different sizes using the disclosed system] The present specification describes the use of the described system to produce products by inkjet printing. Also disclosed are methods for printing objects by inkjet printing as described herein. The method includes jetting an object material including particles to form an article structure having a first sintering temperature. Simultaneously with or prior to the formation of the product structure, the method may include forming a support comprising particles. and spraying the support material to form a support structure, wherein the support structure is a product structure. In one embodiment, the support material is sprayed to support the object. It has a high sintering temperature. The blasted object and the blasted support together constitute the green part. The method includes subjecting the green portion to a temperature equal to or greater than a first sintering temperature and less than a second sintering temperature. The heating at least partially sinters the injection object without substantially sintering the injection support. and removing the substantially unsintered support from the at least partially sintered body. and

[0100] As used herein, "substantially unsintered" means that there is no adhesion between the support particles. However, as long as the support particles are not yet fused together to form a dense solid piece, the support particles may still be substantially This means that the particles remain relatively separate or easily separated.

[0101] As mentioned above, the one or more solid particles that can be used in the methods specifically disclosed herein can be: SiO 2 , Al 2 O 3 , TiO 2 , Y 2 O 3 , CoO, CuO, ZnO, MgO, ZrO 2 , FeCO 3 and combinations thereof. The model inks used are selected from the group consisting of iron, copper, silver, gold, and titanium, and SiO 2 , TiO 2 , BiO 2 Metal oxide selected from WC, Al 4 C 3 , TiC Solids made from metal alloys selected from stainless steel and titanium-based composites. Includes body particles.

[0102] The method includes sintering the printed model at a temperature at least 100° C. lower than the sintering temperature of the support material. and further comprising sintering the printed model at a temperature below the sintering temperature of the support material.

[0103] In one embodiment, sintering can be performed in a single step, multiple steps, or using a laser. When sintering occurs using a laser, laser sintering is External energy, including microwave energy, plasma energy, or high energy lamps and at least one external energy source in combination with the laser, such as a neutron source. include.

[0104] In one embodiment, the method includes heat treating the green body at a temperature and time to form a theoretical The method further includes forming a partially sintered model having a density in the range of 70-85% of the original density.

[0105] Additives used to modify surface properties In one embodiment, the method further comprises adding at least one additive to the support or model. wherein the additive is deposited in a support ink or a model ink; or The additive is deposited using a separate printer head. can be deposited on the surface of the model with a separate printer head to change its properties. and the at least one characteristic is selected from the color or mechanical characteristics of the printed matter. For example, The additive deposited on the surface of the model comprises at least one wear-resistant material comprising a metal or a polymer. A wearable layer may be formed. Non-limiting examples of metals include cobalt, titanium, tungsten, The polymer contains sol-gel derived silica and tetraethoxysilane. TEOS and 3-glycidyloxypropyltrimethoxysilane (GLYMO ) hybrid membrane.

[0106] In one embodiment, the additive may include a polymer that forms a composite with the finished model. It is not possible to obtain a cellulose acetate film by adding it to the ink during printing, or by capillary action after the ink is applied. , which is added to the printing model material. For example, the polymer polyaniline alcohol (PAN) and the printed model may comprise a metal carbide.

[0107] In one embodiment, the method further comprises forming an interface layer between the support material and the model material. The interface layer includes a combination of a support material and a model material. For example, the interface layer may include FeC O 3 Includes.

[0108] In one embodiment, the method includes at least one mechanical, chemical, or thermal treatment step. The method further includes removing the support structure from the model material by a tap.

[0109] As previously mentioned, the additive head assembly may include several heads as shown in FIG. , which contains one head that accepts and jets several ink types. This head assembly The ink required for each inkjet printer is stored in several ink tanks and piping. The ink may include any of several ink types.

[0110] SYSTEMS AND METHODS FOR PRODUCING COLOR-PRINTED PARTS In one embodiment, the inks include a bulk ink that is a construction material ink, a white ink, and a colored ink. As shown in Figure 4, the ink is dissolved in a solvent and then With the exception of pigmented inks, which contain colorants that are not colored, inks must contain a dispersion of solid particles in a carrier liquid. As an example, referring to FIG. 4A, in one embodiment, the bulk of the ink is a carrier liquid. The ink may contain a dispersion of zirconia throughout the body. The colored inks are available in yellow, red, and blue. The ink dispersion may include zirconia mixed with an inorganic pigment. As shown in FIG. 4A, the ink dispersion may include , colorant particles (pigments), pigments mixed with structural particles (zirconia), or zirconia particles The pigment may include pigments embedded in the matrix (see FIG. 4B).

[0111] In another example, the bulk material may include steel, the white ink may include zirconia, and the colored ink may include copper. The four CMYK inks used in color printing: cyan, magenta, yellow, and key (black). In this embodiment, the CMYK particle pigments may be mixed with glass particles, The glass particles form a glossy, transparent coating upon sintering. The roll of structure particles in the color ink dispersion is used to achieve the same layer thickness in the colored area vs. the bulk area. In this embodiment, the ink is used to generate the appropriate solids volume percentage of the ink required for the , the structural particles can be considered as fillers.

[0112] In one embodiment, a method for adding color to a model surface includes: Creating or receiving a 3D digital representation of the desired object, including the object's shape and surface color. It may vary from point to point on the surface, and is based on the Munsell color system (hue, saturation, brightness), CIE XY Z (tristimulus values) or CIELAB (a*, b*, L*) or numbered code system or other color systems. Separating colors into a set of ink colors available to the printer (CMYK subtractive system) color, or spot color, or other). Calculate the number and relative proportion of colored pixels that make up a color spot on the surface of an object. As shown in Figure 5, pixels close to the surface of the object are digitally assigned different shades of color. Hit. ·Determine the orientation of objects on the material being printed and digitally add any necessary support structures. Slice digital objects. Print the object layer by layer (slice), with each head printing the ink assigned to each pixel. The layer thickness of the surrounding colored areas is similar to the thickness of the majority of the layer. Note that the printed object must be "unfired" and in some cases may be identical. This is called a "solid object." · The green object is baked in an oven until the object's material is completely sintered.

[0113] In an alternative embodiment where the bulk material making up the object is not white, the method further comprises: This involves adding a white layer around the object underneath the object. If the color varies from spot to spot on the surface, at least the layer behind the color layer must be white. It is also necessary that the structural particles of the pigmented ink (if present) are transparent. It may be necessary.

[0114] In one embodiment, the color is determined by adding inorganic colorants (pigments) that are compatible with the firing temperature of the object being sintered. Additionally, the colored ink may include a colorant or a colorant mixed with the building material. The building material may be the same as or different from the bulk building material, such as zirconia. If the luke contains steel, the colored ink contains glass.

[0115] If the colored outer layer comprises a different material than the bulk (e.g., the bulk is metal and the colored layer If the ink is ceramic, the size of the particles that contain the ink depends on the sintering temperature of both materials. The ink can be adjusted to be the same within the required tolerance. If the glass contains a homogeneous mixture of various oxide molecules, the composition of the glass itself will be For example, a small amount of lead oxide may be added to the silica material to produce a sintering temperature similar to that of lead oxide. The glass produced by this process reduces the sintering temperature of silica from 1600°C to 1300°C. .

