Radio Frequency (RF) Tunable Resonant Materials and Material Configurations

Abstract

To provide: a novel sensor for sensing an operational condition such as wear on plies and / or treads of a tire; and a tire including the system.SOLUTION: In one aspect, plies and / or treads include resonators that generate resonance signals in response to being activated by an externally generated excitation signal or a locally generated power. Multiple resonators formed of carbon-containing materials are disposed on the plies and / or treads to respond to alterations in a tire by changing characteristics of the resonance signals. Such changes thereof include a frequency shift of the resonant signals and / or attenuation of the resonant signals. The resonators are configured to resonate at a first frequency when structural characteristics of the respective plies or treads are higher than a certain level, and at a second frequency different from the first frequency when they are not higher than the level.SELECTED DRAWING: Figure 7C2

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This patent application is a continuation of U.S. patent application Ser. No. 16 / 829,355, entitled "TIRES CONTAINING RESONATING CARBON-BASED MICROSTRUCTURES," filed March 25, 2020; U.S. patent application Ser. No. 16 / 829,385, entitled "TUNED RADIO FREQUENCY (RF) RESONANT MATERIALS," filed March 25, 2020; U.S. provisional patent application Ser. No. 62 / 824,440, entitled "TUNING RESONANT MATERIALS FOR VEHICLE SENSING," filed March 27, 2019; U.S. provisional patent application Ser. No. 62 / 979,215, entitled "WASTE ENERGY HARVESTING AND POWERING IN VEHICLES," filed February 20, 2020; and U.S. provisional patent application Ser. No. 62 / 979,215, entitled "RESONANT SERIAL NUMBER IN VEHICLE SENSING" filed February 20, 2020. This application claims priority to U.S. Provisional Patent Application No. 62 / 985,550, filed March 5, 2020, entitled "FOR VEHICLE CROSS-SECTION TIRES," all of which are assigned to the assignee hereof, and all of the prior applications to which this disclosure pertains are considered part of and incorporated by reference in this patent application.

[0002] The present disclosure relates to sensors that detect changes in present materials, compositions, and / or performance, and more particularly to techniques for sensing tire ply and / or tread wear. [Background technology]

[0003] Advances in vehicle power types, including hybrid and electric-only systems, have created opportunities for further technology integration. This is especially true as vehicles transition to fully autonomous driving and navigation, where technology (as opposed to trained, competent humans) must constantly monitor the performance and reliability of vehicle components to continuously ensure the safety and comfort of vehicle occupants. Traditional systems, such as tire pressure monitoring systems (TPMS), may not be able to provide the high level of fidelity required for high-performance (e.g., racing) or fully autonomous applications. Such applications may present unique challenges, such as the rapid wear on vehicle components (e.g., tires) encountered in demanding driving or racing, or the absence of a human driver available to check tire performance during vehicle operation. Summary of the Invention

[0004] This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or important features of the claimed inventive subject matter, nor is it intended to limit the scope of the claimed inventive subject matter. Moreover, the systems, methods, and devices of the present disclosure each have several innovative aspects, no single one of which is solely responsible for the desirable attributes disclosed herein.

[0005] One innovative aspect of the inventive subject matter described in this disclosure can be implemented as a tire formed from at least one body including a plurality of plies. At least one of the plurality of plies can include a resonator configured to generate a resonant signal in response to a signal. A carbon-containing material can be distributed in one or more portions of the ply and configured to modify at least one characteristic of the resonant signal.

[0006] In some embodiments, modifying the at least one characteristic can include one or more of shifting a frequency of the resonant signal or attenuating the resonant signal in proportion to an amount of wear of one or more of the plurality of plies, which can be configured to attenuate the resonant signal with a shield. The amount of attenuation can be based on a thickness of one or more of the plurality of plies. The amplitude of the attenuated resonant signal can be indicative of tire wear.

[0007] In some embodiments, the resonator can be configured to resonate at a first frequency when a structural characteristic of each ply of the plurality of plies is above a certain level, and can be configured to resonate at a second frequency different from the first frequency when the structural characteristic of each ply is not above the level. The resonator can be configured to vibrate at a frequency based on the rotational speed of the tire.

[0008] In some implementations, the resonator can begin to vibrate upon receiving an electric charge from a charge-generating device that can be embedded within each ply of the plurality of plies. In some aspects, the charge-generating device can include any one or more of a tribological component and a hexagonal carbon triboelectric energy generator (CH-TENG).

[0009] In some embodiments, the resonator can include a plurality of three-dimensional (3D) assemblies formed from graphene sheets that are bonded together to create a 3D hierarchical open porous structure. In some aspects, the tire can include a sensor formed from a carbon-containing material such that the sensor can be embedded within the tire innerliner.

[0010] In some embodiments, the plurality of plies can include at least a first ply having a first resonator configured to resonate at a first frequency, a second ply having a second resonator configured to resonate at a second frequency different from the first frequency, and a third ply having a third resonator configured to resonate at a third frequency different from the first and second frequencies. In some aspects, the first ply can form an outer layer of the tire. Attenuation of the first frequency can indicate wear or deterioration of the first ply. The second ply can be disposed over the first ply, and the third ply can be disposed over the second ply. Any one or more of the first ply, second ply, and third ply can be in contact with each other.

[0011] Another innovative aspect of the inventive subject matter described in this disclosure can be implemented in a tire including a body with a plurality of plies. Each ply of the plurality of plies can include a charge-generating device and a resonator electrically coupled to the charge-generating device within at least one of the plurality of plies. The resonator can be configured to generate a resonant signal in response to an electric charge generated by the charge-generating device. A tread surrounds the body.

[0012] In some implementations, at least a portion of each ply of the plurality of plies can be configured to attenuate a resonant signal generated by a corresponding resonator. The amount of attenuation can be indicative of wear or degradation of the respective ply. At least one ply of the plurality of plies can be configured to attenuate the corresponding resonant signal by shielding. In some aspects, at least one ply of the plurality of plies can be configured to alter the frequency of the corresponding resonant signal based on degradation of the at least one ply.

[0013] One innovative aspect of the inventive subject matter described in this disclosure can be implemented as a tire including a body and a plurality of plies surrounding the body. At least some of the plurality of plies can include a plurality of carbon-based microstructures distributed in one or more portions of each of the at least some plies. Each ply of the at least some plies can be configured to resonate at one or more corresponding natural frequencies.

[0014] In some embodiments, one or more of the plurality of carbon-based microstructures comprises a plurality of three-dimensional (3D) assemblies formed from graphene sheets, which are bonded together to create a 3D hierarchical open porous structure. The 3D hierarchical open porous structure can comprise mesoscale structuring. One or more of the plurality of carbon-based microstructures can comprise a porous arrangement formed within the 3D hierarchical open porous structure. In some embodiments, the graphene sheets can comprise one or more of single-layer graphene (SLG), few-layer graphene (FLG), or multi-layer graphene (MLG).

[0015] In some embodiments, the additive material can be configured to modify surface functional groups on exposed surfaces of at least some of the plurality of plies. One or more material properties of the carbon-based microstructure can be configured to be defined during synthesis of the carbon-based microstructure.

[0016] In some embodiments, each carbon-based microstructure of the plurality of carbon-based microstructures can be self-assembled. The carbon-based microstructures can be nucleated from homogeneous nucleation. The carbon-based microstructures can be configured to grow at least in part by a vapor flow that can flow at least in part near a plasma. The vapor flow can flow at a pressure range between vacuum and substantially atmospheric pressure.

[0017] In some embodiments, the carbon-based microstructures can be grown from carbon-based gas-phase species, and the growth can be controlled by gas-solid reactions under non-equilibrium conditions. One or more of the plurality of carbon-based microstructures is configured to resonate at a natural frequency in response to a ping from a transceiver capable of interacting with a tire pressure monitoring system (TPMS).

[0018] In some embodiments, the plurality of carbon-based microstructures can be configured to damp one or more resonant signals in proportion to the degree of wear experienced by the tire. The amplitude of each one of the damped resonant signals can indicate the degree of wear. Each ply of at least some of the plies can be configured to generate a respective resonant signal of the one or more resonant signals by resonating in response to an excitation signal.

[0019] In some embodiments, at least one of the plurality of carbon-based microstructures resonates at one or more known signature frequencies. A thickness of the at least one ply can be configured to at least partially attenuate the amplitude of the one or more known signature frequencies. In some aspects, one or more of the plurality of plies can be configured to resonate at a frequency that is shifted away from the one or more known signature frequencies based on a change in dielectric constant.

[0020] Another innovative aspect of the inventive subject matter described in this disclosure can be implemented in a tire including a body and a tread surrounding the body. The tread can include a plurality of plies. At least some of the plurality of plies can include a plurality of microstructures configured to resonate at one or more frequencies specific to each of the plurality of plies. At least one of the microstructures can have a shape resembling any one or more of an oval, ellipse, rectangle, square, circle, line, or combination of lines.

[0021] The details of one or more embodiments of the subject matter described in this disclosure are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages will become apparent from the description, drawings, and claims.

[0022] Embodiments of the inventive subject matter disclosed herein are illustrated by way of example, and are not intended to be limited by, the figures of the accompanying drawings. Like numbers refer to like elements throughout the figures and specification. It should be noted that the relative dimensions of the following figures may not be drawn to scale. [Brief explanation of the drawings]

[0023] [Figure 1A] According to some embodiments, an in-situ vehicle control system is presented that includes various sensors formed from carbon-containing composite materials that are tuned to exhibit a desired radio frequency (RF) signal resonance and response when a ping sound is emitted. [Figure 1B] 1 illustrates a signal processing system for analyzing a frequency-shifted and / or attenuated chirp signal by a sensor formed from a carbon-containing RF-tuned resonant material, according to some embodiments. [Figure 1C] 1 illustrates a signal processing system that analyzes time-varying telemetry signals generated by (or otherwise associated with) self-powered telemetry, according to some embodiments, where these signals are frequency shifted and / or attenuated by sensors formed from carbon-containing RF-tuned resonant materials. [Figure 1D] 1 is a representation of characteristics associated with on-board power telemetry incorporated into a tire of a vehicle, according to some embodiments. [Figure 2A] 1 illustrates a sensing stack including alternating layers of carbon-containing resin and carbon fiber in contact with each other, according to some embodiments. [Figure 2B1] 1 illustrates the frequency shift phenomenon as exhibited by a sensing stack including a carbon-containing RF tuned resonant material, according to some embodiments. [Figure 2B2]1 illustrates the frequency shift phenomenon as exhibited by a sensing stack including a carbon-containing RF tuned resonant material, according to some embodiments. [Figure 2B3] 1 is a graph illustrating an idealized change in RF resonance as a function of deflection, according to some embodiments. [Figure 2B4] 10 is a graph illustrating the change in RF resonance for four and five layer stacks, according to some embodiments. [Figure 2C] 1 illustrates a surface sensor deployment in a vehicle area, according to some embodiments. [Figure 2D] 2D illustrates various current generation systems that can be integrated with the surface sensor deployment shown in FIG. 2C, according to some embodiments. [Figure 2E] 1 is a presentation of characteristics associated with examples of energy recycling in various classes of vehicles, according to some embodiments. [Figure 2F] 1 illustrates a table of various values ​​related to energy harvesting in a vehicle, according to some embodiments. [Figure 2G] 1 illustrates a table of various characteristics related to energy harvesting for a vehicle, according to some embodiments. [Figure 2H] 1 shows a collection of common materials used in triboelectric series organized according to some embodiments depending on polarity and / or polarizability. [Figure 2I] 1 illustrates a signature class classification system for processing signals received from a sensor formed from a carbon-containing RF-tuned resonant material, according to some embodiments. [Figure 3A] 1 illustrates a prior art pressure-based, battery-powered tire condition sensor, such as may be part of (or otherwise associated with) a tire pressure monitoring system (TPMS), according to some embodiments. [Figure 3B] 1 illustrates the operation of a vehicle tire with a sensor including a carbon-containing RF-tuned resonant material embedded in a tire ply, according to some embodiments. [Figure 3C]1 illustrates a series of tire condition parameters sensed from changes in RF resonance of various layers of carbon-containing RF-tuned resonant material, according to some embodiments. [Figure 3D] 10 illustrates a manufacturing technique for tuning multiple plies of a tire by selecting carbon-containing RF-tuned resonant materials from separate, independent reactors for incorporation into the body of a single tire assembly, according to some embodiments. [Figure 3E] 1 illustrates a first set of exemplary condition signatures emanating from a tire formed from a layer of carbon-containing RF-tuned resonant material, according to some embodiments. [Figure 3F1] 10 illustrates a second set of exemplary condition signatures emanating from a new tire formed with a layer of carbon-containing RF-tuned resonant material, according to some embodiments. [Figure 3F2] 10 illustrates a third set of exemplary condition signatures emanating from a tire after wear of several carbon-containing RF-tuned resonant materials, according to some embodiments. [Figure 3F3] 1 shows a graph of measured resonant signature signal strength (decibels, db) versus tire tread layer loss height (millimeters, mm) according to some embodiments. [Figure 3G1] 1 shows a schematic diagram of an exemplary conventional carbon material production chain, according to some embodiments. [Figure 3G2] 1 shows a schematic diagram of an exemplary conventional carbon material production chain, according to some embodiments. [Figure 4] 1 is a presentation of features related to waste energy harvesting and power supply in vehicles, according to some embodiments. [Figure 5A] 1 is a presentation of features related to waste energy harvesting and power supply in vehicles, according to some embodiments. [Figure 5B] 1 shows a schematic diagram illustrating the flow of charge carriers (within a semiconductor material) between hot and cold regions, according to some embodiments, which creates a voltage difference that allows a thermoelectric generator (TEG) to operate in low or no light conditions. [Figure 5C]

[0013] Some embodiments depict carbon-based materials that are incorporated into plies or treads within the body of a tire to tune electrical conductivity and / or are doped to generate power from waste heat. [Figure 5D] 1 shows a chart comparing power output versus heat flux magnitude (delta Celsius) associated with a thermoelectric power generation feature integrated into a tire, according to some embodiments. [Figure 6A] 1 is a presentation of properties associated with three-dimensional (3D) graphene for use in thermoelectric conversion (e.g., when incorporated into composite materials), according to some embodiments. [Figure 6B] 1 illustrates layered p-type-n-type (PN) junction semiconductor materials incorporated into engine components for power harvesting, according to some embodiments. [Figure 7A] 1 is a presentation of tire diagnostic related functionality, according to some embodiments. [Figure 7B] 1 is a graph of conventional materials incorporated into the rubber of a vehicle tire comparing normalized capacitance (C / C) versus rubber thickness (mm), according to some embodiments. [Figure 7C1] 1 shows a schematic diagram illustrating a complete tire diagnostic system and apparatus for impedance-based spectroscopy tire wear sensing, according to some embodiments. [Figure 7C2] 1 illustrates tire information being transferred via telemetry to a navigation system and to equipment for producing printed carbon-based materials, according to some embodiments. [Figure 7C3] 1 is a presentation of information related to tire condition sensing, according to some embodiments. [Figure 7C4] 1 illustrates a schematic diagram related to resonant serial number-based digital encoding of a vehicle tire by ply print encoding of the tire tread layer and / or tire body, according to some embodiments. [Figure 7C5]1 illustrates a schematic diagram related to resonant serial number-based digital encoding of a vehicle tire by ply print encoding of the tire tread layer and / or tire body, according to some embodiments. [Figure 7D] 1 shows a schematic diagram depicting various layers of a tire belt ply configured to generate electrical power or current through piezoelectric functionality, according to some embodiments. [Figure 8A] 1 presents information related to energy harvesting through the application of thermoelectric generators (TEGs), according to some embodiments. [Figure 8B] 1 presents information related to energy harvesting through the application of thermoelectric generators (TEGs), according to some embodiments. [Figure 9] 1 illustrates a cross-sectional schematic of a vehicle chassis, engine, and drivetrain illustrating powertrain losses (unusable for forward propulsion) associated with conventional vehicles, according to some embodiments. [Figure 10] 1 shows a schematic cross-sectional view of a vehicle equipped with a piezoelectric and / or thermoelectric current and / or power generator, according to some embodiments. [Figure 11] 1A-1C illustrate various schematic perspective views of a high-concept tire and various energy (current) delivery challenges, according to some embodiments. [Figure 12] 1 is a presentation of various properties associated with the application or incorporation of graphene into vehicle tires, according to some embodiments. [Figure 13A] 1 is a schematic side view of a vehicle tire incorporating graphene-filled rubber and contacting the ground or pavement, according to some embodiments. [Figure 13B] 1 is a presentation of information related to a triboelectric generator incorporated into a vehicle tire, according to some embodiments. [Figure 14A] FIG. 1 shows a schematic of charge generation on a rolling wheel (with a single electrode and a copper-laminated polydimethylsiloxane, PDMS, patch, according to some embodiments). [Figure 14B]FIG. 1 shows a schematic of charge generation on a rolling wheel (with a single electrode and a copper-laminated polydimethylsiloxane, PDMS, patch, according to some embodiments). [Figure 14C] FIG. 1 shows a schematic of charge generation on a rolling wheel (with a single electrode and a copper-laminated polydimethylsiloxane, PDMS, patch, according to some embodiments). [Figure 14D] 1 illustrates an exemplary rotor and stator configuration for a triboelectric generator or motor, according to some embodiments. [Figure 14E] Schematic diagrams are shown of various alternative triboelectric generators integrated into vehicle tires and the arrangement of an array of compressible hexagonal structure triboelectric energy nanogenerators (CH-TENGs) fixed within a rubber pneumatic tire, according to some embodiments. [Figure 14F] 1 illustrates various types of triboelectric energy generator arrangements intended for incorporation within vehicle tires, according to some embodiments. [Figure 15A] 1 is a presentation of information related to sensor-based monitoring of vehicle tires achieved through a tire pressure monitoring system (TPMS), according to some embodiments. [Figure 15B] 1 is a schematic side view of a substrate incorporating a substrate electrode, according to some embodiments. [Figure 15C] 1 is a schematic diagram of a polyimide-based strain gauge for monitoring tire pressure, according to some embodiments. [Figure 15D] 1 is a schematic cross-sectional view of a Hall sensor incorporating gallium arsenide (GaAs) on ceramic configured to sense deformation of a tire tread of a vehicle, according to some embodiments. [Figure 15E] 1A-1C illustrate various schematic diagrams associated with a non-contact ultrasonic electrical resistor-capacitor parallel circuit integrated onto a steel wire belt within a tire body, according to some embodiments. [Figure 15F] 1A-1C illustrate various schematic diagrams associated with a non-contact ultrasonic electrical resistor-capacitor parallel circuit integrated onto a steel wire belt within a tire body, according to some embodiments. [Figure 15G] 1A-1C illustrate various schematic diagrams associated with a non-contact ultrasonic electrical resistor-capacitor parallel circuit integrated onto a steel wire belt within a tire body, according to some embodiments. [Figure 15H] 1A-1C illustrate various schematic diagrams associated with a non-contact ultrasonic electrical resistor-capacitor parallel circuit integrated onto a steel wire belt within a tire body, according to some embodiments. [Figure 16] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 17] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 18] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 19] 16-18 show Raman shift plots for one or more of the structured carbons shown in FIGS. 16-18 and / or the like, according to some embodiments. [Figure 20] 1 illustrates a schematic perspective view of an exemplary grid arrangement of elements (such as rubber) in a tire tread layer and / or ply, with resonant circuit components embedded within or between these elements, according to some embodiments. [Figure 21] 22 is an exemplary Raman intensity heat map or plot illustrating signal attenuation associated with the resonant circuit shown in FIG. 21 when incorporated into a vehicle tire body ply and / or tread layer during operation, according to some embodiments. [Figure 22] 1 is a schematic diagram illustrating an exemplary arrangement of self-assembled carbon-based particles, according to some embodiments. [Figure 23A]1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23B] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23C] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23D] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23E] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23F] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23G] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23H] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23I] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23J]1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23K] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23L] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23M] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23N] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23O] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23P] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23Q] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23R] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23S]1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23T] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23U] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23V] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23W] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23X] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. [Figure 23Y] 1 illustrates structured carbon, various carbon nanoparticles, various carbon-based aggregates, and various three-dimensional carbon-containing aggregates, according to some embodiments, grown on other materials. DETAILED DESCRIPTION OF THE INVENTION

[0024] Various embodiments of the inventive subject matter disclosed herein generally relate to deploying durable sensors containing carbon-based microstructures within vehicle components, such as within the body plies of conventional, currently commercially available pneumatic tires (referring to those filled with air, nitrogen, or other gases) and next-generation airless solid tires. There are also configurations in which sensors such as these containing carbon-based microstructures (as an alternative to, or in addition to, tire ply embodiments) can be incorporated within the portion of the tire tread, which refers to the rubber above the tire tread perimeter that contacts the road or ground. As tires are used, the tread wears away, limiting its effectiveness in providing traction. Consequently, at least some of the carbon-containing sensors degrade and wear away, allowing the absence of these sensors to be detected by appropriately equipped components.

[0025] The referenced carbon-based or carbon-containing microstructured materials can be utilized for implementation in either of the two scenarios discussed above, including (1) within tire plies and / or (2) within tire treads. These carbon-based or carbon-containing microstructured materials can be tuned during in-flight synthesis (e.g., in a chemical reactor or reaction vessel) to achieve specific and desired radio frequency (RF) signal shifting (referring to frequency shifting) and signal attenuation (referring to signal strength reduction) behavior with respect to the emitted RF signal, for example, by a transceiver mounted in one or more wheel wells of a vehicle equipped with the system of the present disclosure and / or by an LC circuit, also referred to (interchangeably) as a tank circuit, an inductor-capacitor (LC) circuit, or a resonator.

[0026] Because the disclosed configurations function independently of moving parts, such as those often required for conventional tire pressure monitoring systems (TPMS), they are less susceptible to wear and tear resulting from everyday road use and can be configured to communicate with or otherwise electronically cooperate with existing vehicle electronics, such as those implemented in automobiles for tire-related wear detection and communication. The target RF resonant frequency values ​​of the disclosed composite materials made from carbon microstructures can be further tuned by controlling the mechanism responsible for carbon-on-carbon synthesis, also referred to as "growth," within a reaction chamber or reactor. The disclosed carbon microstructures and other materials can exhibit interactions that result in target performance characteristics and behaviors suitable for similar or dissimilar end-use applications, such as low-pressure knobby off-road tires compared to treadless slick racetrack tires.

[0027] overview preface Advances in materials science and engineering have enabled carbon-based microstructured materials, including those with molecular structures, to be finely tuned to resonate, exhibit frequency-shifting behavior, and / or exhibit attenuation (in physics and wireless telecommunications, this refers to the gradual decrease in the intensity of a flux through a medium) at specified radio frequencies (e.g., 0.01 GHz to 100 GHz), which can be further refined to meet the needs of various end-use applications. Carbon-based microstructures can be self-assembled, or "grown," in a reactor from carbon-containing gas-phase species to produce highly modified three-dimensional hierarchical carbon-based structures. These three-dimensional hierarchical carbon-based structures can be embedded within one or more plies and / or treads of the body of a vehicle tire as sensors or within some other intended vehicle-related surface, component, and / or part.

