CN116324329A - System for detecting changes in physical properties of elastomeric materials - Google Patents

Abstract

A system for detecting tire strain in a vehicle is disclosed. In some implementations, the system may include an antenna disposed on one or more of the vehicle or vehicle components and may output electromagnetic acoustic pulses. The system may include a tire having a body formed of one or more tire plies. Any one or more of the tire plies may include Split Ring Resonators (SRRs). Each SRR may have a natural resonant frequency that is proportionally deflectable in response to changes in elastomeric properties of a respective one or more tire plies, including one or more of reversible deformation, stress, or strain. The SRR may include an SRR having carbon particles that may uniquely resonate in response to an electromagnetic acoustic pulse based at least in part on a concentration level of the carbon particles within the SRR.

Description

System for detecting changes in physical properties of elastomeric materials

technical field

The present disclosure relates generally to sensors, and more particularly, to split ring resonators that can sense various properties of vehicle tires.

Background technique

Developments in vehicle powertrain types, including hybrid and pure electric systems, have created opportunities for further technology integration. This is especially true as modern vehicles transition to fully autonomous driving and navigation, where technology (rather than trained and capable humans) must regularly monitor vehicle component performance and reliability to ensure the safety and comfort of vehicle occupants at all times. Traditional systems, such as tire pressure monitoring systems (TPMS), may not be able to provide the high fidelity required for highly skilled (such as racing) or fully autonomous driving applications. Such applications may present unique challenges, such as rapid vehicle component (such as tire) wear encountered in demanding driving or racing, or the absence of a human driver capable of checking tire performance during vehicle operation.

Contents of the invention

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 essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter. Furthermore, the systems, methods, and devices of the present disclosure each have several novel aspects, no single one of which is solely responsible for the desirable attributes disclosed herein.

One novel aspect of the subject matter described in this disclosure can be implemented in a system configured to detect tire strain in a vehicle. In some implementations, include an antenna disposed on or within a vehicle and a tire including a body formed from one or more tire plies. The antenna is configured to transmit electromagnetic acoustic pulses (pings). At least one of the tire plies includes a plurality of split ring resonators (SRRs) having a natural resonant frequency responsive to changes in elastomeric properties of the at least one tire ply, the Elastomeric properties include one or more of reversible deformation, stress or strain. In some implementations, the plurality of SRRs further includes a first SRR including a plurality of first carbon particles configured to be based at least in part on the The concentration level of the first carbon particles is uniquely resonant in response to the electromagnetic acoustic pulse. Additionally or alternatively, the plurality of SRRs further includes a second SRR adjacent to the first SRR and including a plurality of second carbon particles configured to at least Uniquely resonant in response to the electromagnetic acoustic pulse based in part on a concentration level of second carbon particles within the second SRR. In some aspects, the first carbon particles include first aggregates forming a first porous structure, and the second carbon particles include second aggregates forming a second porous structure. The first porous structure and the second porous structure may include mesoscale structures.

Each of the first SRR and the second SRR includes a three-dimensional (3D) layer printed onto a surface of the tire ply. In some aspects, the first SRR is configured to resonate at a first frequency in response to the electromagnetic acoustic pulses, and the second SRR is configured to resonate at a second frequency in response to the electromagnetic acoustic pulses Resonant, the first frequency is different from the second frequency. Each of the first frequency and the second frequency may be associated with an encoded serial number. In some cases, the resonant amplitude of the first SRR or the second SRR is indicative of tire ply wear.

In other implementations, the amount or magnitude of the change in the natural resonant frequency of the SRR caused by the electromagnetic acoustic pulse is indicative of the amount of deformation of the tire ply. In some aspects, each of the first SRR and the second SRR has a decay point associated with a frequency response to an electromagnetic acoustic pulse.

In various implementations, each of the first carbon particles and the second carbon particles are chemically bonded to the tire ply. In some aspects, each of the first SRR and the second SRR has a principal dimension associated with one or more of an S-parameter or a frequency of an electromagnetic acoustic pulse. At least one of the first SRR or the second SRR has one of an oval shape, an elliptical shape, a rectangular shape, a square shape, a circular shape, or a curve.

In some cases, one or more of the first SRR or the second SRR includes a cylindrical SRR. In other cases, the first SRR is external to the second SRR. In some other cases, the first SRR and the second SRR are disposed within an innerliner of a tire. In some other aspects, each of the first SRR and the second SRR has a negative effective permeability.