[0116] In one embodiment, printing pigmented inks and Structural inks are in pixels of the same color. In addition to or instead of colored inks. Additionally, a transparent gloss ink can be deposited after sintering to add gloss to the manufactured object. can be done.

[0117] Systems and methods for creating colored prostheses The described process benefits the dental industry, for example for fabricating artificial teeth. In one embodiment, the normal color of the artificial tooth or crown is off-white or brown. In order to match such colors, zirconia-based inks are used. The disclosed method can be used to print artificial teeth or crowns, such as by using a The pigmented ink comprises a pigment mixed or embedded with zirconia. The present invention relates to a process for producing a colored fluororesin using a colorant that is colored as described herein and is shown in FIG. A graphical representation of an artificial tooth or crown is described.

[0118] System for producing artificial teeth In view of the above, a method for manufacturing a body implant or prosthesis, such as an artificial tooth portion, A system for detecting a cellular signal is also described. In the simplest embodiment, the system comprises at least one The printhead region includes at least one processor. The printhead region includes configured to print additional three-dimensional metal cores from a first ink including metal particles. A first printhead group having a second ink containing ceramic particles, and a second ink containing ceramic particles. a printhead configured to apply and print a surrounding ceramic outer coating; In addition, the at least one processor is configured to hold a metal and The system receives instructions to print a customized artificial tooth part made of titanium and ceramic. The processor is configured to cause the first print head group to print a three-dimensional metal component in the print area. At the same time, a second set of printheads prints a ceramic outer coating on the print area. The first print head group and the second print head group are arranged to print the ink by adding ink. Control the crowd.

[0119] In one embodiment, the received instructions include three-dimensional data representing the entire actual tooth, at least One processor is configured to accurately replicate the actual teeth. In this configuration, the processor ensures that the ceramic outer coating of the artificial tooth is identical to that of the entire natural tooth. The distribution of the first print head group and the second print head group is adjusted so that they have the same dimensions. The control circuit is configured to control the

[0120] Additionally, at least one processor has a metal core with a ceramic outer coating at its height. The first print head group and the second print head group are arranged so that the height of the first print head group is higher than the height of the second print head group. It can be further configured to control

[0121] Additionally, at least one processor may include a metal core that is separated from a ceramic outer coating. The first printhead group and the second printhead group are threaded metal portions protruding from the first printhead group. The sensor may be further configured to control a group of sensor heads.

[0122] The described processor allows flexibility in printing the various materials described herein. For example, the processor can print metal and ceramic on the same layer or on separate, distinct layers. In one embodiment, the print head can be configured to print at least one of the processors. The ceramic core is then coated with a layer of 3D metal before the next layer of 3D metal is deposited. It is further configured to print a layer of an outer coating. The one processor further controls the first printhead group and the second printhead group to: It is constructed to digitally interlace metal and ceramic together.

[0123] An additional printhead is also described that can be used to print the threads of the artificial teeth. In this embodiment, at least one print head region is used to produce a threaded metal part. A third print head that can be configured to print with a removable support material for printing the print head. The data set is configured to hold a group of data.

[0124] A method is also described for printing a ceramic layer after the metal has solidified. The described system provides heat to the print area to solidify the recently deposited ink. The at least one processor may further include a heat source configured with a three-dimensional metal core. After the layer has at least partially solidified, a ceramic outer layer corresponding to the layer of the three-dimensional metal core is formed. It is further configured to print a layer of the coating.

[0125] To avoid thermally induced stress problems, the metal core and ceramic outer coating layer are They share the same or substantially the same sintering temperature. As previously mentioned, this is true for metals and ceramics. To print different parts of the final product, such as using different particle sizes in the coating material This can be achieved by manipulating the particle size of the ink used in The average grain size of the ceramic particles is larger than that of the metal particles, resulting in a metal core and a ceramic outer layer. The coatings may be allowed to substantially share sintering temperatures or shrinkage coefficients.

[0126] The processor used in this embodiment stores three-dimensional color information regarding the coloring of the artificial tooth portion. Further, the processor receives instructions for simulating a color distribution of actual teeth. In addition, multiple printheads are fitted with ceramic outer layers so that a different color is deposited on each pixel. In one embodiment, a plurality of print heads are configured to print a side coating. is configured to print the ceramic in different colors, and the at least one processor is It is further configured to control deposition of ceramic in different colors according to the three-dimensional color information. For example, the printheads may be configured to print non-structured pigments, and at least one The processor also determines the color of the CMYK inks according to the three-dimensional color information. The present invention is configured to control the distribution of non-structural pigments on the mix outer coating.

[0127] In one embodiment, the printheads described herein may be configured to provide mechanical or aesthetic improvements. For example, in one embodiment, a plurality of The printheads are used to deposit glass onto the surface of artificial teeth, which is then sintered and then photoetched. It is further configured to deposit to provide a thick transparent coating.

[0128] With further reference to a system for manufacturing an artificial tooth part, three-dimensional data representing a real tooth In one embodiment, the three dimensional data is a tooth. The system described includes three-dimensional color information representative of the actual coloring of the first pigment in a carrier liquid. At least a first printhead group configured to eject a first material of a color; at least a first printhead configured to jet a second material of a second color of the ink; The printhead includes at least one printhead region configured to support the printheads. In the third embodiment, the system is configured to jet a third material of a third color in a carrier liquid. The printhead further includes at least a third printhead group. At least one of the materials may be sprayed with additional layers to form the artificial tooth portion. It is configured as follows.

[0129] The systems described herein are adapted to access three-dimensional data including three-dimensional color information. The three-dimensional color information further includes at least one processor configured to A digital representation is then generated, the digital representation being a representation of the injected artificial tooth portion. At least one first processor is provided to digitally simulate the color distribution of real teeth. a print head group, at least one second print head group, and at least one first The printer driver 100 then configures the commands to control the three printheads.

[0130] The at least one processor further controls the first, second, and third printhead groups. The process may be configured to control the ejection of the artificial tooth portion. The printer includes at least one first print head group, at least one second print head group, A mixture of colors from the first group of printheads and at least one third group of printheads are mixed to produce a realistic tooth image. In one embodiment, the printed artificial tooth portion is , having a metal core digitally interwoven with a ceramic outer coating. Any or all of the second and third materials may be ceramic materials, such as those described herein. In another embodiment, the second and third materials are understood to include ceramics of the present invention. As previously described herein, it may also contain substantially non-structural pigments.

[0131] Methods for making artificial teeth using the described system A method for adding and manufacturing an artificial tooth portion is also described. In one embodiment, the method includes: Can be configured to print additional 3D metal cores from a first ink having metal particles The method further includes providing a first printhead group having ceramic particles. A second ink containing providing a second printhead group configured to:

[0132] In another embodiment, the method includes the step of: receiving an instruction to print the artificial tooth portion; and The first print head group is controlled to print a three-dimensional metal core in the print area. At the same time, a second set of printheads prints an additional ceramic outer coating on the print area. do.

[0133] [A third printhead for printing additives to improve final product properties] As mentioned above, to aid in the processing of the final product, e.g. to improve the properties of the final object. Additionally, one or more additive materials may be added to the ink. Non-limiting examples of properties that can be improved include: , the colour or mechanical properties of the printed matter.