[0028] Changes in the environment surrounding a vehicle equipped with the materials and systems of the present disclosure can affect the resonance, frequency shift, and / or signal attenuation behavior of the carbon-based structures. Therefore, even the slightest anomalies in the vehicle's tire performance, lifespan, and potential degradation on high-wear surfaces can be detected and communicated to the driver, passengers, or, more generally, for fully autonomous (driverless) vehicles, vehicle occupants in real time (as these changes occur). That is, signals can be attenuated to a certain extent by carbon-containing microstructures embedded at certain concentration levels within one or more plies and / or tread of the tire, allowing the presence of that ply or tread layer to be accurately and repeatedly determined. If the tread (and / or layers within the tread) exposed for contact with a road surface, such as pavement, eventually wears away due to repeated contact with the pavement (as experienced during driving), the response (as indicated by attenuation or lack thereof) to the emitted signal of that tread layer can indicate the presence or absence of that tread layer and the degree of wear. Abrupt or gradual transitions in weather or other environmental conditions can cause differences in the physical properties of the tuned carbon-based microstructures of the present disclosure, and these differences can be detected by observing changes in frequency shift and / or attenuation behavior.

[0029] Changes in the resonant frequencies in the RF range of these materials (such as those on the surface of one or more tread layers or those embedded within the tread layers) can be detected by stimulating the RF resonant material with a signal (having a known frequency) that is further emitted by a patterned resonant circuit (referred to herein as a "resonator," which may be 3D printed on the tire body ply) in response to a signal stimulus from a transceiver (which may be mounted within one or more wheel wells), and then observing the frequency shift of that emitted signal caused by the carbon-containing microstructures, or the degree of signal attenuation (also caused by the carbon-containing microstructures). The signal characteristics can be electronically monitored and analyzed to determine current environmental conditions and changes in weather conditions, such as heavy rain transitioning to sleet or road surfaces becoming slippery and very hazardous. Implementations other than tire plies on vehicles are also envisioned. For example, when the pressure of air flowing over sections of the vehicle's body, including ground effects such as splitters, canards, bumpers, side skirts, rear wings, spoilers, and / or the like, changes while the vehicle is in motion, this air pressure can slightly deform (or reposition) at least some sections of the vehicle's body, causing corresponding changes in the RF resonance of the sculpted carbon-based material used to form the airfoil. These changes in the RF resonance frequency (or frequencies) can be observed and compared to known, discrete calibration points to determine the air pressure measured at one or more predetermined sensing points on the vehicle's body at a given moment with very high fidelity and accuracy (otherwise unattainable with conventional techniques).

[0030] Materials (including composites composed of multiple constituents or materials) can be tuned to accommodate the specific operating needs of tires (on-road and off-road variants) mounted on vehicles. During vehicle operation, the tire is often subjected to extreme conditions in terms of physical stresses, strains, and deformations as well as vibrations. Tires can be constructed to include a body with one or more inner layers (referred to as a "ply" or "plies") surrounded by a tread that protrudes from the body. Both the plies and treads (each tread containing one or more tread layers) of these tires can be formed from materials that can be tuned to specific RF resonant frequencies. Conventional use of tires, such as that encountered during on-road operation of most road tires or during off-road operation of off-road tires (such as in mountainous or other rough terrain), can cause slight deformations in portions of the tire. These deformations can cause changes in the RF resonant frequency of any given material used to form the tire (causing an RF signal to "ping" when detected by that material). Such changes in resonant frequency (as indicated by either a frequency shift and / or attenuation of the emitted signal) associated with any one or more of the carbon-based microstructured materials of the present disclosure can then be detected and compared to known calibration points to ultimately determine conditions inside the tire, such as increased wear in certain areas, as well as environmental conditions (outside the tire) that may be affecting the tire.

[0031] Functionality Disclosed herein are methods, apparatus, and materials relating to an overall system for sensing changes in vehicle components with respect to the operational function of the overall system. As outlined above, articles are shown for constructing such vehicle sensing systems that can both (1) sense changes (such as due to environmental exposure or excessive use) and (2) report using sensors of carbon-based microstructured materials embedded in the surface (such as those used anywhere on the vehicle body) and / or embedded sensors (such as those used in tires).

[0032] Next, a theoretical rationale is presented as to why any minute amount of deviation (e.g., due to air pressure on the vehicle skin or the application of any external force in / on the tire) can be detected by processing the "signature" (which refers to the transmission, subsequent observation, and analysis of an RF signal) of a given tire ply and / or tread layer (or other such equipped surface or region) as indicated by a "ping," frequency domain return, etc. Various mechanisms for calibrating the observed signal signature (in a test setting) and processing the return signature (in an operational setting) are discussed.

[0033] A method (and associated apparatus) for manufacturing tires with embedded passive sensors in the form of tuned carbon structures that interact with the elastomer is also presented. The nature of the return signature when the embedded tire sensor emits a ping is discussed, as is a mechanism for manufacturing tires from multiple plies using various tuned carbons containing various tuned microstructures. These carbon-based microstructures can be on the micron-sized scale, or alternatively, can be any one or more of nanometer, micro, or even meso particle sizes down to the millimeter (mm) level.

[0034] Additional observations that can be utilized for tire (and potentially other areas as well) sensing are also explored, including (1) built-in power signatures from resonances in the GHz and MHz ranges, enabled by tribological generators generating currents during rotation of a vehicle tire and repeated friction and / or contact of that vehicle tire with the pavement or ground, etc. Such tribological components can be integrated or otherwise incorporated into multiple steel belts between elastomer layers in one or more vehicle tire plies.

[0035] Notably, tribological (referring to the study and application of principles of friction, lubrication, and wear in relation to the generation of energy to produce usable electrical current or power) effects can be utilized, for example, by creating patterns for conductive paths (which may be at least partially carbon-based) to accommodate the movement of electrical charge. In doing so, a charge generator (provided by the discussed triboelectric charging components) is created that, upon discharge, directs its charge into a suitably equipped resonator (also referred to as a resonant circuit, etc.) having a tunable natural frequency. As used herein, this natural frequency is in the MHz range (or lower). Thus, the resonator can be charged (and / or powered) by resonating (and thus emitting an RF signal) and discharging the triboelectric generator for the resonator. The resonator can be configured to accommodate repeated charge-discharge cycles and can be any one or more of a variety of shapes and / or patterns, including oval shapes, with unique resonant values ​​or characteristics (based on their materials of formation and / or their construction).

[0036] A change in the shape or orientation of the resonator can result in a corresponding change in any associated resonance constant. As a result, any change in the tire's physical properties due to deformation (under static conditions, such as internal tire pressure, or under dynamic conditions, such as those encountered when driving over Bott's Dots) can alter the shape or orientation of the resonator. Different patterns can be used to respond more sensitively to one type of deformation than another (e.g., referring to the lateral deformation that occurs when moving around a curve compared to the vertical movement that occurs when driving over gravel or a rough surface).

[0037] Individual components within an equipped vehicle can exhibit one or more unique "signatures" defined by carbon-containing microstructured materials. Such signatures result from exposure to RF signals in the KHz (or lower) range. Disclosed arrangements include those that can sense dynamic operating characteristics using embedded sensors (such as within the tire body plies and / or tread layers). Nevertheless, placing the aforementioned triboelectric charge generators within the tire plies near the tread allows for digital observation of vibrations as the tire rotates. Such vibrations, which are in the low Hertz range, can be used for dynamic sensing, such as revolutions per minute (RPM), as well as relatively more static testing, such as transmitting an indication about treadwear.

[0038] The disclosed carbon-based microstructured materials can support wear indication through both (1) externally generated "ping" signal emission and / or transmission to a frequency shift and / or signal attenuation detector, such as provided by a digital signal processing (DSP), computer chip, and / or transducer located within the wheel well or even within the wheel rim, and (2) a self-powered self-pinging function within the tire, facilitated by a tribological power generator embedded within the tire plies or the like providing charge and / or power to the resonator. Option (1) shown above can use an external transceiver (semiconductor chip) for both stimulus and response, while option (2) can utilize a tuned resonant circuit within the tire that is constantly resonating in a way that can be picked up by an external receiver (such as a semiconductor chip, but not necessarily requiring separately supplied transmission power).

[0039] A properly equipped and / or prepared receiver, transceiver and / or the like can distinguish between many different signatures and very accurately and precisely identify (pinpoint) a particular type of wear observed in a specific area, such as deterioration of the inboard-facing sidewall of a right front tire due to hard cornering on a course characterized by elevation changes.

[0040] Definition and Use of Diagrams Some of the terms used in this description are defined below for ease of reference. The presented terms and their respective definitions are not strictly limited to these definitions. Terms may be further defined by the term's use within this disclosure. The term "exemplary" is used herein to mean serving as an example, instance, or illustration, and not necessarily as a desired model representing the best of its kind. Thus, any aspect or design described herein as "exemplary" should not necessarily be construed as preferred or advantageous over other aspects or designs. Rather, use of the word exemplary is intended to present concepts in a concrete manner. As used in this application and the appended claims, the term "or" is intended to mean an inclusive "or" rather than an exclusive "or." Unless otherwise specified or clear from context, "X employs A or B" is intended to mean any of the natural inclusive permutations. That is, if X employs A, if X employs B, or if X employs both A and B, then "X employs A or B" is satisfied under all of the foregoing examples. As used herein, at least one of A or B means at least one of A, or at least one of B, or at least one of both A and B. In other words, the phrase is disjunctive, meaning free from context or expressing a choice between two mutually exclusive possibilities, such as "or" in "She asked whether he would go or stay." As used in this application and the appended claims, the articles "a" and "an" should generally be construed to mean "one or more" unless otherwise specified or clear from the context to refer to the singular form.

[0041] Various embodiments are described herein with reference to the drawings. It should be noted that the drawings are not necessarily drawn to scale, and that elements of similar structure or function are sometimes represented by similar reference symbols throughout the drawings. It should also be noted that these drawings are intended only to facilitate the description of the embodiments of the present disclosure and do not represent an exhaustive treatment of all possible embodiments, nor are they intended to impose any limitations on the scope of the claims. Furthermore, the illustrated embodiments need not express all aspects or advantages of use in any particular environment. The embodiments of the present disclosure are not intended to limit the scope of the claims.

[0042] System Structure 1A shows a block diagram of a vehicle condition sensing system 1A00 (intended to be mounted on a vehicle). The vehicle condition sensing system 1A00 can include a sensor such as an RF-tuned resonant component 108 comprised of a plurality of carbon-based microstructured materials, strong aggregates, weak aggregates, and / or the like, such as those disclosed by Stowell et al. in U.S. Patent Application No. 16 / 785,020, filed February 7, 2020, entitled "3D Self-Assembled Multi-Modal Carbon-Based Particle" (collectively referred to herein as "carbon-based microstructures"). The RF-tuned resonant component 108 can be incorporated into any one or more of an airfoil sensor 104, a glass sensor 1051, a tire sensor 106, and a transceiver antenna 102 on a vehicle, such as a conventional driver-driven automobile, or a fully autonomous pod, or a vehicle capable of operating to move vehicle occupants without a human driver.

[0043] The RF tuned resonant components 108 can be configured to electronically and / or wirelessly communicate, such as by measuring a shift or attenuation of the signal frequency, with any one or more of the transceiver 114, the vehicle central processing unit 116, the vehicle sensor data receiving unit 118, the vehicle actuator control unit 120, and the actuators 122, which may include doors, windows, locks 125, engine control 126, navigation / heads-up display 128, suspension control 129, and airfoil trim 130. The various RF tuned resonant components 108 can induce a shift in the observed frequency of the emitted RF signal via the emitted “chirp” signal 110 and / or via the “return” chirp signal 112 using the transceiver 114 (referred to as a “frequency shift,” which implies any change in frequency). References to a "return" chirp signal in chirp signal 1100 may refer to electronic observation or detection of a frequency shift or attenuation of the emitted chirp signal 110 (rather than an actual reflection or return of the signal from the sensor) to one or more of the RF tuned resonant components 108 integrated into any one or more of the airfoil sensors 104 and / or the like. Chirp signal 110 and return chirp signal 112 may be communicated to (and therefore evaluated by) any one or more of the vehicle central processing unit 116, the vehicle sensor data receiving unit 118, the vehicle actuator control unit 120, and / or the actuators 122. Vehicle condition detection system 1A00 may be implemented using any suitable combination of software and hardware.

[0044] Any one or more of the various depicted sensors of vehicle condition sensing system 1A00 can be formed from carbon-based microstructures that are tuned to achieve specific RF resonant behavior when "pinged" (meaning struck or otherwise contacted) by emitted RF signals. Vehicle condition sensing system 1A00 (or any aspect thereof) can be configured to be implemented in any conceivable vehicle use application, area, or environment, such as during adverse weather conditions including sleet, hail, snow, ice, frost, mud, sand, debris, rough terrain, water, and / or the like.

[0045] RF tuned resonant components 108 can be located around and / or on the vehicle (e.g., in the passenger compartment, engine compartment, or trunk of the vehicle, or on the body). As shown in FIG. 1A , the RF tuned resonant components can include an airfoil sensor 104, a windshield sensor 105, a tire sensor 106, and a transceiver antenna 102, any one or more of which may be implemented in newer vehicles during their manufacture, or (alternatively) may be retrofitted to existing vehicles regardless of the vehicle's age and / or condition. RF tuned resonant components 108 can be formed, in part, using readily available materials such as fiberglass (e.g., for airfoils) or rubber (e.g., for tires) or glass (e.g., for windshields). These conventional materials can be combined with carbon-based materials, growths, weak aggregates, strong aggregates, sheets, particles, and / or the like, which are self-nucleated in-flight from carbon-containing gas-phase species within a reaction chamber or reactor and (1) formulated to improve the mechanical (e.g., tensile, compressive, shear, strain, deformation, and / or the like) strength of the composite material in which they are incorporated, and / or (2) formulated to resonate at a specific frequency or set of frequencies (in the range of 10 GHz to 100 GHz). The variables governing the RF resonant properties and behavior of the material can be controlled independently of the variables responsible for controlling the material strength.

[0046] Radio frequency (RF)-based stimuli (such as those emitted by the transceiver 114 or those emitted by a resonator) can be used to emit RF signals to the RF-tuned resonant component 108, actuator 122 (and / or the like, such as sensors implemented within or on the RF-tuned resonant component 108), which can detect the resonant frequency or frequencies of those RF signals, as well as frequency shifts and patterns (which may be affected by internal or external conditions) observed in the attenuation of the emitted signals. For example, if an RF-tuned resonant component (such as the tire sensor 106) is specially prepared (referred to as being "tuned") to resonate at a frequency of approximately 3 GHz, the tire sensor 106, when stimulated by a 3 GHz RF signal, can resonate or vibrate by resonance (a harmonic phenomenon in which a previously passive string or vibrating body responds to an external vibration with harmonics that resemble the external vibration).

[0047] These resonant oscillations can occur at the stimulated frequency or as harmonics or side lobes derived from the fundamental 3 GHz tone. If a tuned resonant component (of the RF tuned resonant component 108) is tuned to resonate at 2 GHz, when the tuned resonant component is stimulated by a 2 GHz RF signal, the tuned resonant component will emit resonant oscillations as described above. These resonant oscillations can occur at the stimulated frequency or as harmonics or side lobes (in engineering, a local maximum in the far-field radiation pattern of an antenna or other radiation source that is not the main lobe) derived from the fundamental 2 GHz tone. Many additional tuned resonant components can be located proximate to the RF emitter. The RF emitter may be controlled to first emit a 2 GHz ping, then a 3 GHz ping, then a 4 GHz ping, and so on. This series of pings at different and increasing frequencies is called a "chirp."

[0048] Adjacent tire plies (such as those in contact with one another) within a tire body as generally shown by Figures 3F1-3F2 can have different concentration levels or arrangements of carbon-based microstructures to define sensors incorporated within that (respectively referenced) tire body ply and / or tread layer to resonate at different, distinct frequencies that are not harmonic with one another, i.e., the non-harmonic plies can ensure that certain tire body plies and / or tread layers (or other surfaces or materials) are separately and easily discernibly sensed relative to others with the lowest risk of contamination due to harmonic-induced (or otherwise related) signal interference.

[0049] The transceiver 114 (and / or a resonator, not shown in FIG. 1A ) can be configured to transmit the chirp signal 110 to any one or more of the RF-tuned resonant components 108 and digitally recognize the frequency shift and / or attenuation of the chirp signal 111 (referred to in FIG. 1A as a return signal 112) from any one or more of the RF-tuned resonant components 108. Such “return” signals 108 can be processed into digital information that can be electronically communicated to the vehicle's central processing unit 116, which interacts with the vehicle sensor data receiving unit 118 and / or the vehicle actuator control unit 120, which in turn transmits vehicle performance-related signals based on the received sensor data. The return signal 1120 can at least partially control the actuator 122. That is, the vehicle actuator control unit 120 may control the actuators 122 to operate any one or more of the doors, windows, locks 124, engine control 126, navigation / heads-up display 128, suspension control 129, and / or airfoil trim 130 according to feedback received from the vehicle sensor data receiving unit 118 regarding wear or degradation of vehicle components as indicated by RF tuned components in communication with the transceiver 114.

[0050] When monitoring the behavior of the chirp signal 111 (such as a frequency shift and / or attenuation), detection of road debris and adverse weather conditions can, for example, cause the actuator 122 to trigger corresponding changes in the suspension control 129. Such changes can include, for example, loosening the suspension settings to accommodate driving over road debris, followed by tightening the suspension settings to accommodate increased vehicle responsiveness that may be required for driving in heavy rain (and therefore low traction) conditions. The variations in such control by the vehicle actuator control unit 120 are many, and any possible condition external to the vehicle can be detected by the transceiver (as indicated by a frequency shift and / or attenuation of the chirp signal 110 and / or return signal 112).

[0051] Any of the RF-tuned resonant components 108 forming the described sensors can be tuned to resonate when stimulated at a particular frequency, where a defined shift in one or more frequencies (induced by the carbon-based microstructure) can form one or more signal signatures indicative of the material in which the sensor is incorporated or the state of that material.

[0052] The time variation or time deviation (TDEV) of the frequency shift (as shown in the signal signature) in the return signal 112 (which refers to the time stability of the phase x relative to the observation interval τ of the measured clock source, so the time deviation forms a standard deviation-type measurement indicative of the time instability of the signal source) can correspond to time-varying variations in the sensor's environment and / or time-varying variations in the sensor itself. Accordingly, a signal processing system (such as any one or more of the vehicle central processing unit 116, the vehicle sensor data receiving unit 118, and / or the vehicle actuator control unit 120, etc.) can be configured to analyze signals associated with the sensor (such as the chirp signal 110 and the return signal 112) according to TDEV principles. Results of such analysis (such as signature analysis) can be delivered to the vehicle central processing unit 116, which can in turn communicate commands to the vehicle actuator control unit 120 for appropriate responsive action. In some configurations, such responsive action by actuator 122 may include at least some input from a human driver, while in other configurations, vehicle state detection system 1A00 may function in a completely self-contained manner, allowing a vehicle so equipped to address component performance issues as they arise in a completely driverless setting.

[0053] 1B shows a block diagram of a signal processing system 1B00 that may include surface sensors 160 and embedded sensors 170, any one or more of which may be in electronic communication with others regarding environmental changes 150 for a vehicle so equipped (referring to a vehicle equipped with surface sensors 160 and embedded sensors 170). Signal processing system 1B00 may also include a transceiver 114, a signature analysis module 154, and a vehicle central processing unit 116, any one or more of which are in electronic communication with others.

[0054] The signal processing system 1B00 functions to analyze a signal signature (defined by digitally observing the frequency shift and / or attenuation of any one or more of the chirp signals 111 and / or corresponding “return” signals 112) when the sensor formed from the carbon-based microstructure is stimulated. As a result of stimulation by the chirp signal, the sensor becomes resonant at one of the chirp / ping frequencies and “responds” by resonating at or near its corresponding tuned frequency, shifting the emitted frequency, and / or attenuating the amplitude of the emitted signal. If an environmental change (such as wear of the tire body plies and / or tread layers) occurs while the chirp / ping is being emitted, the “return” signal can be monitored for variations in modulation either above or below the tuned frequency. Thus, the transceiver 114 can be configured to receive the “return” signal 112 representative of the surfaces emitting the pings, emitting pings on or against these surfaces, etc.

[0055] The chirp / ping signals can be emitted by the transceiver 114 (e.g., by inaudible RF signals, pulses, vibrations, and / or similar transmissions), and a “return” signal can be received by the same (or a different) transceiver 114. As shown, the chirp signal can occur during a repeating sequence of chirps (such as chirp signal 110). For example, the chirp signal sequence can be formed from a pattern including a 1 GHz ping, then a 2 GHz ping, then a 3 GHz ping, and so on. The entire chirp signal sequence can be repeated continuously in its entirety. There can be a short period between each ping so that a return signal (return signal 112) from the resonant material can be received immediately after the ping ends. Alternatively, or in addition, the signal corresponding to the ping stimulus and the observed “response” signal can occur simultaneously and / or along the same general path or route. The signature analysis module can use digital signal processing techniques to distinguish the observed “response” signal from the ping signal. In situations where the returned response contains energy across many different frequencies (harmonics, side lobes, etc.), a notch filter can be used to filter the stimulus. The returned signal received by the transceiver can be transmitted to the signature analysis module 154, which in turn can transmit a processed signal to the vehicle central processing unit 116. The preceding discussion of FIG. 1B includes a discussion of sensors formed from carbon-containing tuned resonant materials and may also reference sensing stacks as well.

[0056] FIG. 1C shows a block diagram of a signal processing system 1C00, which is substantially similar to the signal processing system 1B00 shown in FIG. 1B, and therefore redundant descriptions of similar features are omitted. Environmental changes 150, such as those indicating precipitation such as rain, snow, hail, sleet, and / or the like, can be indicated by a surface sensor 160 and / or an embedded sensor 170. Unlike the surface sensor 160, the embedded sensor 170 (which can be embedded in a material such as a tire ply) can use and / or be powered by a built-in power telemetry that includes a tribological energy generator (not shown in FIG. 1C). These tribological energy generators can also be embedded in the material in which the sensor is encapsulated. Thus, the tribological energy generator can generate usable current and / or power by, for example, recovering electrostatic charge accumulated between a rotating tire or wheel and the pavement it contacts, to power a resonant circuit (described in further detail herein). The resonant circuit can then resonate and emit an RF signal at a known frequency. As a result, an externally mounted transceiver unit (such as one mounted within each wheel well of the vehicle) can emit an RF signal. In this configuration, the resonant circuit further propagates these RF signals, is tribologically powered, and is embedded in the tire body ply. Similarly, the frequency shift and / or attenuation of the intensity of the emitted signal can be received and analyzed, for example, by the signature analysis module 154 and / or the vehicle central processing unit 166.

[0057] 1D is a presentation of characteristics 1D00 related to self-contained power telemetry (which refers to the collection of measurements or other data at a remote or inaccessible point and their automatic transmission to receiving equipment for monitoring) incorporated into a tire of a vehicle, according to some embodiments. The self-contained power telemetry referred to herein includes utilizing tribological charge generation within the tire, the storage of that charge, and the subsequent discharge of the stored charge into or through a resonant circuit, using "ringing" (which refers to oscillation of the resonant circuit responsive to further emission of an RF signal) that occurs during the discharge of the resonant circuit (which refers to an electrical circuit consisting of an inductor, represented by the letter L, and a capacitor, represented by the letter C, connected together and used to generate an RF signal at a specific frequency or frequencies).