Another novel aspect of the subject matter described in this disclosure can be implemented in tires. The tire includes a body formed from one or more tire plies, any one or more of which includes one or more SRRs, each of the SRRs being associated with a natural resonant frequency , the natural resonant frequency is configured to shift in response to changes in elastomeric properties of the corresponding one or more tire plies, the elastomeric properties including one or more of reversible deformation, stress, or strain.

In some implementations, the one or more SRRs further include a first SRR including a plurality of first carbon particles configured to be based at least in part on the first SRR The concentration level of the first carbon particles within is uniquely resonant in response to the electromagnetic acoustic pulse. Additionally or alternatively, the one or more SRRs further include a second SRR adjacent to the first SRR and including a plurality of second carbon particles configured is uniquely resonant in response to the electromagnetic acoustic pulse based at least in part on a concentration level of second carbon particles within the second SRR.

In some implementations, the first carbon particles include first aggregates forming a first porous structure, and the second carbon particles include second aggregates forming a second porous structure. In some aspects, the first porous structure and the second porous structure comprise mesoscale structures. In other aspects, each of the first SRR and the second SRR includes a 3D layer printed onto the surface of the tire ply. Each of the first SRR and the second SRR may have a decay point. In some aspects, the first SRR and the second SRR each have an attenuation point associated with a frequency response to an electromagnetic acoustic pulse. In one implementation, each of the first SRR and the second SRR includes a 3D layer printed onto the surface of the tire ply.

The first SRR may be configured to resonate at a first frequency in response to the electromagnetic acoustic pulses, and the second SRR may be configured to resonate at a second frequency in response to the electromagnetic acoustic pulses, the The first frequency is different from the second frequency. Each of the first frequency and the second frequency may be associated with an encoded serial number. In some aspects, each of the first carbon particles and the second carbon particles are chemically bonded to the tire ply. In other aspects, each of the first SRR and the second SRR has a principal dimension associated with one or more of an S-parameter or a frequency of an electromagnetic acoustic pulse. In some cases, the resonant amplitude of the first SRR or the second SRR is indicative of tire ply wear.

In other implementations, the amount or magnitude of the change in the natural resonant frequency of the SRR caused by the electromagnetic acoustic pulse is indicative of the amount of deformation of the tire ply. In some aspects, each of the first SRR and the second SRR has a decay point. An attenuation point of each of the first SRR and the second SRR is associated with a frequency response to an electromagnetic acoustic pulse.

In various implementations, each of the first carbon particles and the second carbon particles are chemically bonded to the tire ply. In some aspects, each of the first SRR and the second SRR has a principal dimension associated with one or more of an S-parameter or a frequency of an electromagnetic acoustic pulse. At least one of the first SRR or the second SRR has one of an oval shape, an elliptical shape, a rectangular shape, a square shape, a circular shape, or a curve.

In some cases, one or more of the first SRR or the second SRR includes a cylindrical SRR. In other cases, the first SRR is external to the second SRR. In some other cases, the first SRR and the second SRR are disposed within an innerliner of a tire. In some other aspects, each of the first SRR and the second SRR has a negative effective permeability.

Another novel aspect of the subject matter described in this disclosure can be implemented in tires. The tire includes a tire body formed from one or more tire plies, any one or more of which includes a temperature sensor configured to detect a temperature of the respective tire ply. In some implementations, the temperature sensor includes: a ceramic material organized into a matrix; one or more SRRs, each SRR having a natural resonant frequency configured to respond to a corresponding one or more of the tire plies shifted by one or more of a change in elastomeric properties or a change in temperature; and a conductive layer dielectrically separated from the corresponding one or more SRRs.

In some implementations, the one or more SRRs further include a first SRR including a plurality of first carbon particles configured to be based at least in part on the first SRR The concentration level of the first carbon particles within is uniquely resonant in response to the electromagnetic acoustic pulse. Additionally or alternatively, the one or more SRRs further include a second SRR adjacent to the first SRR and including a plurality of second carbon particles configured is uniquely resonant in response to the electromagnetic acoustic pulse based at least in part on a concentration level of second carbon particles within the second SRR.