[0134] Adding a wear-resistant layer to the model surface Wear-resistant layers are discussed in the context of artificial teeth or orthopedic implants and various industrial components. However, the uses are exemplary only and are not limiting or exclusive. A variety of printed products can benefit from a wear-resistant layer. In one embodiment, an additional head is used. This can be used to deposit additive materials that enhance the wear resistance of the resulting object. They found that an abrasion-resistant layer could be achieved by incorporating additives into the printed model material. Non-limiting examples include the addition of WC to stainless steel, WS to stainless steel, 2 Ma In one embodiment, the addition of C60 or C60, or the use of a WC / Co matrix. WC or WS 2 is added as a third phase to the matrix to improve the friction and resistance of the resulting product. It is possible to reduce wear. 2 Add to printed materials to improve lubricity, adhesion, The fracture toughness and strain energy release rate can be improved. The additional head contains a dispersion of cobalt particles that is added to a dispersion containing tungsten carbide. The material may be printed on the substrate.

[0135] In another embodiment, the abrasion resistant layer may include an epoxy / sol-gel composite. Sol-gel or epoxy combined with sol-gel feedstocks are used to deposit the materials These materials are printed onto the surface of objects. Once the solvent is removed, they harden at temperatures between 100 and 200°C. In one embodiment, these materials turn into ceramics when exposed to additional heat under certain conditions. Without being bound by theory, such conditions are usually The thermal region leads to weight loss of the sol-gel. For example, at up to about 250°C, the sol-gel matrix The first evaporation of the solvent occurs, which is weakly chemically bonded to the water molecules on the surface of the substrate. The additional fragmentation of the bridging organic groups / chains occurs. Decomposition / thermal decomposition occurs at about 300°C and continues up to 650°C. Above 500°C, condensation reactions This starts the formation of a 3D Si-O-Si network. is obtained.

[0136] The GLYMO-TEOS combinations described herein may be used alone or in combination with a crosslinker ( It can be used with additives such as polyvinyl chloride (PVP) to make it more hard. They found that the polymers were relatively easy to jet using inkjet technology and that the environment was suitable for the desired final product. The inventors have found these materials to be desirable in the disclosed methods because they aid in the production of high-quality products. In one embodiment, the process involves jetting these polymers onto the hot surface of the print. This accelerates the hardening and curing process. The result is a dense, transparent, scratch-resistant A thin coating is formed.

[0137] Procedures for preparing these polymer type materials are described in Wu et al., for polycarbonate. Study on Improvement of Mechanical Properties of Sol-Gel Coatings on Thin Solid Films, Vol. 516, No. 6 , 2008, pp. 1056-1062, which is incorporated herein by reference. To be incorporated.

[0138] Adding a barrier between the model and the support In another embodiment, an additive head is used to deposit a buffer / barrier forming additive. This can prevent cross-contamination and / or improve support removal. The form is FeCO as an additive. 3 For example, in one embodiment, In the state, FeCO 3 It has also been used as a support material for 3D printing of iron-based metal alloys. As mentioned above, FeCO 3 At temperatures between 500 and 700°C, iron oxide and CO 2 Thermal decomposition into To provide a supporting structure for the iron-containing model ink, FeCO 3 powder is dispersed in a solution to form a jettable material that can be deposited onto a substrate from an inkjet printhead. In addition to jetting and drying, the 3D printing process involves different A leveling step was added to reduce height variations caused by variations in build speed of the cheats. The leveling step is often performed by rollers. This can cause cross-contamination between the model and the support. Therefore, the support material , which can be removed during post-printing thermal treatment or contaminants on the support can be integrated into the material matrix It is necessary.

[0139] In one embodiment, FeCO3 As a support material for iron and iron alloys such as stainless steel After printing, the support together with the model may be placed in an oven for thermal debinding and FeCO 3 Debinding mainly occurs at temperatures below 500°C, so FeC O 3 The decomposition of CO 2 The pore structure is already available to some extent for the particles to leave the printed area. The remaining iron oxide remains small in volume and brittle. After pyrolysis, the support The model parts must be cooled to room temperature and any remaining iron oxide removed by brushing or air current. It can be easily removed mechanically. After removing the support, the model is transferred to a sintering furnace.

[0140] As mentioned above, FeCO 3 One advantage of the support is that contamination in the model is converted to iron oxide. The decomposition stage is when hydrogen atmosphere or forming gas (5% H 2 , 95 %N 2 During sintering at 1000 K, iron oxide is reduced to metallic iron. Thus, contamination of one of the model materials The concentration of the contaminant is so low that the addition of small amounts of iron (≦2 wt.%) does not significantly affect the molybdenum content. The stoichiometry of our materials, e.g. stainless steel 316, 316L, 17-4 or 314, is It doesn't change much.

[0141] In one embodiment, the thickness of the barrier / buffer layer described is between 0.1 and 0.3 μm. In this way, mixing of the support material and the model material on the surface of the object can be prevented. This can be done.

[0142] Formation of composite materials by supplying additives to model regions In some embodiments, the additive may be applied uniformly or non-uniformly to the model area, depending on the desired effect. For example, after the printing step and before the complete sintering, e.g. or brown areas, another material is added to the open pores of the print by capillary action to create a composite material. It may be desirable to do so.

[0143] In one embodiment, the polyaniline alcohol (PAN) polymer is By adding it to the ink, or by subsequent penetration, the printed model is This particular method uses high pressure filling and is more durable than objects without polymer filling. The PAN participates in the sintering process and is carbonized to form a metal. When PAN was added to the WC printed samples, this process This figure shows one non-limiting example of the type of composite material that can be made using PA Since N carbonizes without losing carbon to WC, the resulting composite has a lower density and elasticity. increases.

[0144] Generally, carbon fibers are made from PAN, an organic polymer, and are bonded together by carbon atoms. Fibers are characterized by long strings of polymerized molecules. They can be spun, stabilized, carbonized, and finished. , is produced by several process steps. Before carbonizing the fibers, linear atomic bonds are must be chemically modified to convert it into a more thermally stable ladder bond. This is achieved by heating the fibers in air at approximately 200°C for 30 to 120 minutes. The fibers pick up oxygen molecules from the air and rearrange their atomic bonding patterns. In the case of PAN, printing is performed at 200°C, so an additional processing step is required. It is not necessary.

[0145] [Sintering - Adjustment of parameters between model and support] Consistent with the present disclosure, after the printing process is completed, the object is placed in an oven for sintering. In some embodiments, the object can be heated in an oven at a predetermined temperature until complete. The sintering process includes the following firing steps: Initial heating to burn the equipment materials; liquefying inorganic additives such as cobalt, if present additional heating to sinter the particles; and a final heating to sinter the particles.

[0146] Some of the heating steps described involve the application of vacuum, pressure, oxidation, etc. Adding inert gases to prevent oxidation and other gases (e.g. For example, hydrogen may be added to help remove oxygen from the body.

[0147] The sintering temperature of the particles is, among other things, a function of particle size. Nanoparticles melt at lower temperatures. Mixtures of nanoparticles and microparticles may promote partial sintering because the particles tend to dissolve in the matrix. This is especially important when designing model inks that sinter at lower temperatures than the support material. By removing the dispersant, the sintering between the model particles was prevented by interference from the dispersant particles. Furthermore, when the dispersant is removed, it weakens the solidified 3D structure. This prevents the formation of "islands" of dispersion particles in the print. Polymeric Dispersants and Other The non-volatile compounds are typically burned or incinerated in a post-printing process.