[0058] The ping sound stimulus can generally be provided in one of two possible configurations of the vehicle component wear detection system of the present disclosure. One of these two possible configurations is: reliability to signals or "pings" generated by a stimulus source such as a conventional transceiver located on the outside of a tire (or other vehicle component intended to be monitored for wear through continued use) as installed within each wheel well of a vehicle so equipped; or The use of in-tire (also referred to as embedded in the tire plies, as well as sensors with carbon-based microstructures) tribological energy generators to recover energy resulting from the otherwise wasted frictional energy between the rotating wheel and / or tire and the ground or pavement in contact with them; Tribology, as generally understood and referred to herein, refers to the science and engineering study of interacting surfaces in relative motion. Tribological energy generating devices such as these can power in-tire resonating devices, which in turn self-transmit tire property telemetry.

[0059] Either of the two "ping" stimulus generators or providers discussed above can have complex resonant frequency (CRf) components in the range of approximately 10-99 GHz (e.g., due to the resonant frequencies of small-dimension structures such as graphene platelets), as well as lower frequency resonances in the KHz range due to the relatively larger-dimension discussed intra-tire resonances. In general, CRf can be considered to be equal to a function of the natural resonant frequency of the elastomer component, the natural resonant frequency of the carbon component, the ratio / assembly of the constituent components, and the geometry of the intra-tire resonator.

[0060] FIG. 2A shows a schematic cross-sectional side view of a sensing stack 2A00 (which may represent any of the sensors discussed in connection with those shown in FIGS. 1A-1D) composed of multiple layers arranged on top of one another, including (sequentially) carbon-containing resin 2042, carbon fiber 2022, carbon-containing resin 2041, and carbon fiber 2021. The term "resin" (in polymer chemistry and materials science) generally refers to a solid or highly viscous substance of plant or synthetic origin that is typically convertible into a polymer (a large molecule or macromolecule composed of many repeating subunits). Synthetic resins are industrially produced resins, typically viscous substances that are converted into rigid polymers during the curing process. To undergo curing, resins typically contain reactive end groups such as acrylates or epoxides. Additionally, the term "carbon fiber" refers to fibers approximately 5-10 micrometers (μm) in diameter and composed mostly of carbon atoms. Carbon fiber offers several advantages, including high stiffness, high tensile strength, low weight, high chemical resistance, high temperature resistance, and low thermal expansion.

[0061] Any one or more of the carbon-containing resin 2042, carbon fibers 2022, carbon-containing resin 2041, and carbon fibers 2021 can be tuned to demonstrate or exhibit one or more specific resonant frequencies when an RF signal emits a ping by incorporating specific concentration levels of any one or more of the aforementioned carbon-containing microstructures. The sensing stack can include any configuration, orientation, order, or layer of any one or more of the carbon-containing resin 2042, carbon fibers 2022, carbon-containing resin 2041, and carbon fibers 2021, and / or fewer or additional layers comprising similar or dissimilar materials. Additional resin layers can be layered between additional carbon fiber layers.

[0062] Each carbon-containing resin layer can be separately formulated to resonate at a different intended or desired tuning frequency. The physical phenomenon of material resonance can be explained in terms of the corresponding molecular composition. For example, a layer having a defined first structure, such as a first molecular structure, can resonate at a first frequency, while a layer having a different second molecular structure can resonate at a different second frequency.

[0063] A material contained within a layer with a particular molecular structure resonates at a first tuning frequency when the layer is in a low-energy state and at a different second frequency when the material within the layer is in an induced high-energy state. For example, a material within a layer exhibiting a particular molecular structure can be tuned to resonate at 3 GHz when the layer is in its natural, undeformed, low-energy state. In contrast, the same layer can resonate at 2.95 GHz when the layer is at least partially deformed from its natural, undeformed, low-energy state. As a result, this phenomenon can be tailored to address the need for high-fidelity and precision detection of even the slightest anomalies, such as those on a tire surface that contacts a road surface such as pavement and experiences severe wear at specific localized contact areas. Race cars racing on demanding race circuits (referring to highly technical, windy tracks characterized by sharp turns and rapid elevation changes) can benefit from such localized tire wear or degradation information to make informed tire replacement decisions, even under time-sensitive race-day conditions.

[0064] The frequency shift phenomenon (such as a transition from a resonance at a frequency of 3 GHz to 2.95 GHz) is shown above and discussed with reference to Figures 2B1-2B2, which depicts the frequency shift phenomenon as shown in a sensing stack including a carbon-containing tuned resonant material.

[0065] As is commonly understood, atoms emit electromagnetic radiation at frequencies characteristic of a given element. That is, atoms of a particular element have characteristic vibrational frequencies that correspond to the properties of that atom. For example, when a cesium atom is stimulated, its valence electrons jump from a low-energy state (e.g., the ground state) to a higher-energy state (e.g., an excited energy state). When the electrons return to their lower-energy state, they emit electromagnetic radiation in the form of photons. In the case of cesium, the emitted photons are in the microwave frequency range at 9.192631770 THz. Larger structures, such as molecules formed from multiple atoms, also resonate (e.g., by emitting electromagnetic radiation) at predictable frequencies. For example, liquid water in the bulk resonates at 109.6 THz. Water under tension (e.g., at the surface of the bulk, in various surface tension states) resonates at 112.6 THz. Carbon atoms and carbon structures also exhibit characteristic vibrational frequencies that depend on the structure. For example, the natural resonant frequency of carbon nanotubes (CNTs) depends on the diameter and length of the CNT tubes. Growing CNTs under controlled conditions to control the tube diameter and length allows for control of the natural resonant frequency of the structure. Thus, synthesizing or otherwise "growing" CNTs is one way to tune to a desired resonant frequency.

[0066] Other structures formed from carbon can be formed under controlled conditions. Such structures include, but are not limited to, carbon nano-onions (CNO), carbon lattices, graphene, carbon-containing strong or weak aggregates, graphene-based, other carbon-containing materials, artificial nanoscale structures, and / or combinations thereof, any one or more of which may be incorporated into sensors for vehicle components according to embodiments of the present disclosure. Such structures can be formed to resonate at specific tuned frequencies, and / or such structures can be modified by post-processing to obtain desired characteristics or properties. For example, desired properties such as high reinforcement values ​​can be achieved through the selection and ratio of material combinations and / or the addition of other materials. Furthermore, the juxtaposition of multiple such structures introduces additional resonance effects. For example, two graphene sheets can resonate with each other at a frequency that depends on the length, width, spacing, spacing geometry, and / or other physical properties of the sheets and / or their juxtaposition with each other.

[0067] As is known in the art, materials have specific, measurable properties. This applies not only to naturally occurring materials, but also to artificial carbon allotropes. Such artificial carbon allotropes can be tuned to exhibit physical properties. For example, carbon allotropes can be engineered to exhibit physical properties corresponding to (a) a particular arrangement of constituent primary particles, (b) the formation of strong aggregates, and (c) the formation of weak aggregates. Each of these physical properties affects the specific resonant frequency of a material formed using the corresponding specific carbon allotrope.

[0068] In addition to tuning a particular carbon-based structure to a particular physical configuration that corresponds to a particular resonant frequency, a carbon-containing compound can be tuned to a particular resonant frequency (or set of resonant frequencies), which set is referred to as a resonant profile.

[0069] Formation of frequency tuning materials Carbon-containing materials (such as those containing carbon-based microstructures) that are tuned to exhibit specific resonant frequencies when pinged by an RF signal can be tuned to exhibit specific resonant profiles by creating specific compounds that combine these materials to have specific electrical impedances. Similarly, different electrical impedances correspond to different frequency response profiles.

[0070] Impedance describes the difficulty that alternating current (AC) flows through an element. In the frequency domain, impedance is a complex number with a real and an imaginary component due to the structure behaving as an inductor. The imaginary component is the inductive reactance (the resistance of a circuit element to the flow of current due to its inductance or capacitance; the greater the reactance, the smaller the current for the same applied voltage). L which is based on the frequency f and inductance L of a particular structure in the following equation: TIFF0007796784000001.tif12114

[0071] As the received frequency increases, the reactance also increases, so that at a certain frequency threshold, the measured strength (amplitude) of the transmitted signal can be attenuated. Inductance L is affected by the electrical impedance Z of the material, which is related to the material properties of magnetic permeability μ and permittivity ε by the following relationship: TIFF0007796784000002.tif21114

[0072] Therefore, tuning the material properties affects the electrical impedance Z, which in turn affects the inductance L and therefore the reactance X. L changes to affect

[0073] Carbon-containing structures with different inductances, such as those disclosed by Anzelmo, et al. in U.S. Patent No. 10,428,197, entitled "Carbon and Elastomer Integration," issued October 1, 2019, which is incorporated herein by reference in its entirety, can exhibit different frequency responses (when used to create sensors in the aforementioned systems). That is, a carbon-containing structure with a higher inductance L (based on electrical impedance Z) will reach a certain reactance at a lower frequency than another carbon-containing structure with a lower inductance.

[0074] When formulating a compound to tune a particular electrical impedance, the material properties of magnetic permeability, permittivity, and conductivity can also be considered. Furthermore, if a first carbon-containing structure resonates at a first frequency, but the structure is subjected to a tension-inducing condition, such as when a second carbon-containing structure is slightly deformed (which slightly changes the physical properties of the structure), the structure is observed to resonate at a second frequency.

[0075] 2B1 shows a first carbon-containing structure resonating at a first frequency, which can be related to an equivalent electrical circuit including a capacitor C1 and an inductor L1. The frequency f1 is given by: TIFF0007796784000003.tif17114

[0076] FIG. 2B2 shows a slight deformation of the same first carbon-containing structure of FIG. 2B1. The deformation causes a change in the physical structure, which in turn changes the inductance and / or capacitance of the structure. These changes can be correlated to an equivalent electrical circuit including capacitor C2 and inductor L2. The frequency f2 is given by: TIFF0007796784000004.tif20114

[0077] 2B3 is a graph 2B300 illustrating an idealized change in measured resonance as a function of deflection. Optionally, one or more variations of graph 2B300, or any aspect thereof, can be implemented in accordance with the embodiments described herein. Graph 2B300 (or any aspect thereof) can be implemented in any environment.

[0078] The embodiment shown in FIG. 2B3 is merely an example. The graph shown illustrates one aspect of deformation, specifically deflection. When a member or surface undergoes deformation (e.g., bending) due to deflection, the deformation can change the member's exhibited resonant frequency when pinged by a signal, such as an RF signal. The shape of that curvature can depend on the properties of the member, such as the properties of the laminates forming the member or surface. This curvature can be steep with small variations, but when the deflection reaches a maximum, the curvature flattens out. Furthermore, the shape of the curvature depends in part on the number of layers in the laminate, the geometry of the carbon structure, how the carbon is bonded to the laminate, etc.

[0079] FIG. 2B4 is a graph 2B400 showing the change in resonance for a four-layer laminate 292 and a five-layer laminate 294. Optionally, one or more variations of graph 2B400, or any aspect thereof, can be implemented in the materials and systems described herein. Materials such as the described laminates can be deployed in many applications. One particular application is for surface sensors, which can be deployed in, on, or across many locations throughout a vehicle. Some such deployments are shown and described in connection with FIG. 2C.

[0080] 2C illustrates an exemplary surface sensor deployment 2C00 at a selected location on a vehicle. The exemplary surface sensor deployment 2C00, or any aspect thereof, may be implemented in or on a vehicle exposed to any possible external environmental condition, such as snow, sleet, hail, etc.

[0081] Tuned resonant sensing carbon-containing materials can be incorporated into or coupled to automotive features, surfaces, and / or components in the context of durable sensors within various exterior surfaces of the vehicle. As shown, the vehicle includes surface sensors on the vehicle's front fairing (e.g., hood), vehicle support members, and vehicle roof. Each of these locations on the vehicle may be subject to stresses and associated deformations during vehicle operation. By way of example, the surface sensor on the front fairing experiences air pressure changes during vehicle operation (e.g., forward motion). Under the force of air pressure, the material comprising the surface may deform slightly and exhibit a change in the resonant frequency of the material proportional to the degree of material change or deformation, in accordance with the phenomenon described in connection with FIGS. 2B1 and 2B2. Such changes can be detected using the "ping" and observation techniques described above.

[0082] The observed emitted signals can be collectively defined as a signature for a particular material or surface and can be further classified. Specific characteristics of the signals can be isolated for comparison and measurement, and calibration points corresponding to the specific isolated characteristics can be determined. Therefore, aspects of the environment surrounding the vehicle can be accurately and reliably determined.

[0083] For example, if deformation of a surface sensor shifts its frequency from 3 GHz to 2.95 GHz, mapping that difference to a calibration curve can yield a value for air pressure. Vehicle components such as panels, roofs, hoods, trunks, or airfoil components can offer relatively large surface areas. In these cases, a transceiver antenna can be positioned on the observable side of the component. Several transceiver antennas can be arranged in an array, with each element of the array corresponding to a section of the large surface area. Each transceiver antenna can be installed on or within the wheel well of a surface sensor deployment 2C00 as shown and can be independently stimulated with pings / chirps. In some cases, each element of the array can be stimulated sequentially, while in other cases, each element of the array is stimulated simultaneously. Vehicle aerodynamics can be measured over a large surface area with signal processing used to distinguish signature returns from proximal array elements.

[0084] The signature return from a particular array element can be analyzed with respect to other environmental conditions and / or other sensed data. For example, the deflection of a particular portion of the airfoil component may be compared to the deflection of a different portion of the airfoil component and then analyzed with respect to the current temperature, and / or the current tire pressure, and / or other sensed aspects of either the vehicle or its environment.

[0085] Figure 2D illustrates various current generation systems that can be integrated with the surface sensor deployment shown in Figure 2C, according to some embodiments. Any one or more of the electrodynamic, photovoltaic, piezoelectric, and / or oscillating current generation systems shown, including a regenerative braking system 2D02, an electrodynamic system 2D18, a photovoltaic system 2D04, a wind turbine system 2D06, a photovoltaic and / or vibration battery 2D08, a piezoelectric tire pressure monitor 2D10, an exhaust system turbine 2D12, an energy harvesting shock absorber 2D14, and / or an auxiliary power unit 2D16, can supplement a triboelectric energy generator incorporated within the plies of the tire body as discussed in Figure 2C and elsewhere.

[0086] A regenerative braking system 2D02 can capture, absorb, store, and convert useful electrical current to power a resonator to capture thermal energy generated during compression of the brake pads on the shoe against the rotating brake rotor. Such power can then be reapplied or otherwise reused to provide a torque boost that enhances the instantaneous off-road linear acceleration of a conventional internal combustion engine-powered vehicle, or a battery-powered vehicle. Incident light (e.g., from parking outdoors in sunlight) can be harvested by a photovoltaic system 2D04, while a wind turbine system 2D06 can further capture, store, and reapply energy.

[0087] Similarly, incident vibration energy (such as that from a truck driving near a parked car so equipped with the system of the present disclosure in FIG. 2D ) can be captured by a vibration battery 2D08, and energy from vibrations encountered while driving on uneven road surfaces can be captured by a piezoelectric tire pressure monitor 2D10. An exhaust system turbine 2D12 (like a turbocharger in an internal combustion engine) can capture and recharge exhaust gases to generate usable power. An energy harvesting shock absorber 2D14 can absorb impacts, retain their mechanical energy, and convert it into useful electrical current to supply an auxiliary power unit 2D16, extending the usable range of a hybrid or all-electric vehicle. Potential auxiliary power sources and systems are too numerous and extensive to specifically enumerate herein, and those skilled in the art will understand that the system of the present disclosure (and the tribological energy generator) can function with any available power capture and reuse system.

[0088] Figure 2E shows the characteristics associated with examples of energy recycling in different classes of vehicles. The vibration energy capture device achieves approximately 800 μW / cm 3 Alternatively, or in addition, an energy source can be provided that provides the required power to sustain mechanically induced vibrations of approximately 800 μW / cm, since the person acts as a charge carrier (such as a capacitor). 3 Light (photovoltaic) and thermal (thermoelectric) energy capture and recycling devices suitable for incorporation into any of the systems of the present disclosure can capture between about 0.1 and 100 mW / cm. 2 (for photovoltaic devices) and 60 μW / cm 2 can be reused by maintaining a temperature gradient of about 5°C. The ambient electromagnetic (EM) radiation radio frequency (RF) is about 0.26 μW / cm 2 can be given for a field strength of 1 V / m, for example.

[0089] Figure 2F shows Table 2F00 for various figures related to energy harvesting in vehicles. Possible scenarios related to increases in energy harvesting are shown in terms of the number of electric vehicles (EVs) sold (e.g., heavy industry) and the percentage of main batteries charged using energy harvesting in, for example, 2011 compared to 2021 (as projected).

[0090] Figure 2G shows Table 2G00 of various characteristics related to energy harvesting for vehicles. Examples of energy harvesting technologies and their applicability to electric vehicles, land, water, and air, are all shown in the following power ranges per vehicle: (1) microwatts to milliwatts, (2) milliwatts to watts, and (3) watts to tens of kilowatts. The power recovery systems described above are organized by potential power recovery and delivery capabilities (e.g., from a few microwatts to a few milliwatts or more).

[0091] FIG. 2H shows a collection 2H00 of common materials used in a triboelectric series, organized according to some embodiments, depending on polarity and / or polarizability. Examples of materials found to have demonstrated positive polarity and / or polarizability include polyformaldehyde 1.3-1.4, while examples of materials found to have demonstrated negative polarity and / or polarizability include polytetrafluoroethylene (Teflon). Those skilled in the art will understand that other possible examples of materials may exist for triboelectric energy generation potential without departing from the scope and spirit of what is shown in FIG. 2H and elsewhere.

[0092] FIG. 2I illustrates a signature classification system 2D00 that processes signals received from a sensor formed from a carbon-containing tuned resonant material. The signature classification system 2D00 can be implemented in any physical environment or weather condition. FIG. 2D relates to incorporating a tuned resonant sensing material into an automotive component to classify signals (e.g., signatures) detected by and / or classified from and / or received from sensors installed in the vehicle. In operation 270, a ping signal at a selected ping frequency is transmitted. The ping signal generating mechanism and ping transmission mechanism can be implemented using any known technique. For example, a transmitter module can generate a selected frequency of 3 GHz and transmit the signal using one or multiple antennas. The design and location of the tuned antenna (such as mounted on and / or within any one or more of the wheel wells or the vehicle) can correspond to the geometry, material, and / or location of any tuned antenna such that the intensity of the ping is sufficient to induce resonance (RF) in the proximity sensor. Several tuned antennas are placed on or within the structural member in proximity to a corresponding sensor. In this way, when the proximal surface sensor is stimulated by a ping, it resonates and returns with a signature. The signature is received (operation 274) and stored in a dataset, which may include received signature 276. The sequence of transmitting pings followed by receiving the signature may be repeated in a loop.

[0093] The ping frequency may be changed during repeated passes through the loop (operation 272). Thus, when operation 274 is performed in a loop, operation 274 generates a first signature 2781, a second signature 2782, up to Nth signature 2783, and so on. NA signature 278 including the first ping and the first return signature may be stored. The number of iterations may be controlled by decision 280. When the “No” branch of operation 280 is taken (e.g., when there are no further pings to send), the received signature may be provided (operation 282) to a digital signal processing module (e.g., an instance of the signature analysis module 154 shown in FIG. 1B). The digital signal processing module classifies the signature (operation 284) against a set of calibration points 286. The calibration points may be configured to correspond to particular ping frequencies. For example, the calibration points 288 may include a first calibration point 2881 that may correspond to a first ping and first return signature near 3 GHz, a second calibration point 2882 that may correspond to a second ping and second return signature near 2 GHz, etc., for any integer value “N” of calibration points.

[0094] In operation 290, the classified signal is sent to a vehicle central processor (e.g., vehicle central processor 116 of FIG. 1B). The vehicle central processor can relay the classified signal to an upstream repository, which hosts a computerized database configured to host and / or execute machine learning algorithms. Thus, a vast amount of stimuli related to signals, classified signals, and signal responses can be captured for subsequent data aggregation and processing. The database may be computationally prepared, referred to as “training,” and provided with a given set of sensed measurements that can be correlated to conditions or diagnoses related to vehicle performance, such as tire degradation due to repeated use. If, during vehicle operation, the measured deflection (e.g., air pressure) of a particular portion of an airfoil component differs from the measured deflection (e.g., air pressure) of a different portion of the airfoil component, a potential diagnosis could be that one tire is underinflated, causing uneven vehicle ground clearance, which in turn could cause proportional unevenness in airflow over, above, and / or around the vehicle, as sensed by deflections on the airfoil component. Other potential conditions or diagnoses can also be determined by the machine learning system. Status and / or diagnostic and / or supporting data can be returned to the vehicle to complete the feedback loop. Instrumentation in the vehicle provides visualization that can be performed (e.g., by the driver or engineer).

[0095] 3A illustrates a battery-powered tire condition sensor 3A00 (prior art). As shown, prior art techniques may rely on battery-powered electronics (e.g., pressure sensor 302, battery 304, and antenna 306), any one or more of which may be placed inside the inflated tire and transmit signals to a receiver outside the inflated tire. This may present various challenges, including: (1) the battery-powered electronics may not survive in harsh environments (external to the vehicle), and (2) the battery-powered electronics may be inaccessible during the life of the inflated tire.

[0096] A good technique may involve passive (generally not battery-powered) sensors or embedding sensing material into the tire material itself (such as on, in, or within the individual tire plies or the tire carcass). Mechanisms for tire sensing, including environmental sensing outside the tire as well as sensing inside the tire, are presented and described in further detail below.

[0097] 3B illustrates the operation of a tire condition sensor 3B00 embedded in (or at least partially within) a tire as one or more discrete (but interconnected or contiguous) layers of carbon-containing tuned resonant material. The tire condition sensor 3B00 can be implemented in any environment. No battery-powered electronics are located inside the tire; rather, one or more various tire tread layers and / or tire body plies of the tire can be constructed of (and / or otherwise include sensors made from) carbon-containing tuned resonant material, each tailored to resonate at a distinct and identifiable frequency from the other tread layers and / or plies.

[0098] FIG. 3C illustrates various physical properties or aspects (tire condition parameters 3C00) associated with incorporating a tuned resonant sensing material into an automotive component (such as a tire). The drawings are presented herein with respect to addressing deployment of survivable sensors in tires, including non-pneumatic and pneumatic tires. Tire configurations can correspond to radial tires, bias-ply tires, tubeless tires, solid tires, run-flat tires, and the like. These tires can be used on all types of vehicles and / or equipment and / or vehicle-related accessories. Such vehicles may include aircraft, all-terrain vehicles, automobiles, construction equipment, dump trucks, bulldozers, farm equipment, forklifts, golf carts, harvesters, lift trucks, mopeds, motorcycles, off-road vehicles, racing cars, lawn mowers, tractors, trailers, trucks, wheelchairs, and the like. These tires may also be used on non-motorized vehicles, equipment, and accessories, such as bicycles, tricycles, unicycles, lawn mowers, wheelchairs, carts, and the like, in addition to or instead of those presented.