[0148] In one embodiment, the present disclosure provides a method for determining particle size and particle size to ensure sintering of the model prior to support. It provides a mechanism by which the sintering temperature can be selected and facilitates support removal after sintering. Control the sintering temperature between the supporting materials to allow easy removal of the non-sintered support from the sintered model. This mechanism for achieving this is exemplified by silica supports, which have large uniform grains. It is made up of child sizes.

[0149] During sintering, the sintered particles substantially adhere to each other, filling the voids located between the particles and increasing the density. The macroscopic result is substantial shrinkage (e.g., 15-60% volume). When only one material shrinks at a certain temperature, it moves away from the other material, causing the two materials to This can cause separation and damage to at least one of the materials. In an embodiment, the sintering temperatures and shrinkage coefficients of the different materials should be substantially the same.

[0150] Sintering temperature and support material The rolls of support are used (a) to support the “negative” wall of the model, and (b) to In one embodiment, the support material is doubled to add a protective envelope around the device. , are not removed from the model prior to sintering the model. In contrast to the requirement that the support material should have a substantially different (higher) sintering temperature than the model material. Therefore, partial or complete sintering of the model material is required while sintering of the support material is almost complete. Little or no damage is done to the model, resulting in a rigid sintered model material without destruction. This embodiment allows the removal of soft, brittle or soluble support material from the substrate. , by selecting a support material with a sufficiently high melting point compared to the model, or by controlling controlled particle size and / or particle size distribution or of different materials This is achieved by adjusting the sintering temperature of the individual ink compositions according to the shape irregularity. can be done.

[0151] An example of a support according to the last embodiment is an ink containing spherical silica particles with a diameter of about 1 micron. and serves as a support for the stainless steel ink. See material comparison in Table 1. . [Table 1]

[0152] From any side, the model is sintered at a temperature ( As shown in the table above, the sintering temperature of the particles is about 1250°C. Depends on the size and chemical composition of the particles. When the grain size is much smaller than that of the sintering temperature decreases substantially as the grain size decreases. Therefore, two materials A and B with different melting temperatures must be sintered at the same temperature. If there is, adjust the particle size of at least one material (e.g., material B) to The sintering temperature can be the same. Figure 6A shows this idea graphically. FIG. 6B shows the relative density of the material versus sintering temperature. In one embodiment, the model material is at least 1° C. above the sintering temperature of the support material. 00° C. lower than the sintering temperature of the support material, for example at least 150° C. lower than the sintering temperature of the support material, Sinter at a temperature 200°C lower, at least 250°C lower, or at least 300°C lower .

[0153] Therefore, one embodiment for obtaining the same sintering temperature is to Control the particle size and / or particle size distribution to achieve sintering temperatures substantially similar to other materials. In another embodiment, the particle shape is controlled. The more regular the shape, the better. (e.g. spherical), the sintering temperature is higher.

[0154] Single-Stage Sintering As mentioned above, in one alternative embodiment, the inventors have proposed a method for producing a sintered product based on a large difference in sintering temperature. We have found a method for producing printed matter that allows the model material to be sintered at a temperature high enough to support it. This allows for a single heating step that does not sinter the material. The model was made to be consistent enough that it could be removed from the support structure (on which it was wrapped) without breaking. This embodiment utilizes the difference in sintering temperature between the model ink and the support ink. .

[0155] Two-stage sintering Referring again to FIG. 6B, the relative densities of the various sintering stages associated with the powder material are shown. In this embodiment, the support material is a graph showing the model material in its pre-sintered stage (powder grain). The point at which the fibers come into contact with each other and necking begins is reached, but before substantial shrinkage begins. This process is used in MI applications where organic content needs to be removed from the part prior to sintering. It is similar to the two-stage debinding and sintering process used in the M industry. The sintering process includes: removing the print from the print substrate; The object is placed in a first oven and heated to a temperature at which the object begins to neck between particles. (This step, called pre-sintering, removes the binder from the object); Cool the object and move the cooling part to the cleaning port to remove the support structure from the object. and placing the object in a high temperature oven for a second sintering step (in this step, the object is heated to a high temperature). (The body is heated and completely sintered).

[0156] During the early stages of sintering, the powder particles bond to each other and necking forms between them. At this stage the material is much harder and less brittle than in the loose powder stage, but shrinkage is minimal. Moreover, due to the low temperature, the support material does not reach the point where it begins to sinter. The process of removing supporting material by either mechanical, physical or chemical means. The process is relatively simple. Removal of the support material during the pre-sintering step reduces the machining and handling of the part. The ring can be used to completely remove the support material. It can also be used to remove the support material prior to the sintering step. By removing the support, cracks can be prevented. If the support is not removed before the sintering process, If not, the support material may also begin to sinter, making its removal more difficult.

[0157] In the case of two-stage sintering, the temperature between the model material and the support material is increased from room temperature to the temperature of the first stage oven. Comment that the desire to have no or little shrinkage differential is limited. In one embodiment, using a two-step process is advantageous in that it reduces the time required for debinding. - It can be more economical because the process can be carried out in relatively inexpensive low-temperature furnaces. The high temperature sintering furnace is reserved for the fast, high temperature sintering stage only.

[0158] As mentioned above, one way to ensure that there is no sintering of the support during the debinding step is to , larger size and more regular shape and "narrower" particle size distribution than the model material and the use of a support material with a high melting point. This is the case, as mentioned above, of the steel nanoparticles. A support material containing 1 micron spherical silica particles is used to support the particle-containing ink. Such a support ink is exemplified by the hydrolysis of alkyl silicates and their Subsequent condensation of silica acid in alcoholic solution results in the production of spherical silica particles of uniform size. Ammonia can be produced by a system of chemical reactions that allows controlled growth. The particle size obtained in this process is less than 0.05 μm in diameter. The diameter can be controlled from 0.01 to 2 μm. The diameter non-uniformity is less than 10%.

[0159] As an example, SiO 2 having a size of about 60 nm (polydisperse) 2 The particles are approximately 900 If larger particles, for example in the micron range, are used, the particles are sintered at 300°C. It is sintered at 1550°C, which is significantly higher than the sintering temperature. Therefore, it contains particles in the micron range. The support allows the model particles to sinter to form a rigid structure, but not to the support particles. Due to differences in sintering temperatures and the resulting microstructures, printing and The molded and sintered model can be removed from the support structure without damage.

[0160] Known wet chemical techniques can be used to produce controlled shapes; porosity levels; and densities, e.g. , micron-sized SiO with tailored properties such as reduced density hollow spheres 2 Manufacture of particles Non-limiting examples of control parameters that can be used to control particle size include: , the nature of the Si precursor; the water / ethanol ratio used to prepare the silica; the reaction time and temperature The process describing the system is described in the literature [W. St ober, A. Fink, E. Bohn, Controlled growth h of monodispersed spheres in the micron size range, J. Colloid and Interface Sc i. 26 (1968) 62-69, which is incorporated herein by reference. is incorporated into.