[0099] The parameters shown in FIG. 3C are one example, and others may be present or otherwise tailored to target unique desired performance characteristics for many possible end-use scenarios, including a truck tire designed for extended life (possibly at the expense of road adhesion), or a soft racing tire designed for maximum road adhesion (possibly at the expense of road adhesion).

[0100] Various carbon structures are used in different formulations with other non-carbon materials, incorporated into tires, and then subjected to mechanical analysis to determine their respective tire properties. Some of these properties can be determined empirically by direct testing, while others are determined based on measurements and extrapolation of data. For example, rolling uniformity can be determined by sensing changes in force as the tire rolls on a uniform surface such as a roller, while tread life is based on short-term abrasion tests, and the results of those short-term tests are extrapolated to arrive at a predicted tread life value.

[0101] Many more tire characteristics can be measured, but some of these measurement techniques can be physically destructive to the tire and therefore can be measured at desired points in the tire's life. In contrast, such destructive measurements can be performed throughout the tire's life using survivable sensors embedded in the tire. For example, RF-based response signal detection that pings sensors embedded in the tire can be used for such sensing. Moreover, each body ply and / or tread layer of the tire can include a durable (also referred to as "survivable") sensor tuned to resonate at a specific frequency, as described.

[0102] The plies used in tires can be formulated to combine carbon-containing structures with other materials to achieve a specific material composition that exhibits desired performance characteristics (such as handling and lifespan). One natural resonant frequency (or multiple natural resonant frequencies) of a specific material composition can be subjected to spectral analysis to create a spectral profile for the specific material composition. This spectral profile can be used as a calibration baseline for that material. As the tire's body plies and / or tread layers undergo deformation, the spectral profile changes, and this change in spectral profile can be used as an additional calibration point. Many such calibration points can be generated by testing, and these calibration points can then be used to measure deformation.

[0103] Analysis of the spectral response results in quantitative measurements of a number of tire parameters. Tire parameters that can be determined from the signature analysis include, for example, tread life 322, handling at first temperature 328, handling at second temperature 326, rolling economy at first temperature 330, rolling economy at second temperature 332, rolling uniformity 336, and braking uniformity 338.

[0104] The spectral response based on return ping signals received from sensors embedded in the material within the tire plies can represent the observed deformation. That is, a particular type of tire deformation corresponds to a specific type of unique response, and a mapping between these responses or response types can be made to degradation types. Furthermore, the time-varying variations in the tire's spectral response as the tire deforms in situ can be used to determine many ambient conditions, some of which are discussed in connection with FIG. 3E. In tires constructed using multiple plies, each body ply and / or tread layer can be formulated to exhibit a specific tuning frequency or a range of specific tuning frequencies. For example, FIG. 3D shows a schematic diagram of a tire constructed from multiple plies, each ply having a different specific tuning frequency or range of specific tuning frequencies.

[0105] Figure 3D shows a schematic diagram 3D00 for fine-tuning or tuning multiple body plies and / or tread layers of a tire by selecting carbon-containing tuning resonant materials for incorporation into the tire assembly or structure, which can be implemented in any environment. Figure 3D shows how different carbons can be mixed into tire composite formulations and integrated into multi-ply tires. The resulting multi-ply tires exhibit different resonant susceptibility and frequency shift characteristics.

[0106] Multiple reactors (e.g., reactor 3521, reactor 3522, reactor 3523, and reactor 3524) each produce (or otherwise transport or provide) a specific carbon additive / filter to a network that is tuned to produce a specific, defined spectral profile. The carbon additives (e.g., first tuned carbon 354, second tuned carbon 356, third tuned carbon 358, and fourth tuned carbon 360) can be mixed with other compositions 350 (carbon-based or non-carbon-based). Any known techniques can be used to mix, heat, pre-treat, post-treat, or otherwise combine the specific carbon additives with the other compositions. Agitators (e.g., agitator 3621, agitator 3622, agitator 3623, and agitator 3624) are presented to illustrate how different tuned carbons can be introduced into various components of a tire. Other techniques for tire assembly may include other construction techniques and / or other components that comprise a tire. Any known technique can be used for multi-ply tires. Additionally, the spectral profile of a particular body ply and / or tread layer (e.g., a group of body plies and / or tread layers 368 including body ply and / or tread layer 3681, body ply and / or tread layer 3682, body ply and / or tread layer 3683, and body ply and / or tread layer 3684) can be determined based on the characteristics of the particular body ply and / or tread layer formulation. For example, based on stimulus and response characteristics, a first body ply and / or tread layer formulation (e.g., body ply and / or tread layer formulation 3641) can exhibit a first spectral profile, while a second body ply and / or tread layer formulation (e.g., body ply and / or tread layer formulation 3642) can exhibit a second spectral profile.

[0107] The resulting various formulations (e.g., body ply and / or tread layer formulation 3641, body ply and / or tread layer formulation 3642, body ply and / or tread layer formulation 3643, and body ply and / or tread layer formulation 3644) are used in different body plies and / or tread layers formed in tire assembly 366, with each of these body plies and / or tread layers exhibiting a corresponding spectral profile.

[0108] 3E illustrates a first set of exemplary condition signatures 3E00 emitted from a tire (exposed to any environment) formed from a layer of carbon-containing tuned resonant material. Several dynamic mechanical analysis tire parameters are illustrated that can be measured based on operation. A given tire or tires can be mounted on one or more wheels of a vehicle and driven by the vehicle in any environment. When the tire is subjected to an RF signal stimulus and simultaneously undergoes deformation through use (e.g., deformation of one or more body plies and / or tread layers of the tire), the carbon-containing tuned resonant material forming the sensor layer within the tire can emit a signature in response to the stimulus that can represent the concurrent deformation of the tire.

[0109] This diagram illustrates only a few examples of deformations of one or more body plies and / or tread layers of a tire as the tire operates under various conditions. When the tire operates under various conditions, the various body plies and / or tread layers of the tire emit different sets of signals (e.g., condition-specific signals 345) in response to stimuli while such conditions exist. As shown, the tire can operate in warm ambient conditions, where signals emitted by the various body plies and / or tread layers of the tire in response to stimuli during such operation are considered warm ambient signals 340. Also shown, the tire can operate in cold ambient conditions, where signals emitted by the various body plies and / or tread layers of the tire in response to stimuli during such operation are considered cold ambient signals 342. Furthermore, the tire can operate under low tire pressure conditions, where signals emitted by the various body plies and / or tread layers of the tire in response to stimuli during such operation are considered low tire pressure signals 344.

[0110] Signal processing (e.g., as may be performed by an instance of the aforementioned signature analysis module 154 of FIG. 1B ) classifies the condition-specific signal 345 against a set of calibration points corresponding to various environmental conditions. The calibration points may correspond to specific ping frequencies and / or a specific set of ping frequencies. The temporal characteristics of the ping emissions may differ to detect different in-situ conditions. For example, when a vehicle operates over Bott's dots (referring to round, non-reflective, raised pavement markers typically made of plastic, ceramic, thermoplastic paint, glass, or, rarely, metal), one or more tires of the vehicle may deform periodically. This period depends on the vehicle's speed and the distance between the first Bott's dot 346 and the next Bott's dot. As shown, the deformations can differ based on various conditions (e.g., warm ambient conditions, cold ambient conditions, low tire pressure, etc.). Furthermore, the different deformations can be caused by specific road conditions, such as road seams 347 or minor road imperfections 348. Any of the aforementioned condition-specific signals and / or any road conditions can be detected based on the signals returned in response to the ping or other stimulus. The above discussion of Figure 3E includes processing of a first set of exemplary condition signatures. Additional condition signature sets are discussed in further detail as follows.

[0111] FIG. 3F1 illustrates a second set of exemplary condition signatures 3F100 emanating from a tire formed with a layer of carbon-containing tuned resonating material. The exemplary condition signatures 3F100, or any aspect thereof, can be emitted in any environment. FIG. 3F1 illustrates multiple body plies and / or tread layers (e.g., body ply and / or tread layer #1, body ply and / or tread layer #2, and body ply and / or tread layer #3) of a new tire. As used in this example and elsewhere with reference to any one or more of the presented embodiments, the term “ply” can refer to a ply or layer within the tire body, or alternatively, a tire tread layer that projects radially outward away from the tire body intended to contact hard pavement, or the ground for off-road tires. In the example, the first body ply and / or tread layer is compounded with (meaning made by a specific compounding) tuned carbon such that the first body ply and / or tread layer resonates at 1.0 GHz when stimulated with a 1.0 GHz ping stimulus (e.g., first ping 374). Similarly, the second body ply and / or tread layer is compounded with tuned carbon such that the second body ply and / or tread layer resonates at 2.0 GHz when stimulated with a 2.0 GHz ping stimulus (e.g., second ping 376). Furthermore, the third body ply and / or tread layer is compounded with tuned carbon such that the third body ply and / or tread layer resonates at 3.0 GHz when stimulated with a 3.0 GHz ping stimulus (e.g., third ping 378). As shown by first response 382, ​​second response 384, and third response 386, all three body plies and / or tread layers can respond at their respective tuned frequencies.

[0112] The transceiver antenna can be positioned in and / or on the wheel well of the corresponding tire. The system that processes any such generated response signal can be configured to distinguish it from other potential responses originating from other surfaces, such as the remaining non-target tires of the vehicle. For example, even if a right front tire mounted on the right front wheel of a vehicle responds to a ping emitted from a transceiver antenna located in the left front wheel well of the vehicle, the response signal from the right front tire will be significantly attenuated (and recognized as such) compared to the response signal from the left front tire of the vehicle.

[0113] When the transceiver antenna is located within the wheel well of a corresponding tire, the response from the corresponding tire is attenuated to the ping stimulus. For example, the response from the corresponding tire may be attenuated by 9 decibels (-9 dB) or more to the ping stimulus, or by 18 decibels (-18 dB) or more to the ping stimulus, or by 36 decibels (-36 dB) or more to the ping stimulus, or by 72 decibels (-72 dB) or more to the ping stimulus. In some cases, the ping signal generator is designed to be combined with a transceiver antenna located within a wheel well such that the ping response of the corresponding tire is attenuated by 75 dB (-75 dB) or less.

[0114] 3F2 shows a third set of exemplary condition signatures 3F200 emitted from a tire after wear of some carbon-containing tuned resonant material. Optionally, one or more variations of the exemplary condition signatures 3F200, or any aspect thereof, can be implemented in light of the architecture and functionality of the embodiments described herein. The exemplary condition signatures 3F200, or any aspect thereof, can be emitted in any environment.

[0115] In this example, the tire is worn. More specifically, the outermost body ply and / or tread layer is completely worn. As a result, a ping stimulus at 1.0 GHz resulted in no response from the outermost ply. This is shown on the chart as First Response Attenuation 387. As the tire tread continues to wear, the ping response from the next body ply and / or tread layer, the ping response from the next body ply and / or tread layer, and so on, attenuates, and this attenuation can be used to measure the total tread wear of the tire. Alternatively, the same tuning carbon can be used for all plies. Tire tread wear, as well as other indications, can be determined based on the signal signature returned from the tire.

[0116] 3F3 shows a graph of measured resonant signature signal strength (decibels, db) versus tire tread layer loss height (millimeters, mm), according to some embodiments. As shown herein, carbon-containing microstructures and / or microstructured materials can be incorporated into sensors, or, depending on the configuration, into one or more tire tread layers at a given concentration level or multiple different concentration levels (within each of one or more tire tread layers), to obtain the unique degradation profile shown. That is, the measured resonant signature (referring to a "signature" that identifies the particular tire tread layer in question) can exhibit attenuation of the emitted signal when a "ping" is emitted by one or more RF signals, as described herein.

[0117] A new tire tread layer can be configured to exhibit a signal strength (measured in decibels, db) of approximately 0. The strength can vary proportionally to the degree of degradation of that tire tread layer. For example, a 2 mm height loss in a tire tread layer (assuming the tire tread layer is in contact with the pavement) can correspond to the measured resonant signature signal strength profile shown. A "ping" signal at 6.7 GHz can be measured at an intensity level of approximately 9 db, etc.

[0118] Thus, unique concentration levels, chemistries, dispersions, distributions, and / or the like of carbon-containing microstructures can be embedded in a tire tread layer (or, in some cases, disposed on one or more surfaces thereof) to provide a unique and easily identifiable measured resonant signature signal strength, as shown. Thus, users of such systems can be instantly notified of the precise extent and location of tire tread wear occurring while driving, rather than being limited to observing the tire while the vehicle is stationary, a process that can be both time-consuming and labor-intensive.

[0119] 3G1 and 3G2 show schematic diagrams of an exemplary conventional carbon material production chain, such as that described by Anzelmo, et al. in U.S. Patent No. 10,428,197, entitled "Carbon and Elastomer Integration," issued October 1, 2019, which is incorporated herein by reference in its entirety. FIG. 3G1 shows a schematic diagram of an exemplary conventional carbon material production chain 3G100, in comparison to FIG. 3G2, which is an example of a carbon material production chain used to produce the carbon-based microstructures described herein. In the conventional carbon material production chain 3G100, as shown in FIG. 3G1, raw materials such as carbon black 3G102, silica 3G104, and other chemicals 3G106 can be transported and placed in a manufacturing facility 3G110, where they are compounded into elastomer compounds and then processed into final products, such as tires 3G120 (rubber-based tires and pneumatic tires).

[0120] Conventional tire supply can include preparation of raw materials (such as rubber bales, carbon fillers, fabrics, steel, and other additives), construction of tire components (including extruding elastomeric compounds for the tread and sidewalls), and construction of the tire 3G120 (with curing the tire and inspecting the finished tire). Nano-mixing of materials (optionally), as well as production of carbon microstructures, mixing of elastomeric compounds, and optionally construction of the final product (such as an automobile tire), can occur on-site.

[0121] In contrast to conventional carbon-containing tire production as presented by the conventional carbon material production chain 3G100 in FIG. 3G1, the hydrocarbons 3G202 and silica 3G204 are mixed (such as by integrating together) in a reactor 3G206 at an on-site manufacturing facility 3G208 and then integrated with elastomer feedstock (such as rubber) to produce an elastomeric compound before being processed into a final product such as a tire 3G208. The differentiation between FIG. 3G1 and FIG. 3G2 shows potential advantages, including eliminating the need to transport difficult-to-handle carbon black material and reducing energy consumption by integrating materials together during the carbon production process.

[0122] Alternatively, the conventional supply chain shown in Figure 3G1 can be used in combination with the graphene-based carbon materials of the present invention: the carbon materials can be produced at one site, and then the carbon materials and other components can be shipped to a manufacturing facility where they are compounded into elastomer compounds and processed into final products such as tires.

[0123] Another advantage of using the graphene-based carbon materials of the present invention is their improved purity compared to carbon black. Impurities in carbon black (such as residual oils) require the carbon to be labeled as carcinogenic. The graphene-containing carbon-based microstructures provided herein have lower volatile organic compounds (VOCs) than carbon black, and therefore do not produce residual oils on the surface of the resulting elastomeric material. Alternatively, the carbon-based microstructures have lower concentrations of residual hydrocarbons (such as polycyclic aromatic hydrocarbons) compared to carbon black, resulting in less residual oil on the surface of the resulting elastomeric material. Furthermore, the carbon materials (including carbon-based microstructures) described herein contain lower concentrations of contaminants (such as ash, metals, and other elemental contaminants) compared to conventionally processed carbon black or graphene. Furthermore, the emissions of CO2, NO2, and other by-products are reduced. x , and SO x All these advantages make the carbon material of the present invention safer to handle and more environmentally friendly than conventional carbon blacks used in elastomers.

[0124] The lower concentration of impurities in the carbon-based microstructures of the present invention compared to carbon black also provides advantages for processing of carbon materials (such as carbon post-processing and elastomer compounding). For example, conventional carbon black processing equipment may require specialized systems to process toxic carbon black particles. In contrast, specialized systems are not required to process the non-toxic or low-toxicity materials of the present invention.

[0125] There are three properties that can affect the ability of a particular carbon material to reinforce an elastomer: (1) surface area, (2) structure, and (3) interfacial activity. Impurities such as coke, ash, and moisture can also be important to the effectiveness of carbon fillers in elastomers. Surface area refers to the total surface area of ​​the carbon material, including those available for interaction with the elastomer. Particle size and shape can affect surface area. Smaller carbon-based microstructures (e.g., average diameter less than 100 nm) typically form larger aggregates (e.g., average diameter 1-10 microns). Structure refers to the shape of the aggregate. Structure can be influenced by the number of particles fused and the arrangement of particles within the aggregate. For example, aggregates with a large number of particles can have complex shapes with large void volumes. Structure can affect the degree of intermixing of the carbon and polymer (e.g., voids can be filled with polymer), thereby affecting the properties of the elastomer / carbon compound.

[0126] Interfacial activity also refers to the strength of the surface interaction between the carbon filler and the polymer and can affect the dispersion characteristics of the carbon material within the elastomer. The surface area of ​​the carbon filler can affect compound mechanical properties such as tensile strength, tear strength, and abrasion resistance. The structure of the carbon filler can affect other compound mechanical properties such as viscosity, shrinkage, and modulus. Surface area can also affect some compound mechanical properties such as hysteresis. Structure can also affect flex fatigue resistance and abrasion resistance in reinforced elastomeric compounds. Interfacial activity can also affect compound mechanical properties such as modulus, hysteresis, and abrasion resistance.

[0127] 4 and 5A are presentations of characteristics related to waste energy harvesting and power supply in vehicles, any one or more of which can affect carbon-containing material performance in the systems of the present disclosure, such as by powering resonators embedded within tire plies. For example, vehicle waste energy harvesting and power supply related functionality 400 can include application spaces 402, which include at least the following: composite materials used in vehicles to recover energy from vehicle motion, vehicle tires that recover energy from vehicle motion, energy capture devices positioned in and around heat sources such as steam pipes or exhaust pipes, and industrial applications that recover energy from equipment motion.

[0128] 5A provides functionality 500A related to thermoelectric generation functionality 502A integrated into a tire for energy transfer occurring within the wheel well of a vehicle. Such energy transfer involves a voltage difference generated by the flow of charge carriers between hot and cold regions (in the tire). The thermoelectric generator (TEG) can function in the dark, and the TEG contains no moving parts, allowing for continuous operation. The TEG can be placed within the tire tread as a layer, and N / P doped carbon with tuned conductivity can generate waste heat >10 mW / cm. 2 This can include being able to generate significant power from the battery, with even a small temperature change (such as Δ10° C.) producing approximately 3.5 W+ and providing usable recovered power.

[0129] 5B shows a schematic diagram illustrating the flow of charge carriers (within semiconductor materials incorporated within the material of a vehicle component) between hot and cold regions, which creates a voltage difference that allows a thermoelectric generator (TEG) to operate in low or no light conditions. Semiconductors 5B00 can be incorporated within the plies of the body of a vehicle tire to capture heat transfer from hot regions, including locations 5B02 and 5B04, through n-type and / or p-type semiconductor materials 5B06, and provide electrical current via circuit 5B10 to, for example, power any of the resonators of the present disclosure.

[0130] 5C illustrates carbon-based materials incorporated into plies or treads within the tire body that are tuned for electrical conductivity and / or doped to generate electrical power from waste heat. Layered p-n (PN) junction semiconductor material segmented for voltage 5C02 may be incorporated into the tire body wall or tread extending therefrom to provide electrical current and thus power the resonator as described. The resonator may include components such as an oscillator, a resonant circuit, and a rectifier, all of which operate in a substantially conventional manner.

[0131] Figure 5D shows a chart 5D00 comparing power output versus heat flux magnitude (delta in degrees Celsius) associated with a thermoelectric generator integrated into a tire. Assume the TEG device includes bismuth telluride (Bi2Te3), which has a Seebeck coefficient (a measure of the magnitude of the thermoelectric voltage induced across the material in response to a temperature difference) of approximately -287 μV / K at 54 °C and / or exhibits the relationship ZT = S2T / ρκ~1. Carbon-based microstructures can be tuned and incorporated into the TEG device to potentially achieve Seebeck performance (referring to bismuth telluride-containing TEG devices) and bending capabilities. In general, the power output (Watts per tire) generated by such a TEG device can increase with increasing temperature gradients.

[0132] Figure 6A is a presentation of properties associated with three-dimensional (3D) graphene for use in thermoelectric conversion 600A (such as when incorporated within a composite material). In addition to those presented previously, carbon-based microstructures can be incorporated into TEG devices by being arranged as layers within a stack of composite components, and carbon doped into n-type and / or p-type (N, P, respectively) semiconducting materials with appropriate tuned electrical conductivity can produce waste heat >10 mW / cm. 2Since significant electrical power can be generated from a temperature gradient of about 200° F., a temperature gradient of about 200° F. can generate about 35 W or more. TEG devices such as those incorporating the carbon-based microstructures of the present disclosure can be contained, for example, within the vehicle engine cover of a conventional internal combustion engine, thereby efficiently capturing and storing and / or reusing radiant heat energy emitted during engine operation to provide a usable electrical current to power the resonator.

[0133] FIG. 6B shows layered p-n (PN) junction semiconductor materials incorporated into engine components for power harvesting. The layered PN semiconductors can be segmented for precise voltage control and incorporated into engine covers, heat shields, or exhaust components. Foam materials may also be used to absorb vibration and / or thermal energy for power harvesting. Overall, these devices, when used in combination with any one or more of the systems and devices described above, can complement energy harvesting and reuse capabilities, powering resonators as needed to efficiently identify wear on vehicle components.

[0134] FIG. 7A is a representation of tire diagnostic-related functionality 700A powered by a piezoelectric energy generator and / or the like. Piezoelectricity is the accumulation of electrical charge in certain solid-state materials (such as crystals) in response to applied mechanical stress. The piezoelectric effect results from the linear electromechanical interaction between mechanical and electrical states in crystalline materials without inversion symmetry. The piezoelectric effect is a reversible process in which materials that exhibit the piezoelectric effect (the internal generation of electrical charge due to an applied mechanical force) can also exhibit the inverse piezoelectric effect: the internal generation of mechanical strain due to an applied electric field.

[0135] Any one or more of the carbon-based microstructures used by the disclosed systems and materials, including carbon nano-onions (CNO), can be used to form piezoelectric layers in sensors on or embedded within vehicle components, such as tires. Graphene can also be used to create energy harvesting patches, which can be integrated into tires. CNO and / or graphene can be tailored to collect, retain, and deliver electrical power (e.g., in the form of electrical current) to a resonator, which can be used in locating degradation of vehicle components, such as tire wear, requiring precision.

[0136] Tuned carbon materials, such as microcarbon nanotubes (m-CNTs), shown in graph 7B00 of Figure 7B, can assist in more accurate tire tread wear sensing (such as by powering a resonator) due to their large intrinsic capacitance. Compared to metals, CNOs can provide an enhanced form of carbon for achieving piezoelectric energy generation.