[0161] SiO 2 The influence of the nature of the Si precursor, water content, and ethanol ratio on the grain size of the materials. To illustrate the effect of the present invention, the inventors examined several variables in the ternary phase diagram shown in FIG. 7. The following reaction conditions were used: temperature 20°C, stirring for 12 hours, pH ~11.

[0162] SiO 2 The precursor material was 9 wt.% SiO 2 Viscosity including content: 12.2c at 25°C Ps, density 1.12 g / cc, and surface tension 32 mN / m.

[0163] Table 2 shows how particle size changes with ethanol / water ratio and silica content. Indicates whether a change has occurred. [Table 2]

[0164] In-situ debinding and sintering In one embodiment, a method is provided to address issues associated with shrinkage during debinding and sintering. In particular, the inventors have demonstrated that cracks in green or brown bodies can be eliminated while In addition, to improve process throughput in order to shorten the debinding process after printing An in-situ debinding and sintering process was discovered.

[0165] In current processes, each printed layer is cured before jetting the successive layer. Typically, curing is done by: This is achieved by evaporating the liquid carrier of the metallic ink to create the green part. Printing is usually done by vaporizing the carrier and fixing the jetted droplets in specific, precise locations. It is done on a hot surface and uses additional heat to completely evaporate the liquid carrier. Heat is provided by a system consisting of fans, lamps, lighting, and suction.

[0166] When nanoparticles are used in the disclosed process, the melting point of the nanoparticles is typically The temperature range is about 200 to 400°C. Therefore, it is necessary to use a heating chuck or lamp. Simple external energy can cause sintering in the substrate or in the previous layer. When micron and submicron particle sizes are used, the melting points of typical metals are consistent with the bulk material. Sintering or even partial sintering using heated chucks or lamps is possible because the material remains in contact with the In particular, the energy flux (Watt / m 2 ) is insufficient to initiate sintering. As a result, high energy flux is achieved over a short time frame to provide a low total energy flux to the sample. An energy flux is required, which can be achieved by laser, microwave, or flash light sintering. Such a system can provide high energy flux (watts) for short periods of time. This allows the surface temperature to rise to a suitable sintering level.

[0167] In one embodiment, a fully sintered part containing micron and submicron metal particles. To obtain the desired properties, a post-printing process consisting of a debinding and sintering procedure can be used. A laser line scanner can be used to burn powders using an in situ process. Although it is possible to combine the two, this process is limited by low throughput due to scan times. Limited.

[0168] To avoid these limitations of in-situ sintering, the printing process is followed by the printing of brown or completely A process for obtaining a precisely sintered part is described herein. Unlike the can technology, the present invention uses flashlight or microwave energy Line scan laser or full area sintering is described. For example, a ceramic material is used for the support and metal powder is used for the model. As another example, nanoparticles in the model area are used. Use doping.

[0169] FIG. 8 illustrates an in situ laser with a model and support material according to one embodiment of the present disclosure. The external energy used for sintering is microwave, generated by a rolling electrostatic charge roller or a flash of light from a high energy lamp The plasma may be

[0170] The disclosed method results in direct selective heating of the printed metallic ink layer, thereby Higher process temperatures and therefore better sintering performance in shorter times are possible. The proposed process is as follows: (i) print the ink and the support; (ii) print the substrate; Use heat from the bottom of the lamp and / or a blower in the lamp system to reduce the (iii) removing the liquid carrier for the mid-range energy flux (see below for details); using a laser scanner with illumination or other energy to remove excess organic material; (iv) Finally, the same equipment with high energy to briefly heat the particles to the sintering temperature (e.g. :Laser) is used.

[0171] In one embodiment, the debinding process is performed using a laser as described and exemplified herein. For example, a process speed of up to 10 mm / sec is used. The goal of the debinding process is to decompose the printed ink by pyrolysis. The first step is to remove the organic components from the model by heating the surface of the model to 300-400°C. When sintering with high energy in a short time, the sintering time should be kept to a minimum to avoid oxidation. During sintering, the metal particles are pulled together by surface energy forces. After removing some of the organic components, the brown intensity of the sample was reduced by partial sintering. A method for achieving this is described. This is followed by furnace sintering to achieve complete debinding. Rapid sintering during the printing process eliminates oxidation. To ensure that the environment is not toxic, use an inert gas such as nitrogen, argon, or hydrogen. Any of the common combinations of these gases can be added to the system. For the laser, about 10-20KW / cm 2 strength, 10-100um line width, and 3 -A line array laser producing 808 nm wavelength with a line length of 300 cm is described. In one embodiment, the pulse duration is CW or A pulsed laser may be used.

[0172] As mentioned above, sintered materials undergo consolidation, which is associated with the elimination of voids and porosity between their constituent particles. Therefore, the model only sinters and shrinks at a certain temperature. When the model shrinks, it peels away from the non-shrinking support material. This release can be used as a means of removing the support. This is useful when the support is located outside the body of the model. In contrast, When surrounded, the support prevents the model from shrinking as needed and helps the model hold during sintering. This feature is not an option as it may cause corruption.

[0173] In other words, the digital application of different materials per pixel in the various non-limiting examples above. In addition, one or more complementary digital thermal treatments can be provided for each pixel to Control the solidification, evaporation, necking, debinding, or sintering levels of the According to this embodiment, local or bulk properties can be achieved. The sintered parts may be green, brown, sintered pixels, or heated, debound, constricted, partially sintered or completely The material may be processed to be fully sintered, etc., or anywhere in between. Different heat treatments may be used for different materials. Since it may provide different mechanical properties, it is possible to perform pixel level determination according to an embodiment of the present invention. The ability to provide digital heat treatment allows the model structure, support structure or their interfaces to be This allows for the distribution of different mechanical properties across the interfaces. For example, a model pixel can be The model areas may be subjected to an in situ heat treatment that creates brown areas. The support pixels are not exposed to in situ heat treatment or these supports are converted to green areas. Alternatively, for example, some supporting pixels may be subjected to a thermal treatment that By in-situ heat treatment, these pixels are turned into brown pixels, and other supporting pixels are turned into brown pixels. You can increase your support while keeping the sphere in the green phase. The pixels in the boundary layer between the body and the model are also or to reduce sensitivity to differences in shrinkage coefficient between the support and the model to prevent cracks. , may be subjected to an in situ heat treatment that turns the (boundary layer pixels) into green pixels. According to another example, some model pixels are subjected to an in situ digital heat treatment to Create these pixels as green pixels that act as strain relief areas in the model. However, other model pixels were exposed to digital in-situ heat treatment to produce brown pixels. Or it may be converted into a partially sintered pixel.

[0174] [Shrinkage - Adjustment of parameters between model and support] Controlling ink shrinkage during processing In view of the foregoing discussion, in accordance with aspects of the present disclosure, different model inks may be used in the same model. When used together, models sharing similar shrinkage coefficients are used to form composite or multi-part objects. The similarity of the shrinkage coefficients is advantageous when using a 100% ink. The first substantial shrinkage occurs when the additive is steamed and sintered. The first shrinkage occurs during debinding (leaving a vacuum) and the second shrinkage occurs during sintering. In the form, shrinkage is achieved by removing the support in the green state or by reducing the shrinkage by 3%. The percent adhesion is controlled after the debinding process to be less than, for example, less than 2%, or even less than 1%.

[0175] Shrinkage during debinding In one embodiment, differential shrinkage during the debinding step is prevented by preventing shrinkage altogether. This can be done by maintaining a vacuum in the oven throughout the process. Due to the vacuum surrounding the part, the internal vacuum remaining after loss of additive causes shrinkage. The second embodiment does not generate pressure when the additive leaves the body (e.g., by evaporation or Based on the proposal that particles move towards each other until they come into intimate contact (by disintegration and evaporation) It is based on the principle that the empty volume previously occupied by the additive is minimized. However, this does not mean that all the volume occupied by the additives will disappear. This is because there is a lot of empty space between the particles of the closest structure. For example, a sphere of uniform radius For granular particles, the vacant space of the nearest structure is more than 30% of the total volume. If they are different from each other, the empty space may be smaller. The amount of additive (e.g., organic material) is adjusted so that both materials are gained in equal amounts while the additive is lost. If the main part of the additive is the binder, this step is called debinding. This is the Inder stage.

[0176] Shrinkage during sintering The particles are separated from each other before being debindered of the binder and other additives. After sintering, the particles only contact each other at individual points. During sintering, the particles fuse together. As a result, the voids between the particle surfaces disappear and the material shrinks. Therefore, the amount of shrinkage depends on the particle size before sintering. Depends on the amount of free space in between.

[0177] In one embodiment, the particles of each material are substantially identical in size and shape to one another. This embodiment takes advantage of the fact that the ratio of free space to particle volume is scale invariant. In another embodiment, the images are substantially the same except that the scale may be different. Size and shape distributions of both materials are described. Another embodiment is small particle By mixing the material with larger particles so that both materials have the same relative free space, This embodiment relates to controlling the relative free space of the material. It relies on the fact that it reduces the empty space between the children to fill it.

[0178] To prevent breakage and cracking, the temperature at which additives are lost is essentially the same for different materials. It is important that the contractions occur simultaneously so that they are identical.

[0179] Shrinkage control with additives As previously mentioned, in embodiments where it is desirable to sinter two or more model materials at the same temperature, Compositional variations can be used to avoid issues with differing shrinkage rates between materials. For example, It is known that model materials may shrink by different amounts during sintering. This is because the voids between each particle may be different. Parameters that affect void size One of the factors is the amount of lost material that is added and mixed into the particle. The material that is lost evaporates or collapses at a temperature lower than the sintering temperature of the molecule. During sintering, the particles move closer together, closing the gaps. This causes shrinkage of the material. Therefore, the shrinkage coefficient is controlled by the additional amount of material lost. To be controlled.

[0180] As mentioned before, different additives, namely, dispersion material, injection improvement material, and binding material, are added to the Of course, one or more of the three materials can be included in the ink formulation. During the previous heat treatment period, all organic material is usually lost. Therefore, the interparticle The amount or size of the voids can be controlled by controlling the amount of added (additive) material. Cut.

[0181] FIG. 9 shows the particulate material before and after evaporation of the dispersant. FIG. 9A shows the dispersant molecules (90 FIG. 9B shows a particle (902) surrounded by a sintered particle (4). The particles (902) remaining after the loss are shown, and the dispersed particles often comprise organic materials.

[0182] Controlling shrinkage rate through packing density In one embodiment, the amount of shrinkage can also be modified by changing the physical shape of the particles. For example, if the particles are cubic compared to spherical particles, they will have different packing ratios (herein The packing limit for spherical particles is about 64%. In terms of morphology, a specific particle distribution can be selected to pack multiple particles to a very high packing density. This allows for a wide range and mix of particle sizes to be used to increase packing density to near 100%. It can be done.

[0183] The packing density of the printed powder depends on the particle shape and size distribution. Similar to the packing of molecules or atoms within a particle. The packing ratio ranges from 0.5 to 0.7. For example, in a crystal lattice, the packing ratio is a simple atomic cube. The binding coefficient is about 0.52; for body-centered cubic (BCC) it is 0.68; for face-centered cubic (FC In the case of C), the ratio is 0.74. On the other hand, when powders of various sizes are present, the smaller the powder, the The tip fits into the space between the larger powder particles.

[0184] Figure 10A shows the low packing density of the model powder associated with only a single large particle size. In contrast, Figure 10B shows a model powder-like distribution associated with a multimodal particle size distribution. In FIG. 10B, the smaller particles are spaced apart from the larger particles, indicating a higher packing density. As a result of this effect, which is related to the bimodal particle size distribution, The powder has a higher packing density, which is less than that of a powder having a lower packing density. In one embodiment, the printed model has a shrinkage that is not The shrinkage to maximum density is less than 10%. We have investigated the particle shrinkage, packing density, and binder It was found that a low distortion region can be obtained by controlling the removal of the dye. According to the discussion, the particles include a solid target particle embedded in an envelope containing an additive material. Note that this will later be burned off during the debinding step.

[0185] The inventors have found that using different particle size distributions for the model powder and the support powder Resulting in a more desirable shrink profile for each of the die and support regions, It was found that the strain area between the model and the support was small. In terms of morphology, a model powder with a multimodal particle size distribution that results in high packing density, and Structured powders with monomodal particle size distributions that result in lower packing densities are described. The use of high packing density model materials in combination with low packing density support materials has been shown to improve the debulking During debinding, the stress in the support material was found to be lower. The low packing density allows for increased free volume of the support material as the binder is lost. While the model shrinks, the support particles are free to move to other positions. For example, in one embodiment , a support material having substantially the same particle size (to achieve a packing density of about 0.5) When the binder is removed, more than 50% free volume is available, which allows for Virtually all stress is released from the model, see Figure 10D.

[0186] In one embodiment, a method for neutralizing shrinkage between a model and a support material for a 3D printing material is disclosed. This method is based on the difference in shrinkage between the support material and the model material during sintering. It seeks to avoid uncontrolled separation and deformation of model parts associated with high stresses and strains. In 11A-11F, when selecting powder for model ink that has a higher shrinkage rate than the support material, Distortion occurs at the beginning of sintering (see Figure 11A), which leads to uncontrolled separation during sintering. This causes deformation of the resulting print (see FIG. 11C). On the other hand, the shrinkage rate of the print is higher than that of the support material. If we select a powder for the low model ink, distortion will occur again at the beginning of sintering (see Figure 11B). ), high compressive stresses are generated during sintering (see FIG. 11D), which may lead to the resulting prints being As a result, in one embodiment, the model and The shrinkage rates of the die and support materials should be balanced and matched as closely as possible to minimize stress during sintering. It is desirable to do so. [Industrial Applicability]

[0187] Disclosed ink compositions, methods of making such compositions and uses of such compositions The method may be applicable to 3D printing objects, such as composites of materials. Such objects and The composite is formed by printing a model using a plurality of model inks according to the present disclosure onto a substrate; The support structure can be removed in a later step. The material is permeated by the supporting material, or vice versa, providing a supporting structure to the finished object. This may include holding.

[0188] 12A and 12B, which show schematic diagrams of objects constructed from different materials. In many cases, the desired object will have various The first object may include a variety of materials and may further include multiple coating layers. The bulk material 1202 of the bodies 1200 and 1201 includes a coating on the outer surface of the first object. A layer of material 1204 is laminated thereon.