[0137] When used in combination with any one or more of the systems, methods, and materials presented above, CNOs can be used to create piezoelectric generators that provide power. These piezoelectric generators can, for example, power wireless strain sensor locations on the side of a tire (e.g., in an inner liner), which can monitor and detect tire damage. Potential tire deformation or strain can be determined or calculated from the degree of friction caused by the road surface, and such information can be used to optimize tire control systems in associated automobiles. For example, tire-related information can be wirelessly transmitted to appropriately equipped receivers (after calculations based on the signal's frequency shift and / or attenuation behavior, as discussed above). These receivers may be positioned within the tire and / or may be interfaced with resonators to provide a comprehensive tire information solution. The disclosed embodiments can also be interfaced with conventional telemetry methods and devices to communicate wear-related information of vehicle components, for example, to vehicle navigation systems.

[0138] 7B shows a graph 7B00 of conventional materials incorporated into the rubber of a vehicle tire, comparing normalized capacitance (C / C0) versus rubber thickness (mm). As shown, m-CNTs consistently outperform conventional materials such as silver and gold in terms of normalized capacitance compared to the thickness of the rubber in which the silver, gold, or m-CNTs (which may be incorporated into piezoelectric, thermoelectric, or other advanced energy harvesting and replenishment functions) reside. Carbon-based nanomaterials of the present disclosure match or exceed the performance figures shown for m-CNTs.

[0139] 7C1 shows a schematic diagram 7C00 illustrating a complete tire diagnostic system and apparatus for impedance-based spectroscopy tire wear sensing. A tire 7C20, such as a rubber pneumatic tire filled with air or nitrogen gas (N), can include conventional tire components having a body 7C20, an inner liner 7C12, a bead filler region 7C22, a bead 7C16, one or more belt plies 7C04, 7C06, 7C08, and 7C10, a tread 7C02, and impedance-based spectroscopy wear-sensing printed electronics 7C18 (alternatively, a sensor including carbon-based microstructures for monitoring frequency shift and attenuation of signals by resonators embedded within any one or more of the belt plies 7C04-7C10).

[0140] As shown herein, wireless strain sensors can be placed on the surface or on the side of (or embedded within) an innerliner to monitor tire condition for automotive safety (such as detecting damaged tires). Monitoring tire deformation or strain can (indirectly) provide information representative of the degree of friction between the tire and the road surface in contact, which can be used to optimize the vehicle's tire control system. Tire information can be wirelessly transmitted to a receiver positioned within the tire hub based on a resonant sensor platform.

[0141] FIG. 7C2 illustrates a system 7C200 that provides tire-wear-related information transmitted via telemetry to a navigation system and equipment for manufacturing printed carbon-based materials. System 7C200 can function with any one or more of the systems, methods, and materials disclosed herein, such as sensors including carbon-based microstructures, and redundant descriptions of the same will be omitted. Impedance spectroscopy, also referred to as electrochemical impedance spectroscopy (EIS), refers to an impedance measurement transduction method that involves applying a sinusoidal electrochemical perturbation (potential or current) over a wide range of frequencies when measuring a sample, such as a sensor including carbon-based microstructures incorporated into one or more tire belt plies of a tire 7C202. A printed carbon-based resonator 7C204 can be incorporated into one or more tire components, such as the tire belt ply. Each of the printed carbon-based resonators 7C204 may have the generally oval configuration shown, or some other shape or configuration that is tailored to achieve specific desired resonance characteristics suitable for efficiently and accurately detecting wear of vehicle components by monitoring frequency shift and / or attenuation (such as first response attenuation indicative of wear of a tire body ply and / or tread layer having a natural resonant frequency of approximately 1.0 GHz).

[0142] The roller assembly 7C210, which can form the printed carbon-based resonator 7C204, includes a reservoir 7C212 (e.g., a vat) of carbon-based microstructures and / or microstructured materials (e.g., graphene), an anilox roller 7C214 (a hard cylinder, typically constructed from a steel or aluminum core coated with an industrial ceramic (containing millions of very fine dimples on its surface), known as a cell), a printing cylinder 7C216, and a pressed copper cylinder 7C218. During operation, graphene extracted from the reservoir 7C212 can be rolled, pressed, drawn, or otherwise fabricated into an oval-shaped (or any other shaped) printed carbon resonator 7C204 by the rollers of the roller assembly 7C210. ​​The proper functioning of the system 7C200 requires the alignment of the printed carbon resonator 7C204.

[0143] As such, any combination of the aforementioned features can be used to fabricate a tire including a resonator. This resonator refers to an actual or "equivalent" tank, LC, and / or resonant circuit in which the carbon-containing microstructure itself can resonate in response to an RF signal emitted from a transceiver and / or energy provided by an advanced energy source, such that other sensors disposed within or on any one or more components of the tire, such as the tire tread, one or more plies, inner liner, etc., can exhibit frequency shift or signal attenuation characteristics or behaviors. The described resonators do not necessarily need to be embodied as actual electrical and / or integrated circuits (ICs). Because the described resonators can be easily realized as tuned carbon-containing microstructures, they can avoid common degradation concerns that can arise when implementing traditional discrete circuits within degradable materials, such as tire tread layers. Such resonators may resonate in response to an externally supplied "ping" (such as provided by a transceiver located within the wheel well of the vehicle), or the resonators may respond to being charged by co-located (referring to within the same tire tread layer, but possibly at different locations within that tire tread layer), self-powered, self-pinging functionality facilitated by any variation or number of power or charge generators (e.g., thermoelectric generators, piezoelectric energy generators, triboelectric energy generators, etc.).

[0144] Any of the described resonators (and other resonators and / or resonant circuits) can emit and / or be configured to emit an oscillating RF signal (or other form of electromagnetic radiation, depending on the overall configuration) whenever the tire is rolling or otherwise deforming. When a vehicle tire undergoes wear due to use (such as on-road or off-road driving), the tire tread layer in contact with the pavement or ground (earth) can undergo deformation (such as from "crushing," which refers to at least partial flattening of sections of the vehicle tire tread layer exposed during rotation or rolling, and / or as observed from lateral motion, such as experienced during a turn) either instantaneously or over time, such that the frequency shift and / or attenuation behavior of the resulting signal can change in response to such "crushing," where the associated signal can oscillate over one or more known amplitude ranges. Additionally or alternatively, as the tire deforms, the observed signal can oscillate within a known frequency range corresponding to a particular resonator, thereby allowing for accurate and precise identification of the type of degradation occurring and monitoring the tire tread condition while the vehicle is stationary, rather than requiring the driver, passengers, and / or other vehicle occupants to be present in the vehicle. Such frequency-shifting oscillations can be observed as the frequency shifts back and forth between two or more frequencies within the known frequency range.

[0145] FIG. 7C3 presents information 7C300 related to tire condition sensing that can be incorporated into any of the systems, methods, and sensors of the present disclosure. Wireless-enabled strain sensors (strain refers to a geometric measure of deformation representing relative displacement between particles within a body of material caused by external constraints or loads) on the side of the innerliner can monitor tire condition for automotive safety (such as by detecting damaged tires). Additionally, monitoring tire deformation or strain can indirectly provide information related to the degree of friction between the tire and the road surface, which can be used to optimize the vehicle's tire control system. Such tire information can be wirelessly transmitted to a receiver (and / or transceiver) positioned within the wheel hub based on a resonant sensor (e.g., impedance spectroscopy, IS, sensor) platform.

[0146] 7C4-7C5 show schematic diagrams, including schematic diagram 7C400 and schematic diagram 7C500, both relating to a resonant serial number-based digital encoding system 7C404 for determining wear on a vehicle tire through ply print coding. The resonant serial number-based digital encoding system 7C404 may be incorporated into and / or function in conjunction with any of the systems, methods, and sensors of the present disclosure. By providing a digital encoding of the tire through ply print coding, the resonant serial number-based digital encoding system 7C404 provides cradle-to-grave tire tracking (and associated performance metrics) and usage profile without the need for traditional electronics that are subject to routine wear and tear on the tire.

[0147] In addition to tire wear sensing by impedance spectroscopy (IS) and / or electrochemical impedance spectroscopy (EIS), additional resonators can be digitally encoded onto the print pattern to provide a recognizable serial number for telemetry-based tire performance tracking. Thus, vehicles so equipped can track tread wear, total mileage, age, etc., without the need for conventional radio frequency identification systems (RFID) or any other type of electronics. Tires incorporating the discussed printed carbon-based resonators can be given unique serial numbers by sequentially printing them onto the body ply and / or tread layer.

[0148] Figure 7C5 shows a schematic diagram 7C510 for resonant serial number encoding in a tire. It shows the serial number "6E" encoded within a specially prepared printed carbon resonator array that is configured to resonate according to a "ping" stimulus response diagram 7C512, thereby allowing for easy and reliable identification of that particular body ply and / or tread layer of a vehicle tire so equipped.

[0149] 7D shows a schematic diagram 7D00 illustrating various layers of a tire belt ply 7D02 configured to generate power or current through piezoelectric functionality, such as may be incorporated into any one or more of the example tires outlined above and discussed herein in connection with the various presented systems, methods, and materials. Generally, such belt plies may be part of a conventional rubber pneumatic tire for a vehicle (such as an automobile, sport utility vehicle, light truck, or truck) and may include any one or more of a bead, body, reinforcing belt, cap ply (optional), sidewall, and tread (also optional and absent in certain racing tires, such as slicks).

[0150] 8A presents information 800A related to energy harvesting through the application of thermoelectric generators (TEGs), including details regarding the functionality of any one or more of the presented systems, methods, and / or materials. Thermoelectric generation can be based on the principles of the Seebeck, Peltier, and Thomson effects, in which a voltage difference is generated by the flow of charge carriers between a hot and cold region.

[0151] An optimal thermoelectric material (suitable for incorporation into the TEG of the present disclosure) should have a high Seebeck coefficient (V=αΔT), high electrical conductivity, and low thermal conductivity to support a high temperature gradient at the junction. The polarity of the output voltage can depend on the polarity of the temperature difference across the TEG.

[0152] A TEG can consist of a solid-state daisy-chain circuit of pairs of oppositely doped thermoelectric structural posts, called "legs." The N-type and P-type semiconductor legs can be arranged electrically in series and sandwiched between two thin, thermally conductive ceramic plates. A commonly used semiconductor material is bismuth telluride (Bi2Te3).

[0153] V for a given size max (Maximum voltage) * The thermoelectric module with the highest Imax (maximum current) product provides the ideal power. Typical modules can be square, with side sizes ranging from approximately 10 mm to 50 mm, and thicknesses ranging from 2 mm to 5 mm. A notable performance feature that distinguishes TEGs over other alternative energy generation devices is their ability to operate in the dark, greatly expanding the range of potential applications. TEGs are also solid-state devices with no moving parts, allowing for continuous operation and containing no materials that need replenishment. Additionally, in certain configurations, the heating and cooling functions of some TEGs can be reversed.

[0154] 8B is a presentation of information-related energy harvesting functionality 800B, such as TEGs and other advanced alternative generators that can provide current or power to the resonators. For example, strain gauge sensors can be incorporated into elastomeric materials to sense weight and determine, for example, the unladen weight of a tractor and trailer. Sensors such as these can be designed to trigger alarms if tires exhibit weight or load imbalances (such as due to cargo shifting) and increased forces.

[0155] TEGs can work in conjunction with resonators incorporated into nitrogen-filled race tires to monitor for increases in other gases (such as oxygen and / or argon) that could indicate a leak or an upcoming tire blowout (puncture) situation. Tire structures can incorporate any combination of TEGs, piezoelectric energy generators, triboelectric energy generators, and other advanced energy harvesting means to capture, retain, and repurpose energy during vehicle operation to provide the current needed for resonator vibration, allowing the resonators to function in conjunction with any of the systems presented. Additionally, information on the wear and degradation of vehicle components can be electronically transmitted by appropriately equipped systems (mounted within the vehicle itself or elsewhere at a remote location) to notify stakeholders or even law enforcement, as well as provide high-quality, continuous, and reliable vehicle operation information. This information can be used and factored into predictive sales (based on vehicle driving behavior), promotional offers, insurance policies, road times, and more.

[0156] 9 shows a schematic cross-sectional view 900 of a vehicle chassis, engine, and drivetrain illustrating powertrain losses associated with a conventional vehicle (e.g., unavailable for forward propulsion). By applying any of the systems, methods, and materials of the present disclosure to counteract such powertrain losses, energy that would otherwise be lost can be efficiently captured and repurposed to power any of the resonators of the present disclosure for detecting vehicle component material degradation by monitoring signal responses. For example, in a conventional automobile powered by a front-mounted internal combustion engine (such as that shown by diagram 900 in FIG. 9), input 902 provides a conventional finite energy source, such as gasoline, to the engine. An idling engine results in 17% of its input energy becoming waste 904, another 2% being lost in incidental operations 906, 62% being lost due to engine friction, engine pumping losses, and waste heat (collectively referred to as engine-related losses 908), and 5.6% being lost in drivetrain losses due to friction and slippage 910, leaving only 12.6% residual energy 912 available to actually move the vehicle down the road.

[0157] FIG. 10 shows a schematic cross-sectional view of a vehicle equipped with a piezoelectric and / or thermoelectric current and / or power generator. The vehicle 1000 (shown as a mini-compact, but alternatively can be any form of passenger car, sedan, coupe, truck, sport utility vehicle, sports car, etc.) can be powered by a conventional internal combustion engine, equipped with hybrid power, or equipped with an electric motor for exclusive electric operation. In an example configuration, the vehicle 1000 can include four tires 1012, an air conditioning (A / C) converter 1014, a drive motor 1002, power steering 1006, a horsepower (HP) distribution machine 1010, an external charging socket 1004, and a battery system 1016. The vehicle 1000 can be equipped with piezoelectric energy generation means (e.g., generators, devices, motors, and / or the like). These piezoelectric energy generating means capture energy and convert the captured energy into electrical current, which may be useful for other applications or uses, such as powering any of the resonators, resonant circuits, and / or the like of the present disclosure for accurate and precise detection of the condition of vehicle components with respect to wear and degradation.

[0158] Piezoelectricity, as introduced earlier, implies the accumulation of electric charge in certain solid materials (such as crystals) in response to applied mechanical stress. The word piezoelectricity refers to electricity resulting from pressure and latent heat. Mechanistically, the nature of the piezoelectric effect is closely related to the occurrence of electric dipole moments in solids. The latter can either be induced by ions on crystal lattice sites where the charge of the surroundings is asymmetric (such as in BaTiO3) or carried directly by molecular groups (such as sucrose). The dipole density or polarization (dimensionality [C m / m]) for these crystals is 3 ]) can be calculated by summing the dipole moments per volume of the crystallographic unit cell. Since all dipoles are vectors, the dipole density P is a vector field.

[0159] The change in polarization P upon application of mechanical stress is crucial for the piezoelectric effect. This can be caused either by a dipole-induced rearrangement of surroundings or by a reorientation of molecular dipole moments under the influence of external stress. Piezoelectricity can then manifest itself as a variation in polarization strength, its direction, or both, as detailed in - Orientation of P within the crystal, Crystal symmetry, and applied mechanical stress, Depends on.

[0160] Changes in P manifest themselves as variations in the surface charge density on the crystal faces, such as variations in the electric field that prevails between crystal faces caused by changes in the bulk dipole density. For example, a 1 cm 3 A cube of quartz can generate a voltage of 12,500V.

[0161] Such principles can be configured to supply voltage and / or current to any of the resonators of the present disclosure functioning in conjunction as discussed above, such as delivering (1) high power or (2) both low power (as shown in informational caption 1108 of FIG. 11 ). High power application can include capturing rotational energy generated from the tire via a rotating hub, induction, or wireless means. Low power application can include integration with remote and / or on-board (referring to being integrated with the vehicle 1000) energy harvesting systems (such as the TEG system and / or triboelectric energy generators of the present disclosure). Integration with distributed sensor arrays activated by electromagnetic (EM) signal communication (e.g., at 465 Mhz or the like) can be used to facilitate backscatter or inductive coupling.

[0162] FIG. 11 shows various schematic perspective views of advanced concept tires and various energy (electric current) delivery challenges. Tires 1100 and / or 1102 can be Goodyear® BH03 Piezo Concept Tires manufactured by The Goodyear Tire & Rubber Company of Akron, Ohio, or any similar such advanced self-powered tires. Any of the systems, methods, and materials (including carbon-containing microstructures) of the present disclosure can be configured to function with such advanced tires, which are self-powered for providing continuous power to resonators for accurate vehicle component material degradation detection. Tires 1100 and / or 1102 can include tread and / or sipes 1104, 1106 and exhibit a carbon black-containing configuration referred to as an “Ultra Black” texture for efficient heat absorption that can be captured by thermoelectric (TE) generators or functions.

[0163] Figure 12 presents various properties related to the use or incorporation of graphene (e.g., carbon-based microstructures or constituents in carbon-based microstructures) into vehicle sensors configured to provide frequency shifting and / or attenuation functions to monitor the degradation performance of vehicle components. Graphene refers to an allotrope of carbon in the form of a single layer of atoms in a two-dimensional hexagonal lattice, with one atom forming each vertex. It is the basic structural element of other allotropes, including graphite, charcoal, carbon nanotubes, and fullerenes. It can also be considered an infinitely large aromatic molecule and is the ultimate example of a family of flat polycyclic aromatic hydrocarbons.

[0164] Graphene is 2,630m 2 / g, which is higher than carbon black (900 m 2 / g), or carbon nanotubes (CNTs) (approximately 100-1000 m 2 / g, similar to activated carbon, is much greater than previously reported. Graphene's unique properties include high strength (per unit area), thermal conductivity ranging from about 3,000 W / mK to about 5,000 W / mK, and the ability to achieve n-type conductivity by doping with certain elements, such as nitrogen (N), sulfur (S), boron (B), phosphorus (P), fluorine (F), and / or chlorine (Cl).

[0165] Formula ZT=σS 2 T / κ provides a quantitative relationship for the thermoelectric (TE) performance of a measured material and can be defined as follows: S is the Seebeck coefficient (a measure of the magnitude of the thermoelectric voltage induced in response to a temperature difference across the material when induced by the Seebeck effect), "σ" and "κ" are the electrical and thermal conductivities, respectively, and T is the absolute temperature. The goal of thermoelectric conversion includes increasing electrical conductivity while simultaneously decreasing thermal conductivity.

[0166] Graphene may require nanostructuring, for example, to tailor certain graphene sheet configurations that are not well suited for "daisy-chaining" (connecting several devices together in series) within typical high-power thermopile architectures to be optimal as a support substrate for epitaxially grown BiSbTe (e.g., for thermal management), to achieve dots ("0D"), tubes / ribbons ("1D"), or sheets (2D) and low dimensionality at interfaces (phonon scatterers) to reduce thermal conductance, and to achieve bandgap engineering to increase electrical carriers (p / n) and improve sensitivity / performance.

[0167] Graphene can also be used as a multifunctional element, which may offer one or more of the following advantages: allowing for combination with (or acting as) a thermal conductor (in the case of thermal management / PMC composite systems, graphene-on-graphene materials, etc.), reinforcing / stiffening, distributed sensor (pressure, friction, shear integrity), and acting as an energy harvester.

[0168] FIG. 13A is a schematic side view of a vehicle tire 13A00 incorporating graphene-filled rubber and contacting the ground or pavement. As shown, the vehicle tire 13A00 includes a tire rim (ground) 13A02 and a steel belt (conductor) 13A04 wrapped around the vehicle tire 13A00. The graphene-filled rubber can be incorporated into or otherwise used to form one or more tire plies of the tire body. Such graphene-filled rubber can provide a conductivity percolation threshold (referring to the minimum concentration of filler that can convert an insulating material into a conductive material; i.e., the percolation threshold is the minimum concentration of filler material, such as graphene-filled rubber, that forms an electrical path throughout the sample). When a vehicle is loaded, the tire can support its weight, as reflected as a load 1306 and / or other weights placed on the tire through the vehicle chassis or from occupants.

[0169] The vehicle tire 13A00 can be equipped with a triboelectric generator within one or more plies of the tire body to supply captured energy in the form of usable electrical energy to the resonator as previously disclosed. The triboelectric energy conversion principle used herein assists in the conversion of mechanical energy to electricity, and couples the friction and electrical induction of triboelectric charging to a power sensor to diagnose the general health (referring to wear and deterioration) of the tire in a continuous manner.

[0170] Under normal (per commuter) conditions, approximately 5-7% of the energy generated by friction between a vehicle tire 13A00 and the ground (e.g., pavement) can be dissipated. Without a triboelectric generator (or other advanced energy recovery means) to capture and retain such dissipated energy, the energy can be undesirably lost to the surrounding environment. Therefore, any of the carbon-based microstructures disclosed herein, such as those self-nucleated in-flight in a reaction chamber or reactor from carbon-containing gas-phase species such as methane (CH4), as disclosed by Stowell, et al. in U.S. Patent Application No. 16 / 785,020, entitled "3D Self-Assembled Multi-Modal Carbon-Based Particle," filed February 7, 2020, can be used to form sensors suitable for indicating wear or degradation of vehicle components, as discussed above.

[0171] Alternatively, or in addition, such carbon-based microstructures can be incorporated within the triboelectric energy generator itself, optimized to create carbon-containing triboelectric conductors with adjustable (tunable) polarizability, and organized and / or connected in series to accommodate various power source and generation scenarios or needs. Carbon-containing triboelectric energy generators as so described can optionally be uniformly dispersed throughout a given tire ply, extending across the entire width of the tire, rather than just circumferentially around the tire, instead of having sensors locally (smaller than the width of the tire). Thus, such tire ply-wide carbon-containing triboelectric energy generators (and / or localized sensors in communication with localized triboelectric energy generators dispersed across one or more tire plies) can both: The advantage of a large contact area at the tire surface for optimal charge generation / surface charging (abrasion - refers to the removal or destruction of material from an object by vaporization, chipping, or other erosive processes due to friction, creation of a new surface, and possible changes in resistance and potentially tread-related wear / life); The tuned graphene and rubber composite has the advantage that its dielectric constant can be optimized for electrostatic induction (which refers to the redistribution of charge in an object caused by the influence of nearby charges; bringing a charged object close to a material creates or generates static electricity in that material, resulting in a redistribution of charge in the material, resulting in an excess of either positive (+) or negative (-) charge on one side); The advantage of graphene is that it can be tuned to achieve specific tire properties (e.g., optimized wet or dry handling, rolling resistance, etc.) and charge generation (wettability) for optimal end-use applications; The advantage is that tire vibrations (which refer to bending of the material under load and unload and can be related to changes in impedance) can be captured and converted into useful power; can be provided.

[0172] FIG. 13B presents information 13B00 related to a triboelectric generator incorporated into a vehicle tire. A vehicle-specific application of the triboelectric generator described herein applies to the capture and reuse of approximately 5-7% of the energy that would otherwise be lost due to rolling friction between the tire and the pavement in contact with the tire. Specifically, a tread containing silica, cement, and metal (or metal-containing composite) can function as an electron-donating material, which is in contact with an electron-accepting material in a sensor or carbon-based microstructure, such as graphene, incorporated into the body of a pneumatic tire, such as a rubber tire, or into the entire ply.

[0173] In some examples, the role of graphene, which specifically refers to 3D hierarchical carbon-based microstructures synthesized from weak aggregates including multiple graphene sheets bonded together, can be tuned to function as an electrical conductor at its percolation threshold (the minimum concentration of filler that converts an insulating material into a conductive material), providing a relatively large contact area with the exposed tire surface for optimal charge generation. This can be particularly true in configurations where the entire width of one or more tire plies incorporates at least some carbon-based microstructures, making the entire body ply and / or tread layer at least partially conductive. The conductive material can support electrical charges generated from ablation (the vaporization of carbon-containing rubber within the tire body ply and / or tread layer as it is removed or destroyed upon contact with the pavement) by a triboelectric generator.