[0189] Referring to FIG. 12B, in one embodiment, a plurality of layers 1204 and 1206 are provided on a bulk material 1202. and 1206. In an alternative technique, one layer is printed with one material and another A layer is printed with another material. In special cases, the outer surface of the object or the surface of the object and the top layer The coating-like material 1206 between the object and the surface is impregnated. Including a gradual decrease in the ratio of impregnated material to bulk material as distance increases. In this way, changes in color, thermal, or mechanical properties can be observed as the gradient changes. It is possible to create functionally graded materials that realize a variety of functions.

[0190] Referring to FIG. 13A, an object constructed of a mixture of materials according to the present disclosure is shown. In this embodiment, the object 1300 has two or more The object 1300 includes a mixture of the first material (1304) and the second material (1305). 06). Referring to FIG. 13B, a close-up of a section of object 1300 shows The material blending is done by applying the material 1 to each pixel (1312 and 1314). It can be seen that it is composed of 304 and 1306.

[0191] Methods and systems for printing mixed materials One technique for printing an object with a mixture of materials according to the present disclosure at a given location in a layer is to print the layer This is done by distributing one material to certain pixels and another material to other pixels. Multiple inks and ink heads can be used to create a print between the object material and the object support. According to one embodiment, one ink is used for printing the object and the supporting structure. Both can be used to build up (layer by layer) the different inks on the object or the support. The layer is distributed only in the part belonging to only one of the materials, thereby causing a difference in the mechanical properties of both materials. This difference can give the finished object improved desired properties or improve the printability. For example, WC particles can be used to facilitate removal of the support from the object after printing. The first ink can be used to print both the object layer portion and the support layer portion. A second ink, such as a dye or particles, can be dispensed only on the object portion of the layer. After the printed composite is baked in an oven, a substantial difference between both materials is introduced ( A support of only WC grains would not be sintered, and the body would be sintered or at least sintered with WC in cobalt. (formed in a solid matrix). This difference allows the support to be removed from the object.

[0192] [System for printing mixed materials] As shown, the method comprises the steps of: forming a composite three-dimensional product from at least two different materials; A manufacturing system is described. In one embodiment, the system includes a first object material layer. a first group of print nozzles configurable to print additively and to print a layer of a second object material; a second nozzle group configurable to print by adding a second nozzle group; In one embodiment, the first object material is a metal. , the second object material is ceramic.

[0193] The above-mentioned system receives an instruction to print a composite three-dimensional product, and performs a first printing process according to the instruction. at least one printhead configured to control the first printhead group and the second printhead group; For example, in one embodiment, the first print head may further include a processor. The first and second printheads are arranged to sequentially form a product from multiple additive layers. The first nozzle group and the second nozzle group are controlled in this manner to form a common layer on a pixel-by-pixel basis. Depositing a first object material and a second object material, respectively, and then depositing the first object material in a subsequent layer. In one embodiment, subsequent layers are deposited on the first object material and the second object material, respectively. A second object material pixel located above the pixel and a first object material pixel located above the second object material pixel 1 includes at least one of the object material pixels.

[0194] In one embodiment, the controller is configured to interface the first object material with the second object material. The device is configured to allow the user to

[0195] In one embodiment, the controller is configured to: The encapsulation is also configured to encapsulate a portion of the encapsulation.

[0196] In one embodiment, the first set of nozzles deposits a layer of a first object material from a first ink composition. and a second group of nozzles configured to print a second ink composition from the second ink composition. In one embodiment, the first ink is configured to print an additional layer of the object material. The first ink composition and the second ink composition are jetted together in liquid form and when combined The composition is selected so that there is substantially no phase separation or diffusion between the first ink and the second ink. Includes powder.

[0197] In one embodiment, the product is a raw portion, and the raw portion comprises between 2% and 20% by volume, e.g. The binder may be present in an amount ranging from 4% to 15%, or from 5% to 10%.

[0198] In one embodiment, the raw portion is 50% to 70% by volume, for example 55% to 65% by volume. It contains a range of amounts of solid particles.

[0199] In one embodiment, the green part has a porosity in the range of 2% to 20%, for example 5% to 10%. Yes.

[0200] In another embodiment (see flow diagram in FIG. 14), supports that remain an integral part of the finished product are In this embodiment, the support can be used to create a composite material. can infiltrate the porous model to produce a composite material. No need to remove the support. This method allows for materials that can be created using a single sintering step, which This simplifies processing and reduces the cost of producing the composite material. The composite material can exhibit improved physical and chemical properties.

[0201] [Method of forming composites by printing mixed materials] Referring to FIG. 14, an exemplary process 1400 includes a metal oxide substrate 1408. It starts with a printing step 1405 which forms a model 1406 on the At temperatures between 500 and 800°C, oxygen is removed from the metal oxide and it is reduced to the metal. This involves heating the print at 400°C. The decomposition of the metal oxide causes the model to be surrounded by another metal. When heating at high temperatures was continued, the model and supporting particles 1412 did not change in size. As a result, brown portions 1414 are formed. Finally, at high temperature 1420 The supporting metal melts and infiltrates the porous model, forming a composite of the model material and the supporting metal. 1425 is formed.

[0202] In one embodiment, a model made of tungsten carbide (WC) and cobalt oxide (CoO and a support made of CoO. The method uses the fact that the oxide is lost at temperatures above 500°C: 3 O 4 →CoO→C o. In addition, WC, due to its grain shape (sharp edges), can be easily disintegrated without changing the geometric shape. It is known that WC starts sintering at temperatures above 900°C. In other words, WC is not round. Therefore, particles larger than one tenth of a nanometer begin to harden at 900°C. This is because the sharp edges of the particles connect to the surfaces of nearby particles and form physical connections between the particles.

[0203] When the temperature reaches 1400°C, the cobalt penetrates the inherent porosity of the WC to create a composite material. Complete.

[0204] In addition to the one-step sintering process, this method eliminates the use of support material (the support material is discarded). In this process, the model and the support Many combinations of materials can be used and there is no contamination between the support and the model material. For example, it is very easy to prepare a support ink from metal oxides or ferrous carbonate. It is known that...

[0205] In one embodiment, a model material comprising WC and a support material comprising ferrous carbonate are disclosed. At 800°C, ferrous carbonate changes to ferrous oxide, and at temperatures above 900°C, it becomes oxidized. It is known that WC loses its strength when heat-treated at 1500°C.

[0206] Model materials containing WC were prepared using a variety of support materials, including metal oxides, including copper oxide and cobalt oxide. Further support options include Fe oxide and Co oxide. At high temperatures (e.g. >500°C), oxides decompose. If the temperature is increased further, permeation will occur.

[0207] [Additive printing system for simultaneous printing and coloring] As previously mentioned, the disclosed system can be colored to provide a product having a desired color. The composite can be further modified by printing an external coating. In this embodiment, the colored structural particles are used to simultaneously print the product. An additive printing system for printing and coloring is further described.

[0208] [System for simultaneously printing and coloring products] The above description is relevant to this embodiment and the following description. In one embodiment, the first a first group of printheads configurable to apply and print a first colored build material of a color of and printing a second colored construction material having a second color different from the first color. and a second printhead group configured to hold at least one print head. A system including a head region is described.

[0209] In one embodiment, the systems described herein provide for the desired structural and color properties of a product. The system further comprises at least one processor configured to receive the reflecting information. Based on information reflecting the desired structural and color characteristics of the product, a first group of printheads and a second group of printheads are The two print head groups are adjusted to form a simulated product. The colored particles are mixed in controlled proportions for the desired color characteristics.

[0210] The systems described herein include at least a third color that is different from the first and second colors. at least a third colored construction material that can be configured to be printed on the substrate; The print heads may further comprise a print head group. In one embodiment, the first colored structural material, the second the colored structural material, and the third colored structural material, after sintering, have a simulated desired color characteristic. The mixture can be sintered so that

[0211] In one embodiment, at least a third group of printheads includes at least a third deposition A color structure material can be added and printed, the color structure material can be configured to include a plurality of subgroups, each subgroup being The groups can be configured to be printed with different colored build materials.

[0212] As previously described herein, the first colored structural material, the second colored structural material, and at least The third colored structural material may include ceramic particles. The child is Al2 O 3 , TiO 2 , Y 2 O 3 , CoO, CuO, ZnO, MgO, ZrO 2 , and FeCO 3 may be selected from at least one of the following:

[0213] In one embodiment, a first colored structural material, a second colored structural material, and at least a third colored structural material are The colored construction materials include those previously described herein. For example, the first, second and third colored The structural materials are iron, copper, silver, gold, titanium, and SiO 2 , TiO 2 , BiO 2 , W.C., Al. 4 C 3 At least one selected from the group consisting of titanium-based composites, titanium carbide ... The particles may include metallic particles such as one metal, metal oxides, carbides, and metal alloys.

[0214] In one embodiment, a first colored structural material, a second colored structural material, and at least a third colored structural material are The colored structural material includes synthetic structural particles as previously described herein. For example, synthetic structural particles Polyaniline alcohol (PAN) polymer, ethylene vinyl acetate copolymer, ethylene Cellulose, Carboxymethylcellulose, Hydroxypropylmethylcellulose, Vinegar a cellulose polymer selected from cellulose acetate and a copolymer selected from polybutyral; The copolymer may include sol-gel derived silica, tetraethoxysilane (TE OS) and 3-glycidyloxypropyltrimethoxysilane.

[0215] 1. An additive manufacturing system for forming an object having a desired surface color, comprising: an inner core portion; a first group of printheads configurable to print a three-dimensional object having an outer surface; a color coating having a different color from the color of the first color coating; At least one printhead region configured to hold two printheads. The second group of printheads is configured to deposit a plurality of different colors.

[0216] The additive manufacturing system can be used to create a desired shape of an object and a color that varies across the surface of the object. receiving a 3D digital representation of an object including a desired surface coloration with shading; and applying the desired surface coloration to the object; at least one configured to analyze and identify a color shade in a desired surface coloration; The device may further include a processor.

[0217] The processor controls the first group of print heads to additively form the three-dimensional object. During the addition of the body, a second print deposits a mixture of varying colors across the surface of the object. The heads are controlled to simulate shades of color corresponding to desired variable surface coloration across the surface of the object. The device may be further configured to emulate

[0218] In one embodiment, the at least one processor analyzes the desired coloring for each pixel. A second set of printheads is then used to deposit different colors to simulate the desired coloring for each pixel. For example, the second printhead group is configured to print CMYK [cyan, magenta, Uses multiple printheads separated into colors (center, yellow, and key (black)) It may also be configured to print colored ceramic materials.

[0219] In one embodiment, the first printhead group is configured to print cores from metal. The metal subgroup includes a ceramic core and an outer surface adjacent to the metal core that is printed from a ceramic material. and a ceramic subgroup made up of, for example, stainless steel. and titanium, Ti64; the ceramic subgroup includes S iO 2 , TiO 2 , ZrO 2 , BiO 2 At least one of the following is configured to print: do.

[0220] In one embodiment, the second group of printheads are made of a glossy after sintering material such as glass. The method can be configured to deposit a material to provide a transparent coating having a good adhesion. In an embodiment, a first group of print heads is configured to print the inner core. a first subgroup and a second subgroup configured to print an outer surface portion. When printing artificial teeth using an additive manufacturing system, The first group of print heads includes a first subgroup configured to print the inner core of the artificial tooth. A second subgroup configured to print a loop and an outer surface portion of an artificial tooth.

[0221] It is contemplated that the disclosed inks may be printed using inkjet printing technology without departing from the scope of the present disclosure. The ability to make various modifications and variations to the methods of forming the titanium parts and Alternative implementations will be apparent to those skilled in the art in light of the specification and practice disclosed herein. It will be apparent to one skilled in the art upon consideration of the following detailed description and examples. . [Explanation of symbols]

[0222] 100 Additive Manufacturing Equipment 102 Print area 106 Printhead 110 Ink Reservoir 120 Controller 122 Printing surface

Claims

1. 1. A system for manufacturing a product, comprising: a first group of printheads configurable to additively print at least a first portion of the product with a first material having a first average grain size, the first average grain size selected to provide a first sintering characteristic; and a second group of printheads configurable to apply and print at least a second portion of the product with a second material having a second average particle size, the second average particle size selected to provide a second sintering characteristic; at least one print head region configured to hold receiving information reflecting desired characteristics of said product; Coordinating the first and second printheads to dispense the first and second materials in layers to impart different properties to different portions of the product based on information reflecting desired properties of the product. At least one processor configured to Including, The at least one processor is further configured to cause the first material and the second material to intermix and intersperse with one another during deposition.

2. The system of claim 1 , wherein the at least one processor is configured to determine a distribution of the first material and the second material to achieve a desired characteristic of the product.

3. The system of claim 2 , wherein the desired property of the product comprises a thermal, mechanical, chemical, electrical, or physical property.

4. 4. The system of claim 3, wherein the desired properties of the product include coefficient of thermal expansion, thermal conductivity, thermal diffusivity, wear resistance, brittleness, ductility, elasticity, stiffness, toughness, yield strength, color, density, hardness, corrosion, oxidation resistance, and combinations thereof.

5. The system of claim 1 , wherein the sintering characteristics include at least one of a sintering temperature and a shrinkage coefficient.

6. 10. The system of claim 1, wherein the at least one processor is configured to coordinate the first and second printhead groups to dispense the first and second materials in different amounts determined by weight or volume.

7. The system of claim 1 , wherein the first material and the second material share at least one element but have different average grain sizes and different sintering temperatures.

8. The system of claim 1 , wherein the first material and the second material have different chemistries but the same sintering temperature.

9. The system of claim 1 , wherein the first and second materials, when mixed and interspersed with one another, form a unitary structure without separation in different portions of the product.

10. 10. The system of claim 9, wherein the ratio between different materials that are mixed and interspersed with one another varies in different portions of the product depending on the desired characteristics of the product.

11. The system of claim 10 , wherein at least one of the first material and the second material is deposited to permeate the other to form one or more strings in the other.

12. The system of claim 1 , wherein the at least one printhead region is further configured to hold a third group of printheads.

13. 13. The system of claim 12, wherein the third printhead group is configurable to print with an additional removable support material that temporarily supports the printed first material and the second material.

14. The system of claim 1 , wherein the first portion comprises a core of an object and the second portion comprises a periphery of the object.

Images