[0174] Moreover, graphene incorporated within tire body plies and / or tread layers can serve multiple desirable purposes, including tuning to achieve optimal tire properties, such as tuning to optimize handling under wet or dry conditions, rolling resistance, etc. Also, tire vibrations during loading and unloading conditions can affect the impedance changes observed within such partially conductive tires, where generated charge can be captured and reused for material degradation detection purposes.

[0175] 14A-14C show a schematic diagram 1400 of charge generation on a rolling wheel (with a single electrode and copper-laminated polydimethylsiloxane, PDMS, patch) demonstrating the sequential charge generation of a wheel rolling on a ground surface, such as road pavement. Whether used to form sensors on a surface, embedded within a tire ply, or mixed into a rubber compound to form a carbon-containing tire ply, any one or more of the carbon-based nanostructures of the present disclosure can function with a triboelectric energy generator including the design shown by schematic diagram 1400. As shown, the triboelectric energy generator can include a next component, a metal sheet 1406, which can be connected to an electrical load 1404 (referring to an electrical component or part of a circuit that consumes active power), which in turn is connected to a metal film 1402 in contact with a polymer film 1408 that contacts the ground surface 1410.

[0176] That is, the apparatus represented by diagram 1400 may function to power a resonator to be in electronic communication with sensors and carbon-based microstructures in or on a tire body ply and / or tread layer and other locations, and may include at least the following: We designed a single-electrode triboelectric nanogenerator (S-TENG) using a rough PDMS thin film to simulate a tire surface, and found that it can effectively harvest the friction energy wasted from a rolling tire. The design of the S-TENG is very simple and scalable, and can be easily integrated into a wide variety of potential end-use applications; The triboelectric output increases monotonically (referring to a function between a set of sequences that maintains or reverses a given sequence) depending on the tire load and travel speed; The S-TENG was successfully implemented in the tire of a toy vehicle, instantly powering six commercially available light-emitting diodes (LEDs) while the vehicle was moving on the ground. This development offers a promising solution for improving the fuel economy of conventional vehicles or the cruising ability of electric vehicles, This may correspond to the principle, function, and / or observation that

[0177] Triboelectric nanogenerators (TENGs) are generally energy harvesting devices that convert mechanical energy into electricity based on the well-known principle of triboelectric charging. An innovative design of a single-electrode TENG (S-TENG) using PDMS has been developed to harvest the waste friction energy from a rolling tire when simulating a tire surface, and can be integrated with the systems, methods, and materials disclosed herein. By fixing a PDMS S-TENG on a rubber wheel, we successfully systematically investigated its friction energy harvesting performance. The electrical output of the S-TENG on the wheel showed a monotonically increasing trend with increasing wheel speed and weight load.

[0178] The maximum instantaneous power was obtained to be approximately 1.79 mW at a load resistance of 10 MΩ, corresponding to the highest energy conversion efficiency of 10.4%. An array of multiple S-TENGs was also implemented on the tires of a toy vehicle, instantly powering six commercially available green light-emitting diodes (LEDs) while the vehicle was moving on the ground. This successful demonstration supports the promising solution of harvesting wasted friction energy from rolling tires, which can improve the fuel efficiency or cruising capacity of electric vehicles, and can be used to power the presented resonator.

[0179] 14D shows an exemplary rotor and stator configuration 14D00 for a triboelectric generator or motor, according to some embodiments. While a variety of known materials can be used, the example shown in configuration 14D00 can include (at least) an outer shell 14D02, a copper layer 14D04, a fluorinated ethylene propylene (FEP) material, which is a copolymer of hexafluoropropylene and tetrafluoroethylene (and differs from polytetrafluoroethylene resin in that it is melt-processable using conventional injection molding and screw extrusion techniques), an aluminum rotor 14D16, a sponge layer, and an acrylic core 14D14.

[0180] In operation, the acrylic core 14D14 can rotate in a 14D08 direction and be enveloped by multiple layers, each layer surrounding and in contact with both the preceding and following layers. That is, the acrylic layer 14D14 can be surrounded by a sponge layer 14D06 (which may be inwardly compressible to reduce in thickness as needed to accommodate charge capture and transfer and then recover), which can be surrounded by a copper layer 14D04 (which may include a quantity of FEP and an outer shell 14D02 dispersed therein).

[0181] Stator 14D16 can rotate in the opposite direction to 14D14 to collect the charge generated by triboelectric charging, as shown in enlarged cross section 14D12. Observed physical values ​​and parameters (e.g., when used in combination with any of the previously described triboelectric power generating means) include the following: Peak power density of 250mW / m2 at a load resistance of 20MΩ and a rotation speed of 1000r / min. Simultaneously power 16 spotlights in parallel and charge a 200μF off-the-shelf capacitor to 120V in 170 seconds; 15mW / cm measured at a 10MΩ load resistance 3 and the power density of At a load resistance of approximately 1MΩ, the output is 267mW / cm at 1000 rpm. 2 and the peak power of Includes (at least).

[0182] FIG. 14E shows a schematic diagram relating to a vehicle with an advanced self-powered system 14E00 (e.g., including a triboelectric energy generator in its representative form as an "equivalent" circuit, as described in further detail below, as well as in its actual form realized as electrical and / or discrete circuits) incorporated into a tire 14E04 (of any type, such as a conventional pneumatic tire or a next-generation solid airless tire) of the vehicle 14E02. The system 14E00 can include an arrangement of an array of compressible hexagonally structured triboelectric energy nano-generators (CH-TENGs) 14E06 secured within the body 14E08 or within one or more tread layers of the tire 14E04. The CH-TENGs 14E06 can be substantially similar to (and function accordingly with) any of the triboelectric power generation means of the present disclosure, except that each triboelectric energy generator has a substantially hexagonal shape. Another potential representation 14F02 is shown in FIG. 14F.

[0183] The CH-TENG 14E06 can generate an electric charge that can be used to create a current suitable for powering a resonator, which can further emit a signal emitted by the transceiver 14E10 (which can both transmit and receive electromagnetic radiation in the form of a signal). Certain configurations of the CH-TENG 14E06 can also include conventional electronic components such as rectifiers and capacitors that can communicate with wireless tire pressure sensors that can be part of a tire pressure monitoring system (TPMS) to provide an overall tire wear monitoring solution.

[0184] System 14E00 may include at least three (3) types of components, functions, and / or subsystems related to detecting and communicating anomalies to a tire: transmitting an RF signal, such as by a transceiver 14E10, or further by a resonator; resonating in response to an RF signal (more specifically, generating a respective resonant signal by resonating in response to an excitation signal), such as performed by a conventional LC, resonant, and / or tank circuit (or any other discrete circuit element) and / or by a carbon-containing microstructure tuned to resonate and / or attenuate the signal at a known frequency and / or intensity level; Shifting the frequency of the RF signal and / or attenuating the RF signal, as performed by a sensor made of a carbon-containing material or by an entire surface, such as a tread layer and / or ply, of a vehicle tire containing the mixture, such as at a fixed or variable concentration level; This may include equipment that functions by

[0185] Generally, resonators can be realized in discrete form, i.e., as an LC circuit, also called a resonant circuit, tank circuit, or tuned circuit. This type of resonator is an electrical circuit made up of discrete components, such as an inductor, represented by the letter L, and a capacitor, represented by the letter C, connected together. The circuit functions as an electrical resonator, the electrical analog of a tuning fork, capable of storing energy and releasing it oscillating at the circuit's natural resonant frequency.

[0186] LC circuits can be used to either generate a signal at a specific frequency or extract a signal at a specific frequency from a more complex signal. This function is called a "bandpass filter." They are key components in many electronic devices, especially radio equipment, where they are used in circuits such as oscillators, filters, tuners, and frequency mixers.

[0187] However, incorporating discrete electronic components into areas where abrasion is likely to be high, such as a vehicle tire tread layer exposed to contact with the pavement or ground, can be problematic given the possible undesirable degradation and failure of such components, such as conventional LC circuits as described above, due to, for example, wear and tear and / or elevated temperatures.

[0188] Thus, in some embodiments, the resonator can be fabricated solely from carbon-containing microstructures and related materials, independent of any discrete electronics. Such carbon-containing microstructures can form sensors that can be embedded within tire plies, tire tread layers, or both of a tire body. Furthermore, the carbon-containing microstructures can be incorporated into tire-forming materials (e.g., rubber) present within one or more plies and / or tire tread layers, for example, at various similar concentration levels (or even the same concentration levels), which can affect signal generation performance.

[0189] Sensors, plies, and / or tire tread layers made from carbon-containing microstructures can effectively and completely replace conventional discrete circuit components, such as the resonant circuits described above, by providing comparable (or at least substantially identical) functionality and performance, and can therefore be represented by an equivalent circuit 14E12. This equivalent circuit can be powered by, or not by, the CH-TENG 14E06, by resonating in response to an excitation signal (such as that emitted by a transceiver) to generate a respective resonant signal. An equivalent circuit refers to a theoretical circuit that retains all the electrical properties of a given circuit (such as a resonant circuit), but is composed of linear, passive elements (and thus does not necessarily use conventional discrete circuit elements).

[0190] Thus, unwanted breakdowns in conventional discrete circuits can be avoided by implementing sensors, plies, and / or tire tread layers made from carbon-containing microstructures that function as equivalent circuits. In such a configuration, there are no discrete electronic devices installed inside the tire. Rather, one or more various tire tread layers and / or tire body plies of the tire can be composed of (and / or otherwise include sensors made from) carbon-containing tuned microstructured resonant materials. These carbon-containing tuned microstructured resonant materials resonate at a known frequency or within a known frequency range, facilitating accurate and precise identification of component wear.

[0191] FIG. 14F shows various types of triboelectric energy generator configurations 14F00 intended for incorporation into vehicle tires. Such configurations may be substantially hexagonal, as shown by enlarged cross section 14F12, or may take any of the forms shown by Structures I-VI (represented by representations 14F02, 14F04, 14F06, 14F08, 14F10, and 14F12, respectively), given that the CH-TENG is contained within a tire ply (as shown in body 14E08 of tire 14E04 shown in FIG. 14E) and can compress in response to tire compression during cyclic compression and decompression cycles (colloquially referred to as "collapse") commensurate with contact of the tire body ply and / or tread layer with the ground. The cyclic compression-decompression behavior can facilitate the charge recovery function of the CH-TENG.

[0192] FIG. 15A is a presentation of information 15A00 related to sensor-based monitoring of vehicle tires achieved through a tire pressure monitoring system (TPMS). Generally, a tire pressure monitoring system (TPMS) refers to an electronic system designed to monitor air pressure in pneumatic tires of various types of vehicles. A TPMS reports real-time tire pressure information to the vehicle driver via either a gauge, a pictogram display, or a simple low-pressure warning light. TPMS can be divided into two different types: direct (dTPMS) and indirect (iTPMS). TPMS are offered both at the OEM (factory) level and as an aftermarket solution. The goal of a TPMS is to prevent traffic accidents, poor fuel economy, and increased tire wear due to under-inflated tires through early recognition of dangerous tire conditions.

[0193] Any of the disclosed methods, systems, and materials can be functionally combined with any type of TPMS to support TPMS functionality and provide additional, enhanced, tire degradation information. As presented, an iTPMS can monitor either speed, vibration, or wheel radius, and can employ more advanced methods, including determining deformation and friction (essentially "piggybacking" off existing anti-lock braking systems (ABS) sensor suites) using a Kalman filter (also known as a linear quadratic estimation (LQE), an algorithm that uses a series of measurements observed over time, including statistical noise and other imprecisions, to estimate the joint probability distribution of the variables for each time frame, thereby producing estimates of unknown variables that tend to be more accurate than those based on a single measurement alone) in addition to strain, temperature, and acceleration. A dTPMS can also utilize the following: Two surfaces come into contact (wheel rim, valve, Nb2O5 active material) with a capacitive sensor and / or energy generator, The film is much harder than rubber (peelability) but is a polyimide-based strain gauge. Surface acoustic wave (SAW) sensors are a class of microelectromechanical systems (MEMS) that rely on modulation of surface acoustic waves to sense physical phenomena, where the sensor converts an input electrical signal into a mechanical wave, which, unlike the electrical signal, can be susceptible to being affected by the physical phenomenon, and the device then converts this wave back into an electrical signal, where changes in amplitude, phase, frequency, or time delay between the input and output electrical signals can be used to measure the presence of the desired phenomenon, and the SAW sensor is an interdigitated electrode on a piezoelectric substrate; A Fabry-Perot interferometer (FPI) or etalon, which is an optical cavity made from two parallel reflective surfaces (such as thin mirrors), so that light waves can pass through the optical cavity only if they are resonant with the optical cavity. Hall effect sensors, which refer to devices used to measure the magnitude of magnetic fields, whose output voltage is directly proportional to the strength of the magnetic field passing through it, and Hall effect sensors are used in proximity sensing of tread deformation (GaAs on ceramic), positioning, speed sensing, and current sensing applications; and MEMS (Microelectromechanical Systems, specifically referring to the technology of microscopic devices with moving parts) and Non-contact ultrasonic system (mounted on the wheel rim inside the tire) A resistor-capacitor parallel circuit integrated on the steel wire belt; It may be combined with or integrated with other features and / or technologies (at least):

[0194] Graphene and / or other ordered carbon-based sensors may be combined with the aforementioned TPMS systems to provide the following sensor types and / or variations: Capacitance and Strain gauges and Piezoelectric sensors (ZnO-coated carbon nanotubes, CNTs) Any one or more of the following may be used.

[0195] 15B is a schematic side view of substrate assembly 15B00 incorporating substrate 15B04. Substrate assembly 15B00 is part of an ABS sensor suite and can interact with or function with any of the systems, methods, and materials of the present disclosure, for example, incorporating carbon-based microstructures or the like to provide power (in the form of electrical current) to the resonator. Substrate assembly 15B00 can have diaphragm thickness 15B06 that can expand (or compress) near silicon-containing region 15B02 in response to an external force (indicated by arrows) above gap 15B08. Gap 15B08 can be disposed above insulating layer 15B10 on the top surface of substrate electrode 15B12.

[0196] 15C is a schematic diagram of a polyimide-based strain gage system 15C00 configured to monitor tire pressure and may include computing resources 15C02, strain gages 15C04 responsive to externally applied forces 15C10, and miniaturized functionality to accommodate tire ply fitments 15C12 on the tire body ply and / or tread layer 15C08. The polyimide-based strain gage system 15C00 may be part of a TPMS in communication with any of the systems, methods, and materials of the present disclosure to extend tire pressure sensing functionality with more detailed tire condition degradation related information.

[0197] FIG. 15D is a schematic cross-sectional view of a Hall sensor system 15D00 incorporating gallium arsenide (GaAs) on ceramic configured to detect deformation of a vehicle tire tread. The Hall sensor system 15D00 is part of a TPMS in communication with any of the systems, methods, and materials of the present disclosure, and can extend tire pressure detection functionality with more detailed tire condition degradation-related information. The Hall sensor system 15D00 can include a steel cord 15D04 (as part of the vehicle tire). A gallium arsenide (GaAs) Hall effect generator 15D06 functions in conjunction with a magnet 15D08 within the body 15D10 (of the tire) above the tread element that contacts the road (shown as pavement 15D12). The Hall sensor system 15D00 functions to generate charge and / or current that can be used to power a resonator during vehicle operation to ascertain tire condition information.

[0198] 15E shows a schematic diagram associated with a non-contact ultrasonic parallel resistor-capacitor circuit 15E00 integrated onto a pair 15E04 of steel wire belts 15E02 within a tire body. The function of the non-contact ultrasonic parallel resistor-capacitor circuit 15E00 can generate a charge and / or current that can be used to power a resonator (as disclosed herein) during vehicle operation to ascertain tire condition information. The pair 15E04 of steel wire belts 15E02 can be positioned a defined distance 15E10 apart to exhibit quantifiable values ​​of dielectric constant 15E06 and / or resistivity 15E08.

[0199] FIG. 15F shows another suitable configuration of a non-contact ultrasonic electrical resistor-capacitor parallel circuit 15E00 (non-contact refers to no contact between the individual steel wire belts), where the steel wires are electrically coupled to and / or electrically connected with corresponding electrodes as may be required to store and transfer charge and / or conduct current and power the resonator as disclosed herein.

[0200] Figure 15G shows a simplified schematic diagram of a representation of a non-contact ultrasonic electrical resistor-capacitor parallel circuit 15E00 (shown in Figure 15E), which in some embodiments can be another type of "equivalent circuit" that features no discrete circuitry, but instead implements a theoretical circuit composed of carbon-containing microstructures that exhibit all the electrical properties of a given circuit. As an example, this equivalent electrical circuit can include carbon-containing microstructure resonant materials that mimic the function of at least a capacitor (C) and a resistor (R), which can be optionally configured to resonate when needed for detection of frequency shift behavior and / or signal attenuation exhibited by the resonant materials.

[0201] 15H shows a schematic diagram 15H00 of an electrical resistor-capacitor parallel circuit 15H10 (including multiple wires 15H12) integrated onto a steel wire belt 15H06 of a vehicle tire 15H02. The steel wire belt 15H06 can be located near a tire component (such as a sidewall) 15H04 without interfering with the tire tread pattern 15H08. The electrical resistor-capacitor parallel circuit 15H10 can generate usable charge and / or power or current through any one or more of the aforementioned means, such as by triboelectric principles, or otherwise, and supply such power to a resonator of the present disclosure.

[0202] 16-18 show various three-dimensional carbon-containing aggregates grown on structured carbon, various carbon nanoparticles, various carbon-based aggregates, and other materials. What is disclosed can be examples of carbon-based microstructures as referred to herein.

[0203] Figure 19 shows a Raman shift plot for one or more of the structured carbons and / or the like shown in Figures 16-18. The peak is at about 2670 cm -1 , 1600cm -1 , and 1380 cm -1 (or around that time).

[0204] 20 shows a schematic perspective view 2000 of an exemplary grid arrangement 2008 of components (such as rubber) within a tire body ply and / or tread layer, with resonant circuit (also referred to herein as "resonator") components 2002, 2004, and 2006 embedded within or between these elements. Any conceivable configuration is possible for the resonant circuit components, and such configurations can affect oscillation and / or resonance functions for further signal generation, such as may be relevant to identifying tire degradation as presently disclosed herein.

[0205] FIG. 21 is an exemplary Raman intensity heat map or plot illustrating the signal attenuation associated with the resonant circuit shown in FIG. 20 when incorporated into a vehicle tire body ply and / or tread layer and during operation.

[0206] FIG. 22 is a schematic diagram illustrating an exemplary arrangement of self-assembled carbon-based particles having various weakly aggregated patterns 2206, 2208, and 2210 shown, any one or more of which can constitute concentrated regions 2204 that can affect the resonant performance of the material in which the carbon-based microstructures are incorporated.

[0207] Usage Overview Deployment example Any one or more of the aforementioned techniques and materials can be combined in a manufacturing process for a surface sensor intended to be embedded within a vehicle-related material and / or a surface such as a tire ply. The automotive surface sensor can be manufactured by selecting a carbon allotrope based at least in part on a specified frequency, mixing the carbon allotrope with other components of a composite material, and then using the composite material to form the automotive surface sensor. The automotive surface sensor resonates at a specified frequency when stimulated by electromagnetic radiation (an RF signal) of the specified frequency.

[0208] Additionally, any or all of the aforementioned techniques and materials can be combined into a tire manufacturing process. Automotive tires can be manufactured by selecting a carbon allotrope based at least in part on a specified frequency, mixing the carbon allotrope with other ingredients used in one or more tire materials, and then combining the one or more tire materials with additional tire components and assembling the tire. The tire material resonates at a specified frequency when stimulated by electromagnetic radiation of the specified frequency. Furthermore, such resonance can be triggered by proximal electromagnetic radiation (such as a ping) of the specified frequency. Specifically, by way of example, a tuned antenna emitting proximal electromagnetic radiation of the specified frequency can be located within the wheel well of the vehicle.

[0209] Structured Carbon Overview Additional Structured Carbon Examples 23A through 23Y illustrate carbon-based materials, growths, weak aggregates, strong aggregates, sheets, particles, and / or the like, such as those self-nucleated in-flight within a reaction chamber or reactor from carbon-containing gas phase species such as methane (CH), as disclosed by Stowell, et al. in U.S. Patent Application No. 16 / 785,020, filed February 7, 2020, entitled "3D Self-Assembled Multi-Modal Carbon-Based Particle."

[0210] The carbon-based nanoparticles and aggregates described can be characterized by a high degree of "uniformity" (e.g., a high mass fraction of the desired carbon allotrope), a high degree of "order" (e.g., a low concentration of defects), and / or a high degree of "purity" (e.g., a low concentration of elemental impurities), in contrast to the less uniform, less ordered, and less pure particles achievable with conventional systems and methods.

[0211] The nanoparticles produced using the methods described herein can comprise multilayer spherical fullerenes (MWSFs) or combined MWSFs, and exhibit high uniformity (e.g., ratios of graphene to MWSFs between 20% and 80%), a high degree of order (e.g., I of 0.95 to 1.05), and a high degree of solubility (I of 0.95 to 1.05). D / I G The nanoparticles produced using the methods described herein can have a high degree of purity (e.g., a Raman signature having a ratio of carbon to other elements (other than hydrogen) greater than 99.9%). The nanoparticles produced using the methods described herein comprise MWSFs or combined MWSFs, where the MWSFs do not include a core composed of impurity elements other than carbon. The particles produced using the methods described herein can be aggregates comprising the above nanoparticles having large diameters (e.g., greater than 10 μm).

[0212] While conventional methods have been used to produce particles containing highly ordered multilayered spherical fullerenes, they can lead to end products with various drawbacks. For example, high-temperature synthesis techniques result in particles containing a mixture of many carbon allotropes, resulting in low uniformity (e.g., less than 20% fullerenes relative to other carbon allotropes) and / or small particle sizes (e.g., less than 1 μm, or even less than 100 nm). Catalytic methods can also result in products containing catalytic elements, resulting in relatively low purity (less than 95% carbon relative to other elements). These undesirable properties often result in undesirable electrical properties (e.g., conductivity less than 1,000 S / m) in the resulting carbon particles.

[0213] The carbon nanoparticles and aggregates described herein can be characterized by Raman spectroscopy, which indicates a high degree of structural order and uniformity. The uniform, ordered, and / or pure carbon nanoparticles and aggregates described herein can be produced using improved thermal reactors and methods that are relatively fast and low cost, as described below.

[0214] The term "graphene," as commonly understood and as referred to herein, connotes a carbon allotrope in the form of a two-dimensional, atomic-scale, hexagonal lattice with one atom forming each vertex. The carbon atoms in graphene are arranged in a SP 2 Furthermore, graphene has a bond at approximately 1580 cm -1 G mode, approximately 1350cm -1 The Raman spectrum has two main peaks: the D mode (when using a 532 nm excitation laser) at 1000 kHz and the D mode (when using a 532 nm excitation laser).

[0215] The term "fullerene," as commonly understood and as referred to herein, connotes a molecule of carbon in the form of a hollow sphere, ellipsoid, tube, or other shape. Spherical fullerenes are sometimes called buckminsterfullerenes or buckyballs. Cylindrical fullerenes are sometimes called carbon nanotubes. Fullerenes are structurally similar to graphite, consisting of stacked graphene sheets of linked six-membered rings. Fullerenes may also contain five-membered (or sometimes seven-membered) rings.

[0216] The term "multi-layer fullerene," as commonly understood and as referred to herein, refers to a fullerene having multiple concentric layers. For example, a multi-walled nanotube (MWNT) contains multiple rolled layers (concentric tubes) of graphene. A multi-layered spherical fullerene (MWSF) contains multiple concentric spheres of fullerene.

[0217] The term "nanoparticle," as commonly understood and as referred to herein, connotes a particle having a size ranging from 1 nm to 989 nm. Nanoparticles can include one or more structural characteristics (e.g., crystalline structure, defect concentration, etc.) and one or more types of atoms. Nanoparticles can be any shape, including, but not limited to, spherical, ellipsoidal, dumbbell-shaped, cylindrical, elongated cylindrical, rectangular prism-shaped, disk-shaped, wire-shaped, irregular, dense (e.g., less void), porous (e.g., more void), etc.

[0218] The term "aggregate," as commonly understood and as referred to herein, connotes a plurality of nanoparticles bound together by van der Waals forces, covalent bonds, ionic bonds, metallic bonds, or other physical or chemical interactions. The size of the aggregate can vary considerably but is generally greater than about 500 nm.

[0219] Carbon nanoparticles can include two (2) or more bonded multilayer spherical fullerenes (MWSFs) and a graphene layer coating the bonded MWSFs, and can be formed independently from a core composed of impurity elements other than carbon. As described herein, carbon nanoparticles can include two (2) or more bonded multilayer spherical fullerenes (MWSFs) and a graphene layer coating the bonded MWSFs. In such an arrangement, the MWSFs do not contain a void (referring to a space without carbon atoms larger than about 0.5 nm or larger than about 1 nm) in their center. The bonded MWSFs can be sp 2 -hybrid orbital carbon atoms (as opposed to conventional spheres of randomly ordered, non-uniform amorphous carbon particles, which may otherwise fail to achieve any one or more of the unexpectedly desirable properties disclosed herein).

[0220] The average diameter of the nanoparticles containing the conjugated MWSF is in the range of 5 to 500 nm, or 5 to 250 nm, or 5 to 100 nm, or 5 to 50 nm, or 10 to 500 nm, or 10 to 250 nm, or 10 to 100 nm, or 10 to 50 nm, or 40 to 500 nm, or 40 to 250 nm, or 40 to 100 nm, or 50 to 500 nm, or 50 to 250 nm, or 50 to 100 nm.

[0221] The carbon nanoparticles described herein form aggregates, where many nanoparticles join together to form larger units. The carbon aggregates can be multiple carbon nanoparticles. The overall diameter of the carbon aggregate can range from 10 to 500 μm, or 50 to 500 μm, or 100 to 500 μm, or 250 to 500 μm, or 10 to 250 μm, or 10 to 100 μm, or 10 to 50 μm. The aggregates can be formed from multiple carbon nanoparticles, as defined above. The aggregates can be highly uniform (e.g., graphene to MWSF ratios of 20% to 80%), highly ordered (e.g., I D / I G The Raman signature may include a combined MWSF, such as a Raman signature with a ratio of 0.95 to 1.05, and one that is highly pure (e.g., greater than 99.9% carbon).

[0222] Carbon nanoparticle aggregates, primarily those with diameters within the above range, particularly those greater than 10 μm, are generally easier to collect than particles smaller than 500 nm or aggregates. This ease of collection reduces the cost of the manufacturing equipment used to produce carbon nanoparticles and increases the yield of carbon nanoparticles. Particles greater than 10 μm in size also pose fewer safety concerns compared to the risks of handling small nanoparticles, such as the potential health and safety risks associated with inhaling small nanoparticles. Therefore, the reduced health and safety risks further reduce production costs.

[0223] The carbon nanoparticles disclosed herein may have a graphene to MWSF ratio of 10% to 90%, 10% to 80%, 10% to 60%, 10% to 40%, 10% to 20%, 20% to 40%, 20% to 90%, 40% to 90%, 60% to 90%, or 80% to 90%. The graphene to MWSF ratio of the carbon aggregates may be 10% to 90%, 10% to 80%, 10% to 60%, 10% to 40%, 10% to 20%, 20% to 40%, 20% to 90%, 40% to 90%, 60% to 90%, or 80% to 90%. The ratio of graphene in the carbon nanoparticles to the bonded MWSF is 10% to 90%, or 10% to 80%, or 10% to 60%, or 10% to 40%, or 10% to 20%, or 20% to 40%, or 20% to 90%, or 40% to 90%, or 60% to 90%, or 80% to 90%. The ratio of graphene in the carbon aggregates to the bonded MWSF is 10% to 90%, or 10% to 80%, or 10% to 60%, or 10% to 40%, or 10% to 20%, or 20% to 40%, or 20% to 90%, or 40% to 90%, or 60% to 90%, or 80% to 90%.

[0224] Raman spectroscopy can be used to characterize carbon allotropes to distinguish their molecular structures. For example, graphene can be characterized using Raman spectroscopy to determine information such as order / disorder, edges and grain boundaries, thickness, number of layers, doping, strain, and thermal conductivity. MWSFs have also been characterized using Raman spectroscopy to determine the degree of order in the MWSF.

[0225] Raman spectroscopy is used to characterize the structure of MWSFs or bonded MWSFs used with reference to those incorporated within various tire-related plies of a tire, as discussed herein. The dominant peaks in the Raman spectrum are the G mode and the D mode. The G mode is sp 2The D mode is due to vibrations of carbon atoms in the -orbital hybrid carbon network, and is associated with breathing of defective carbon hexagons. In some situations, defects may be present but not detectable in the Raman spectrum. For example, if the presented crystal structure is perpendicular to the basal plane, the D peak will increase. Alternatively, if a perfectly planar surface parallel to the basal plane is presented, the D peak will be zero.

[0226] When using 532 nm incident light, the Raman G mode is typically located at 1582 cm for planar graphite. -1 , but can be shifted down in the MWSF or combined MWSF (e.g., 1565 cm -1 or 1580cm -1 The D mode appears at approximately 1350 cm in the Raman spectrum of the MWSF or combined MWSFs. -1 The ratio of the intensity of the D-mode peak to the G-mode peak (e.g., I D / I G ) is related to the degree of order of the MWSF, and I D / I G A low I indicates a high degree of order. D / I G A value around or less than 1 indicates a relatively high degree of order, and I D / I G A value greater than 1.1 indicates a low degree of order.

[0227] As described herein, carbon nanoparticles or carbon aggregates containing MWSF or bound MWSF have a first Raman peak at about 1350 cm when using incident light at 532 nm. -1 The second Raman peak is at approximately 1580 cm -1 The ratio of the intensity of the first Raman peak to the intensity of the second Raman peak (e.g., I D / I G) can be in the range of 0.95 to 1.05, or 0.9 to 1.1, or 0.8 to 1.2, or 0.9 to 1.2, or 0.8 to 1.1, or 0.5 to 1.5, or less than 1.5, or less than 1.2, or less than 1.1, or less than 1, or less than 0.95, or less than 0.9, or less than 0.8.

[0228] As defined above, the carbon aggregates comprising MWSF or bound MWSF have high purity. The carbon to metal ratio of the MWSF or bound MWSF carbon aggregates is greater than 99.99%, or greater than 99.95%, or greater than 99.9%, or greater than 99.8%, or greater than 99.5%, or greater than 99%. The carbon aggregates have a carbon to other element ratio of greater than 99.99%, or greater than 99.95%, or greater than 99.9%, or greater than 99.5%, or greater than 99%, or greater than 90%, or greater than 80%, or greater than 70%, or greater than 60%. In the carbon aggregate, the ratio of carbon to other elements (excluding hydrogen) is greater than 99.99%, or greater than 99.95%, or greater than 99.9%, or greater than 99.8%, or greater than 99.5%, or greater than 99%, or greater than 90%, or greater than 80%, or greater than 70%, or greater than 60%.

[0229] As defined above, carbon aggregates containing MWSF or combined MWSF have a high specific surface area. Carbon aggregates have a Brunauer, Emmett, and Teller (BET) specific surface area of ​​10 to 200 m 2 / g, or 10 to 100 m 2 / g, or 10-50m 2 / g, or 50-200m 2 / g, or 50-100m 2 / g, or 10 to 1000m 2 / g.

[0230] Carbon aggregates comprising MWSF or bonded MWSF, as defined above, have high electrical conductivity. Carbon aggregates comprising MWSF or bonded MWSF, as defined above, are compressed into pellets, and the conductivity of the pellets is greater than 500 S / m, or greater than 1,000 S / m, or greater than 2,000 S / m, or greater than 3,000 S / m, or greater than 4,000 S / m, or greater than 5,000 S / m, or greater than 10,000 S / m, or greater than 20,000 S / m, or greater than 30,000 S / m, or greater than 40,000 S / m, or greater than 50,000 S / m, or greater than 60,000 S / m, or greater than 70,000 S / m. 000 S / m, or between 500 S / m and 100,000 S / m, or between 500 S / m and 1,000 S / m, or between 500 S / m and 10,000 S / m, or between 500 S / m and 20,000 S / m, or between 500 S / m and 100,000 S / m, or between 1,000 S / m and 20,000 S / m, or between 10,000 S / m and 100,000 S / m, or between 10,000 S / m and 80,000 S / m, or between 500 S / m and 10,000 S / m. In some cases, the density of the pellets is about 1 g / cm 3 , or approximately 1.2 g / cm 3 , or about 1.5 g / cm 3 , or about 2 g / cm 3 , or approximately 2.2 g / cm 3 , or about 2.5 g / cm 3 , or about 3 g / cm 3 Additionally, tests were conducted in which compressed pellets of carbon aggregate material were formed at compressions of 2,000 psi and 12,000 psi with annealing temperatures of 800°C and 1,000°C. Higher compression and / or higher annealing temperatures generally resulted in pellets with higher electrical conductivity, including within the range of 12,410.0 S / m to 13,173.3 S / m.

[0231] High-purity carbon allotropes produced using a heat treatment system The carbon nanoparticles and aggregates described herein can be produced using thermal reactors and methods. Further details regarding the thermal reactors and / or methods used can be found in U.S. Patent No. 9,862,602, entitled "CRACKING OF A PROCESS GAS," issued January 9, 2018, which is incorporated herein by reference in its entirety. Additionally, thermal reactors can be used with carbon-containing and / or hydrocarbon precursors (referring to at least methane, ethane, propane, butane, and natural gas) to produce the carbon nanoparticles and carbon aggregates described herein.

[0232] The carbon nanoparticles and aggregates described herein are produced using a thermal reactor having a gas flow rate of 1 slm to 10 slm, or 0.1 slm to 20 slm, or 1 slm to 5 slm, or 5 slm to 10 slm, or greater than 1 slm, or greater than 5 slm. The carbon nanoparticles and aggregates described herein are produced using a thermal reactor having a gas resonance time of 0.1 seconds (s) to 30 s, or 0.1 s to 10 s, or 1 s to 10 s, or 1 s to 5 s, or 5 s to 10 s, or greater than 0.1 s, or greater than 1 s, or greater than 5 s, or less than 30 s.

[0233] The carbon nanoparticles and aggregates described herein can be produced using a thermal reactor having a production rate of 10 g / hr to 200 g / hr, or 30 g / hr to 200 g / hr, or 30 g / hr to 100 g / hr, or 30 g / hr to 60 g / hr, or 10 g / hr to 100 g / hr, or greater than 10 g / hr, or greater than 30 g / hr, or greater than 100 g / hr.

[0234] Thermal reactors (or other cracking devices) and thermal reactor processes (or other cracking processes) can be used to purify, pyrolyze, dissociate, or decompose raw process gases into their constituent parts to produce the carbon nanoparticles and carbon aggregates described herein, as well as other solid and / or gaseous products, such as hydrogen gas and / or less ordered hydrocarbon gases. The raw process gases are typically, for example, hydrogen gas (H 2 ), carbon dioxide (CO 2 ), C 1 ~C 10 The carbon nanoparticles and carbon aggregates may include, for example, multi-walled spherical fullerenes (MWSFs), bonded MWSFs, carbon nanospheres, graphene, graphite, highly ordered pyrolytic graphite, single-walled nanotubes, multi-walled nanotubes, other solid carbon products, and / or the carbon nanoparticles and carbon aggregates described herein.

[0235] The methods for producing carbon nanoparticles and carbon aggregates described herein can include pyrolysis methods, such as those using an elongated, longitudinal heating element optionally enclosed within an elongated casing, housing, or body of a pyrolyzer. The body can include one or more tubes or other suitable enclosures made of, for example, stainless steel, titanium, graphite, quartz, or the like. The pyrolyzer body is generally cylindrical, with a central, elongated, longitudinal axis oriented vertically, and a feedstock process gas inlet at or near the top of the body. The feedstock process gas can flow longitudinally downward through the body or a portion thereof. In a vertical configuration, both gas flow rate and gravity assist in the removal of solid products from the pyrolyzer body.

[0236] The heating elements may include any one or more of heat lamps, one or more resistive wires or filaments (or twisted wires), metal filaments, metal strips or rods, and / or other suitable thermal radical generators or elements capable of heating to a specific temperature (e.g., molecular decomposition temperature) sufficient to pyrolyze the molecules of the feed process gas. The heating elements may be disposed, located, or arranged within the body of the pyrolysis apparatus so as to extend centrally along its central longitudinal axis. In configurations with only one heating element, the heating element may be disposed on or concentrically disposed about the central longitudinal axis. Alternatively, in configurations with multiple heating elements, the heating elements may be disposed generally symmetrically, concentrically spaced, or offset in parallel positions near, around, and parallel to the central longitudinal axis.

[0237] Pyrolysis to produce the carbon nanoparticles and aggregates described herein can be accomplished by flowing a raw process gas over, in contact with, or near a heating element within a longitudinally elongated reaction zone generated by heat from a heating element and defined by and contained within the body of the pyrolysis apparatus, and heating the raw process gas to or at a specific molecular decomposition temperature.

[0238] The reaction zone can be considered to be the area surrounding the heating element and close enough to the heating element that the raw process gas receives sufficient heat to pyrolyze its molecules. Thus, the reaction zone is generally axially aligned or concentric with the central longitudinal axis of the body. Pyrolysis occurs under specific pressures. The raw process gas is circulated around or across the exterior of the reaction zone or heating chamber vessel, which cools and preheats the raw process gas before it enters the reaction zone.

[0239] The carbon nanoparticles and aggregates and / or hydrogen gas described herein are produced without the use of a catalyst, and therefore the process can be completely catalyst-free.

[0240] The disclosed methods and systems advantageously can be rapidly scaled up or down for different production levels as needed, such as providing a stand-alone hydrogen and / or carbon nanoparticle production station, hydrocarbon source, or fuel cell station, and being expandable to provide large capacity systems such as refineries and / or the like.

[0241] A pyrolysis apparatus for decomposing a feedstock process gas to produce the carbon nanoparticles and aggregates described herein includes a body, a feedstock process gas inlet, and an elongated heating element. The body has an interior volume about a longitudinal axis. The interior volume has a reaction zone concentric with the longitudinal axis. The feedstock process gas can flow into the interior volume through the feedstock process gas inlet during a pyrolysis operation. The elongated heating element can be disposed within the interior volume along the longitudinal axis and is surrounded by the reaction zone. During the pyrolysis operation, the elongated heating element is heated by electrical power to a molecular decomposition temperature to create the reaction zone, and the feedstock process gas is heated by heat from the elongated heating element, which pyrolyzes the molecules of the feedstock process gas into molecular constituents within the reaction zone.

[0242] The method for decomposing a raw process gas to produce carbon nanoparticles and aggregates described herein can include at least one of the following: (1) providing a pyrolysis apparatus having an interior volume having a longitudinal axis and an elongated heating element disposed within the interior volume along the longitudinal axis; (2) heating the elongated heating element with electrical power to a molecular decomposition temperature to create a longitudinally elongated reaction zone within the interior volume; (3) flowing the raw process gas into the interior volume and through the longitudinally elongated reaction zone (e.g., the raw process gas is heated by heat from the elongated heating element); and (4) pyrolyzing the raw process gas molecules within the longitudinally elongated reaction zone into their constituents (e.g., hydrogen gas and one or more solid products) as the raw process gas flows through the longitudinally elongated reaction zone.

[0243] The raw process gas used to produce the carbon nanoparticles and aggregates described herein can include hydrocarbon gases. Cracking results in the production of gaseous hydrogen (H 2 The carbon nanoparticles and aggregates may further include carbon nanoparticles and aggregates of various forms described herein. The carbon nanoparticles and aggregates may include two or more MWSFs and a graphene layer coating the MWSFs, and / or bonded MWSFs and a graphene layer coating the bonded MWSFs. The raw process gas is preheated (e.g., to 100°C to 500°C) by flowing the raw process gas through a gas preheating region between the heating chamber and the shell of the pyrolysis apparatus and then flowing the raw process gas into the interior volume. There, the nanoparticle-laden gas flows into the interior volume and mixes with the raw process gas through a longitudinally elongated reaction zone to form a coating of solid product (e.g., graphene layer) around the nanoparticles.

[0244] Post-treatment of high purity structured carbon The carbon nanoparticles and aggregates comprising the multilayered spherical fullerenes (MWSFs) or bonded MWSFs described herein can be produced and collected without the need for any post-processing or manipulation. Alternatively, some post-processing can be performed on one or more of the MWSFs of the present disclosure. Some examples of post-processing relevant to the creation and use of resonant materials include mechanical treatments such as ball milling, pulverization, attrition milling, microfluidization, and other techniques that reduce particle size without damaging the MWSFs. Some further examples of post-processing include exfoliation processes (referring to the complete separation of layers of carbon-containing materials, such as the creation or extraction of graphene layers from graphite), which include shear mixing, chemical etching, oxidation (such as the Hummer process), thermal annealing, doping by adding elements (such as sulfur and / or nitrogen) during annealing, steam treatment, filtration, and freeze-drying. Some examples of post-processing include sintering processes, such as spark plasma sintering (SPS), direct current sintering, microwave sintering, and ultraviolet (UV) sintering, which can be performed at high pressures and temperatures in an inert gas. Multiple post-treatment methods can be used together or sequentially to produce functionalized carbon nanoparticles or aggregates containing multilayer spherical fullerenes (MWSFs) or bound MWSFs.

[0245] Materials can be mixed together in various combinations, amounts, and / or ratios. Different carbon nanoparticles and aggregates comprising MWSF or bonded MWSF described herein can be mixed together, if any, before one or more post-processing operations. For example, different carbon nanoparticles and aggregates comprising MWSF or bonded MWSF with different properties (e.g., different processing steps, different sizes, different compositions, different purity runs, etc.) can be mixed together. Carbon nanoparticles and aggregates comprising MWSF or bonded MWSF described herein can be mixed with graphene to vary the ratio of bonded MWSF to graphene in the mixture. Different carbon nanoparticles and aggregates comprising MWSF or bonded MWSF described herein can be mixed together after post-processing. Different carbon nanoparticles and aggregates comprising MWSF or bonded MWSF with different properties and / or different post-processing methods (different sizes, different compositions, different functionality, different surface properties, different surface areas, etc.) can be mixed together in any amount, ratio, and / or combination.

[0246] After the carbon nanoparticles and aggregates described herein are produced and collected, they are processed by mechanical comminution, grinding, and / or exfoliation. Processing (by mechanical comminution, grinding, exfoliation, etc.) can reduce the average particle size. Processing (by mechanical comminution, grinding, exfoliation, etc.) increases the average surface area of ​​the particles. Processing by mechanical comminution, grinding, and / or exfoliation shears off portions of the carbon layers, producing sheets of graphite that are mixed with the carbon nanoparticles.

[0247] Mechanical comminution or grinding can be accomplished using a ball mill, planetary mill, rod mill, shear mixer, high-shear granulator, autogenous mill, or other type of mechanical process used to break solid materials into smaller pieces by pulverizing, crushing, or cutting. Mechanical comminution, grinding, and / or scraping can be done wet or dry. Mechanical comminution can be accomplished by grinding for a period, idling for a period, and then repeating several cycles of grinding and idling. The grinding period can be 1 minute (min) to 20 min, or 1 min to 10 min, or 3 min to 8 min, or about 3 min, or about 8 min. The idling period can be 1 min to 10 min, or about 5 min, or about 6 min. The number of grinding and idling cycles can be 1 min to 100 min, or 5 min to 100 min, or 10 min to 100 min, or 5 min to 10 min, or 5 min to 20 min. The total time for grinding and idling is 10 minutes to 1,200 minutes, or 10 minutes to 600 minutes, or 10 minutes to 240 minutes, or 10 minutes to 120 minutes, or 100 minutes to 90 minutes, or 10 minutes to 60 minutes, or about 90 minutes.

[0248] The comminution step in a cycle is accomplished by rotating the mill in one direction (e.g., clockwise) for the first cycle and then rotating the mill in the opposite direction (e.g., counterclockwise) for the next cycle. Mechanical comminution or grinding is accomplished using a ball mill, with the comminution step being accomplished using a rotation speed of 100-1000 rpm, or 100-500 rpm, or about 400 rpm. Mechanical comminution or grinding is accomplished using a ball mill with grinding media having a diameter of 0.1 mm to 20 mm, or 0.1 mm to 10 mm, or 1 mm to 10 mm, or about 0.1 mm, or about 1 mm, or about 10 mm. Mechanical comminution or grinding is accomplished using a ball mill with grinding media composed of metals such as steel, oxides such as zirconium oxide (zirconia), yttria-stabilized zirconium oxide, silica, alumina, magnesium oxide, or other hard materials such as silicon carbide or tungsten carbide.

[0249] After the carbon nanoparticles and aggregates described herein are produced and collected, they can be processed using elevated temperatures, such as thermal annealing or sintering. The elevated temperature processing can be performed in an inert environment, such as nitrogen or argon. The elevated temperature processing can be performed at atmospheric pressure, under vacuum, or at reduced pressure. The elevated temperature processing can be performed at temperatures between 500°C and 2,500°C, or between 500°C and 1,500°C, or between 800°C and 1,500°C, or between 800°C and 1,200°C, or between 800°C and 1,000°C, or between 2,000°C and 2,400°C, or about 8,00°C, or about 1,000°C, or about 1,500°C, or about 2,000°C, or about 2,400°C.

[0250] After the carbon nanoparticles and aggregates described herein are produced and collected, additional elements or compounds are added to the carbon nanoparticles during post-processing operations to incorporate the unique properties of the carbon nanoparticles and aggregates into other material mixtures.

[0251] Either before or after post-processing, the carbon nanoparticles and aggregates described herein can be added to solids, liquids, or slurries of other elements or compounds to form additional material mixtures that incorporate the unique properties of the carbon nanoparticles and aggregates. The carbon nanoparticles and aggregates described herein can be mixed with other solid particles, polymers, or other materials.

[0252] Either before or after post-processing, the carbon nanoparticles and aggregates described herein find use in a variety of applications beyond those related to the creation and use of resonant materials, including, but not limited to, transportation applications (auto and truck tires, couplings, mounts, elastomeric "o" rings, hoses, sealants, grommets, etc.) and industrial applications (rubber additives, polymeric functionalization additives, epoxy additives, etc.).

[0253] Figures 23A and 23B show transmission electron microscope (TEM) images of as-synthesized carbon nanoparticles. The carbon nanoparticles in Figure 23A (at a first magnification) and Figure 23B (at a second magnification) comprise bonded multilayer spherical fullerenes (MWSFs) with graphene layers, which coat the bonded MWSFs. In this example, the ratio of MWSFs to graphene allotropes is approximately 80% due to the relatively short resonance time. The MWSFs in Figure 4A are approximately 5 nm to 10 nm in diameter, which can be 5 nm to 500 nm using the conditions described above. The average diameter of the entire MWSF ranges from 5 nm to 500 nm, or 5 nm to 250 nm, or 5 nm to 100 nm, or 5 nm to 50 nm, or 10 nm to 500 nm, or 10 nm to 250 nm, or 10 nm to 100 nm, or 10 nm to 50 nm, or 40 nm to 500 nm, or 40 nm to 250 nm, or 40 nm to 100 nm, or 50 nm to 500 nm, or 50 nm to 250 nm, or 50 nm to 100 nm. Because no catalyst was used in this process, there are no central seeds containing contaminants. In this example, the aggregate particles produced had particle sizes of approximately 10 μm to 100 μm, or approximately 10 μm to 500 μm.

[0254] Figure 23C shows the Raman spectrum of the as-synthesized aggregates of this example taken with incident light at 532 nm. D / I G is approximately 0.99-1.03, indicating that the assembly is composed of highly ordered carbon allotropes.

[0255] Figures 23D and 23E show exemplary TEM images of carbon nanoparticles after size reduction by ball milling. Ball milling was performed in cycles of counterclockwise milling for 3 minutes (min), followed by idling for 6 minutes, followed by clockwise milling for 3 minutes, followed by idling for 6 minutes. The milling was performed at 400 rpm. The milling media was zirconia, and the size ranged from 0.1 mm to 10 mm. The total size reduction process time was 60 to 120 minutes. After size reduction, the aggregate particles produced in this example had a particle size of approximately 1 μm to 5 μm. The reduced carbon nanoparticles were bonded MWSFs with graphene layers, which coated the bonded MWSFs.

[0256] Figure 23F shows the Raman spectrum from these aggregates after size reduction taken with incident light at 532 nm. In this example, the I D / I G The particle size after size reduction is about 40 m 2 / g~50m 2 / g Brunauer, Emmett and Teller (BET) specific surface area.

[0257] The purity of the aggregates produced in this sample was measured using mass spectrometry and X-ray fluorescence (XRF) spectroscopy. The ratio of carbon to other elements, excluding hydrogen, measured in 16 different batches ranged from 99.86% to 99.98%, with an average of 99.94% carbon.

[0258] In this example, carbon nanoparticles were produced using a thermal hot wire processing system. The precursor material was methane, flowing at 1 slm to 5 slm. With these flow rates and tool geometry, the resonant time of the gas in the reaction chamber was approximately 20 to 30 seconds, resulting in a carbon particle production rate of approximately 20 g / hr.

[0259] Further details regarding such processing systems can be found in the aforementioned US Pat. No. 9,862,602, entitled "CRACKING OF A PROCESS GAS." [Example]

[0260] Example 1 Figure 23G (shown enlarged as Figure 16), Figure 23H (shown enlarged as Figure 17), and Figure 23I (shown enlarged as Figure 18) show TEM images of the as-synthesized carbon nanoparticles of this example. The carbon nanoparticles comprise bonded multilayer spherical fullerenes (MWSFs) with graphene layers, which coat the bonded MWSFs. The ratio of multilayer fullerenes to graphene allotropes in this example is approximately 30% due to the relatively long resonance time, which allows for thicker or more graphene layers to coat the MWSFs. Because no catalyst was used in this process, there are no central seeds containing contaminants. In this example, the as-synthesized aggregate particles produced had particle sizes ranging from approximately 10 μm to 500 μm. Figure 23J shows the Raman spectrum from the aggregate of this example. The Raman signature of the as-synthesized particles in this example indicates thick graphene layers coating the MWSFs in the as-synthesized material. Furthermore, the as-synthesized particles have a diameter of approximately 90 μm. 2 / g~100m 2 / g Brunauer, Emmett and Teller (BET) specific surface area.

[0261] Example 2 Figures 23K and 23L show TEM images of the carbon nanoparticles of this example. Specifically, these images show the carbon nanoparticles after size reduction by grinding in a ball mill. The conditions for the size reduction process were the same as those described above in connection with Figures 23G to 23J. After size reduction, the particle size of the aggregate particles produced in this example was approximately 1 μm to 5 μm. The TEM images show that the MWSF embedded and bound in the graphene coating can be observed after size reduction. Figure 23M shows a Raman spectrum from the aggregate of this example after size reduction taken with incident light at 532 nm. The I for the aggregate particles in this example after size reduction D / I G is approximately 1, indicating that the bound MWSF, which was embedded in the graphene coating during synthesis, becomes detectable by Raman after size reduction and is well-ordered. 2 / g~100m 2 / g Brunauer, Emmett and Teller (BET) specific surface area.

[0262] Example 3 Figure 23N is a scanning electron microscope (SEM) image of a carbon aggregate showing graphite and graphene allotropes at a first magnification. Figure 23O is an SEM image of a carbon aggregate showing graphite and graphene allotropes at a second magnification. Layered graphene is clearly visible within the wrinkles of the carbon. The 3D structure of the carbon allotropes is also visible.

[0263] The particle size distribution of the carbon particles of Figures 23N and 23O is shown in Figure 23P. The cumulative particle size distribution 406 based on mass is plotted on the y-axis (Q 3 (x) [%]). The histogram of the mass particle size distribution 408 corresponds to the axis on the right side of the graph (dQ 3 (x) [%]). The median particle size is approximately 33 μm. The 10th percentile particle size is approximately 9 μm, and the 90th percentile particle size is approximately 103 μm. The particle mass density is approximately 10 g / L.

[0264] Example 4 The size distribution of carbon particles captured from the multi-stage reactor is shown in Figure 23Q. The cumulative particle size distribution 414 based on mass is plotted on the y-axis (Q 3 (x) [%]). The histogram of the mass particle size distribution 416 corresponds to the axis on the right side of the graph (dQ 3 The median particle size of the particles trapped is approximately 11 μm. The 10th percentile particle size is approximately 3.5 μm, and the 90th percentile particle size is approximately 21 μm. The graph in Figure 23Q also shows the y-axis (Q 0 Figure 4 shows the cumulative particle size distribution 418 based on the number of particles collected (x [%]). The median particle size based on the number is about 0.1 μm to about 0.2 μm. The mass density of the collected particles is about 22 g / L.

[0265] Returning to the discussion of Figure 23P, the graph also shows the results of a second set of examples. Specifically, in these examples, particles were size reduced by mechanical comminution and then a cyclone separator was used to process the size-reduced particles. The cumulative particle size distribution 410 based on the mass of the size-reduced carbon particles captured in this example is shown on the left y-axis of the graph (Q 3 (x) [%]). The histogram of the particle size distribution 412 based on mass corresponds to the right axis of the graph (dQ 3 (x) [%]). In this example, the median particle size of the size-reduced carbon particles captured is approximately 6 μm. The 10th percentile particle size is between 1 μm and 2 μm, and the 90th percentile particle size is between 10 μm and 20 μm.

[0266] Further details regarding the manufacture and use of cyclone separators can be found in U.S. Patent Application No. 15 / 725,928, filed October 5, 2017, entitled "MICROWAVE REACTOR SYSTEM WITH GAS-SOLIDS SEPARATION," which is incorporated herein by reference in its entirety.

[0267] High-purity carbon allotropes produced using a microwave reactor system In some cases, carbon particles and aggregates, including graphite, graphene, and amorphous carbon, can be produced using a microwave plasma reactor system with precursor materials, including methane, isopropyl alcohol (IPA), ethanol, or condensed hydrocarbons (e.g., hexane). In other examples, the carbon-containing precursor is optionally mixed with a feed gas (e.g., argon). The particles produced in this example include graphite, graphene, and amorphous carbon, and do not include seed particles. The ratio of carbon to other elements (other than hydrogen) in the particles in this example was greater than or equal to about 99.5%.

[0268] In one specific example, hydrocarbons were the input material of a microwave plasma reactor, and the separated output of the reactor included hydrogen gas and carbon particles, including graphite, graphene, and amorphous carbon. The carbon particles were separated from the hydrogen gas in a multi-stage gas-solid separation system. The solids loading of the separated output from the reactor was between 0.001 g / L and 2.5 g / L.

[0269] Example 5 Figures 23R, 23S, and 23T are TEM images of as-synthesized carbon nanoparticles. These images show examples of graphite, graphene, and amorphous carbon allotropes. Layers of graphene and other carbon materials can be clearly seen in the images.

[0270] The size distribution of the trapped carbon particles is shown in Figure 4U. The cumulative particle size distribution 420 based on mass is plotted on the y-axis (Q 3 (x) [%]). The histogram of the mass particle size distribution 422 corresponds to the axis on the right side of the graph (dQ 3 (x) [%]). In this example, the median particle size captured by the cyclone separator was approximately 14 μm. The 10th percentile particle size was approximately 5 μm, and the 90th percentile particle size was approximately 28 μm. The graph in FIG. 4U also shows the y-axis (Q 04 shows a cumulative particle size distribution 424 based on the number corresponding to the particle size distribution (x [%]). In this example, the median particle size based on the number was about 0.1 μm to about 0.2 μm.

[0271] Example 6 Figures 23V, 23W, and 23X are images showing three-dimensional carbon-containing structures grown on other three-dimensional structures. Figure 23V is a three-dimensional carbon structure grown on carbon fiber at 100X magnification, while Figure 23W is a three-dimensional carbon structure grown on carbon fiber at 200X magnification. Figure 23X is a three-dimensional carbon structure grown on carbon fiber at 1601X magnification. Three-dimensional carbon grown on the fiber surface is shown. Figure 23Y is a three-dimensional carbon structure grown on carbon fiber at 10,000X magnification. This image shows growth not only on the basal plane, but also on the edge planes.

[0272] More specifically, Figures 23V-23Y show exemplary SEM images of 3D carbon material grown on fibers using not only plasma energy from a microwave plasma reactor but also thermal energy from a thermal reactor. Figure 23V shows an SEM image of fibers 431 and 432 intersecting, with 3D carbon material 430 grown on the surface of these fibers. Figure 23W is a high-magnification image (scale bar is 300 μm compared to 500 μm in Figure 4V) showing 3D carbon material 430 on fiber 432. Figure 23X is an even more enlarged view (scale bar is 40 μm) showing 3D carbon material 430 on fiber surface 435; the 3D nature of carbon material 430 can be clearly seen. Figure 23Y shows a close-up view of the carbon alone (scale bar is 500 nm), demonstrating the interconnections between the basal surface 432 of the fiber and the edge surfaces 434 of the numerous subparticles of the 3D carbon material grown on this fiber. Figures 23V-23Y demonstrate the ability to grow 3D carbon on 3D fibrous structures, such as 3D carbon grown on 3D carbon fibers.

[0273] Growth of 3D carbon on fibers can be achieved by introducing multiple fibers into a microwave plasma reactor and etching the fibers using the plasma within the reactor. The etching creates nucleation sites, which initiate the growth of 3D carbon structures as carbon particles and subparticles are created by hydrocarbon dissociation within the reactor. Direct growth of 3D carbon structures on these fibers, which are essentially three-dimensional, provides highly integrated 3D structures containing pores through which the resin can penetrate. This 3D reinforcing matrix for resin composites (containing 3D carbon structures integrated with high-aspect ratio reinforcing fibers) results in improved material properties, such as tensile strength and shear, compared to composites containing conventional fibers with smooth surfaces, which typically delaminate from the resin matrix at these smooth surfaces.

[0274] Functionalization of exposed carbon surfaces Carbon materials, such as any one or more of the 3D carbon materials described herein, can have one or more exposed surfaces prepared for functionalization, such as to promote adhesion and / or add elements such as oxygen, nitrogen, carbon, silicon, or curing agents. Functionalization refers to the addition of functional groups to a compound through chemical synthesis. In materials science, functionalization can be used to achieve desired surface properties; for example, functional groups can be used to covalently attach functional molecules to the surface of a chemical device. Carbon materials can be functionalized in situ, i.e., in the same reactor where the carbon material is produced. Carbon materials can also be functionalized during post-processing. For example, the surface of fullerenes or graphene can be functionalized with oxygen- or nitrogen-containing species that form bonds with polymers in a resin matrix to improve adhesion and provide stronger bonds, increasing the strength of the composite.

[0275] A functionalization surface treatment can be performed on any one or more of the carbon-based materials of the present disclosure (e.g., CNTs, CNO, graphene, 3D carbon materials such as 3D graphene) utilizing a plasma reactor (e.g., microwave plasma reactor) described herein. Such treatments can include in situ surface treatments during fabrication of the carbon material, which can be combined with a binder or polymer in a composite, or post-fabrication surface treatments of the carbon material while it is still in the reactor.

[0276] Various aspects of the present disclosure can also be described as follows.

[0277] 1. The main body and a plurality of plies surrounding the body, at least some of the plurality of plies including a plurality of carbon-based microstructures distributed within one or more portions of each of the at least some plies, each ply of the at least some plies configured to resonate at one or more corresponding natural frequencies; Including tires.

[0278] 2. The tire of claim 1, wherein one or more of the plurality of carbon-based microstructures comprises a plurality of three-dimensional (3D) assemblies formed from graphene sheets, the graphene sheets being bonded together to create a 3D hierarchical open porous structure.

[0279] 3. The tire of claim 2, wherein the 3D hierarchical open porous structure comprises mesoscale structuring.

[0280] 4. The tire of claim 2, wherein one or more of the plurality of carbon-based microstructures further comprises a porous arrangement formed within the 3D hierarchical open porous structure.

[0281] 5. The tire of claim 2, wherein the graphene sheets comprise one or more of single layer graphene (SLG), few layer graphene (FLG), or multilayer graphene (MLG).

[0282] 6. The tire of claim 1, further comprising an additive material configured to modify surface functional groups on exposed surfaces of said at least some of said plurality of plies.

[0283] 7. The tire of claim 1, wherein one or more material properties of the carbon-based microstructure are configured to be defined during synthesis of the carbon-based microstructure.

[0284] 8. The tire of claim 1, wherein each carbon-based microstructure in the plurality of carbon-based microstructures is self-assembling.

[0285] 9. The tire of claim 1, wherein the carbon-based microstructures are nucleated from homogeneous nucleation.

[0286] 10. The tire of claim 1, wherein the carbon-based microstructure is configured to be grown at least in part by steam flow.

[0287] 11. The tire of claim 10, wherein the steam flow is configured to flow at least partially adjacent to a plasma.

[0288] 12. The tire of claim 11, wherein the vapor flow is at a pressure range between vacuum and substantially atmospheric pressure.

[0289] 13. The tire of claim 1, wherein the carbon-based microstructures are grown from carbon-based gas phase species.

[0290] 14. The tire of claim 13, wherein the carbonaceous gas phase species are configured to be controlled by gas-solid phase reactions under non-equilibrium conditions.

[0291] 15. The tire of claim 1, wherein one or more of the plurality of carbon-based microstructures are configured to resonate at a natural frequency in response to a ping from a transceiver.

[0292] 16. The tire of claim 15, wherein the transceiver is configured to interact with a tire pressure monitoring system (TPMS).

[0293] 17. The tire of claim 1, wherein the plurality of carbon-based microstructures are configured to attenuate one or more resonant signals in proportion to the degree of wear experienced by the tire.

[0294] 18. The tire of claim 17, wherein the amplitude of each one of the damped resonant signals is indicative of the degree of wear.

[0295] 19. The tire of claim 17, wherein each ply of the at least some plies is configured to resonate in response to an excitation signal, thereby generating a respective resonant signal of the one or more resonant signals.

[0296] 20. The tire of claim 1, wherein at least one of the plurality of carbon-based microstructures resonates at a known signature frequency or at a plurality of known signature frequencies.

[0297] 21. The tire of claim 20, wherein the thickness of the at least one ply is configured to at least partially attenuate the amplitude of the one known signature frequency or the plurality of known signature frequencies.

[0298] 22. The tire of claim 21, wherein one or more of the plurality of plies are configured to resonate at a frequency that is shifted away from the one known signature frequency or the plurality of known signature frequencies based on a change in dielectric constant.

[0299] 23. The main body and a tread surrounding the body and including a plurality of plies, at least some of the plurality of plies including a plurality of microstructures configured to resonate at one or more frequencies specific to each of the plurality of plies; Including tires.

[0300] 24. The tire of claim 23, wherein at least one of the microstructures has a shape resembling any one or more of an oval, an ellipse, a rectangle, a square, a circle, a line, or a combination of lines.

[0301] In the foregoing specification, the present disclosure has been described with reference to specific embodiments thereof. However, it will be apparent that various modifications and changes may be made thereto without departing from the broader spirit and scope of the present disclosure. For example, the process flows above are described with reference to a sequence of process actions. However, the sequence of many of the described process actions can be changed without affecting the scope or operation of the present disclosure. The specification and drawings are to be regarded in an illustrative sense, and not in a limiting sense.

[0302] (Appendix 1) A tire formed from at least one body including a plurality of plies, At least one ply of the plurality of plies comprises: a resonator configured to generate a resonant signal in response to a signal; a carbon-containing material distributed within one or more portions of the ply and configured to modify at least one characteristic of the resonant signal; The tire comprising: (Supplementary Note 2) The tire of claim 1, wherein modifying the at least one characteristic includes one or more of shifting a frequency of the resonant signal or attenuating the resonant signal in proportion to an amount of wear of one or more of the plurality of plies. (Supplementary Note 3) The tire of claim 1, wherein one or more of the plurality of plies is configured to attenuate the resonant signal by shielding. (Appendix 4) The tire of claim 3, wherein the amount of damping is based on a thickness of one or more plies of the plurality of plies. (Supplementary Note 5) The tire of claim 3, wherein the amplitude of the attenuated resonance signal is indicative of tire wear. 6. The tire of claim 1, wherein degradation of one or more of the plurality of plies is indicated by a change in the at least one characteristic of the resonant signal. (Supplementary Note 7) The tire according to claim 1, wherein the resonator is configured to resonate at a first frequency when a structural characteristic of each of the plurality of plies is higher than a certain level, and is configured to resonate at a second frequency different from the first frequency when the structural characteristic of each of the plies is not higher than the level. (Supplementary Note 8) The tire according to claim 1, wherein the resonator is configured to vibrate at a frequency based on the rotational speed of the tire. (Supplementary Note 9) The tire according to claim 1, wherein the vibration of the resonator is initiated upon receiving an electric charge from a charge generating device. (Supplementary Note 10) The tire according to claim 9, wherein the charge generating device is embedded within each of the plurality of plies. (Supplementary Note 11) The tire according to claim 10, wherein the charge generating device includes a tribological component. (Supplementary Note 12) The tire of claim 10, wherein the charge generating device comprises a hexagonal carbon triboelectric energy generator (CH-TENG). (Supplementary Note 13) The tire of claim 1, wherein the resonator includes a plurality of three-dimensional (3D) assemblies formed from graphene sheets. (Appendix 14) The tire of claim 13, wherein the graphene sheets are bonded together to create a 3D hierarchical open porous structure. (Supplementary Note 15) The tire of claim 1, further comprising a sensor formed by the carbon-containing material. (Supplementary Note 16) The tire of claim 15, wherein the sensor is embedded within an inner liner of the tire. (Supplementary Note 17) The plurality of plies are a first ply including a first resonator configured to resonate at a first frequency; a second ply including a second resonator configured to resonate at a second frequency different from the first frequency; a third ply including a third resonator configured to resonate at a third frequency different from the first frequency and the second frequency; The tire of claim 1, comprising at least (Appendix 18) The tire of claim 17, wherein the first ply forms an outer layer of the tire. (Supplementary Note 19) The tire of claim 17, wherein the attenuation of the first frequency indicates wear or deterioration of the first ply. (Supplementary Note 20) The second ply is disposed on the first ply, the third ply is disposed on the second ply; 18. The tire of claim 17. (Supplementary Note 21) The tire according to claim 17, wherein any one or more of the first ply, the second ply, and the third ply are in contact with each other. (Appendix 22) A body including a plurality of plies, each ply of the plurality of plies being: a charge generating device, and the body having a resonator electrically coupled to the charge generating device within at least one of the plurality of plies and configured to generate a resonant signal in response to charges generated by the charge generating device; a tread surrounding the body; Including tires. 23. The tire of claim 22, wherein at least a portion of each ply of the plurality of plies is configured to attenuate the resonant signal generated by a corresponding resonator. (Appendix 24) The tire according to claim 23, wherein the amount of attenuation indicates wear or deterioration of each of the plies. 25. The tire of claim 23, wherein at least one ply of the plurality of plies is configured to attenuate corresponding resonant signals by shielding. (Supplementary Note 26) The tire of claim 23, wherein at least one ply of the plurality of plies is configured to change a frequency of a corresponding resonant signal based on degradation of the at least one ply.

Claims

1. a tire including a plurality of tire plies, at least one tire ply of the plurality of tire plies comprising one or more resonators associated with a natural resonant frequency configured to shift in response to changes in one or more tire characteristics of the at least one tire ply of the plurality of tire plies, the one or more tire characteristics including one or more of deformation, stress, or strain; the one or more resonators comprise: a first resonator including a plurality of first carbon particles configured to resonate in response to an electromagnetic signal based at least in part on a concentration level of the first carbon particles in the first resonator.

2. 10. The tire of claim 1, wherein the one or more resonators further comprise a second resonator adjacent to the first resonator, the second resonator including a plurality of second carbon particles configured to resonate in response to an electromagnetic signal based at least in part on a concentration level of second carbon particles in the second resonator.

3. 3. The tire of claim 2, wherein the first carbon particles include first aggregates that form a first porous structure, and the second carbon particles include second aggregates that form a second porous structure.

4. 3. The tire of claim 2, wherein the first resonator and the second resonator are 3D printed on a surface of the at least one tire ply.

5. 3. The tire of claim 2, wherein the first resonator is configured to resonate at a first frequency in response to the electromagnetic signal and the second resonator is configured to resonate at a second frequency in response to the electromagnetic signal, the first frequency being different from the second frequency.

6. The tire of claim 5 , wherein the amplitude of the emitted signal of the first resonator or the second resonator is indicative of the degree of wear of the at least one tire ply.

7. The tire of claim 2 , wherein a shift in the natural resonant frequency of the first resonator and the second resonator in response to the electromagnetic signal corresponds to a deformation of the at least one tire ply.

8. The tire of claim 2 , wherein the first resonator is positioned outwardly of the second resonator.

9. The tire of claim 2 , wherein the first resonator and the second resonator are disposed within an innerliner of the tire.

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