In some implementations, the first carbon particles include first aggregates forming a first porous structure, and the second carbon particles include second aggregates forming a second porous structure. In some aspects, the first porous structure and the second porous structure comprise mesoscale structures. In other aspects, each of the first SRR and the second SRR includes a 3D layer printed onto the surface of the tire ply. Each of the first SRR and the second SRR may have a decay point. In some aspects, the first SRR and the second SRR each have an attenuation point associated with a frequency response to an electromagnetic acoustic pulse. In one implementation, each of the first SRR and the second SRR includes a 3D layer printed onto the surface of the tire ply.

The first SRR may be configured to resonate at a first frequency in response to the electromagnetic acoustic pulses, and the second SRR may be configured to resonate at a second frequency in response to the electromagnetic acoustic pulses, the The first frequency is different from the second frequency. Each of the first frequency and the second frequency may be associated with an encoded serial number. In some aspects, each of the first carbon particles and the second carbon particles are chemically bonded to the tire ply. In other aspects, each of the first SRR and the second SRR has a principal dimension associated with one or more of an S-parameter or a frequency of an electromagnetic acoustic pulse. In some cases, the resonant amplitude of the first SRR or the second SRR is indicative of tire ply wear.

In other implementations, the amount or magnitude of the change in the natural resonant frequency of the SRR caused by the electromagnetic acoustic pulse is indicative of the amount of deformation of the tire ply. In some aspects, each of the first SRR and the second SRR has a decay point. An attenuation point of each of the first SRR and the second SRR is associated with a frequency response to an electromagnetic acoustic pulse.

In various implementations, each of the first carbon particles and the second carbon particles are chemically bonded to the tire ply. In some aspects, each of the first SRR and the second SRR has a principal dimension associated with one or more of an S-parameter or a frequency of an electromagnetic acoustic pulse. At least one of the first SRR or the second SRR has one of an oval shape, an elliptical shape, a rectangular shape, a square shape, a circular shape, or a curve.

In some cases, one or more of the first SRR or the second SRR includes a cylindrical SRR. In other cases, the first SRR is external to the second SRR. In some other cases, the first SRR and the second SRR are disposed within an innerliner of a tire. In some other aspects, each of the first SRR and the second SRR has a negative effective permeability.

Description of drawings

The details of one or more implementations 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 be apparent from the description, drawings, and claims. Please note that relative dimensions in the following drawings may not be drawn to scale.

Figure 1 presents a field vehicle control system including various sensors.

2 depicts a signal processing system that analyzes an RF signal frequency shifted and/or attenuated by a sensor formed from a carbon-containing tuning RF resonant material, according to some implementations.

Figure 3 illustrates a signature classification system, according to some implementations.

4 depicts a series of tire condition parameters sensed as a function of changes in RF resonance of various layers of carbon-containing tuning RF resonant material, according to some implementations.

5 depicts a schematic diagram of an apparatus for tuning multiple plies of a tire, according to some implementations.

6 and 7 depict example sets of condition signatures that may be transmitted from a new tire formed from a layer of carbon-containing tuning RF resonant material, according to some implementations.

8 depicts a top-down schematic diagram of an example split ring resonator (SRR) configuration including two concentric SRRs, according to some implementations.

9 depicts a schematic diagram illustrating a complete tire diagnostic system and apparatus for tire wear sensing by impedance-based spectroscopy, according to some implementations.

10 and 11 depict schematic diagrams related to tire information communicated via telemetry to a navigation system and equipment for manufacturing printed carbon-based materials, according to some implementations.

12 depicts resonant serial number-based digital encoding of a vehicle tire via tire tread and/or tire body ply printed encoding, according to some implementations.

13 illustrates resonance mechanisms that contribute to the aggregation phenomenon caused by different proximal presence resonator types, according to some implementations.

14 is an example temperature sensor including one or more of the presently disclosed SRRs, according to some implementations.

15 is a graph of measured resonance signature signal strength (in decibels dB) versus height of tire tread layer loss (in millimeters mm), according to some implementations.

16 is a graph of measured resonance signature signal strength (in decibels in dB) versus natural resonance frequency of an SRR showing resonance response displacement proportional to tire ply deformation, according to some implementations.

17 is a graph of signal strength versus chirp frequency for an SRR that may resonate corresponding to an encoded serial number, according to some implementations.

18A-18Y depict carbonaceous materials used as forming materials for producing any of the presently disclosed resonators, such as SRRs, according to some implementations.

Similar reference numbers and names in the various drawings indicate similar elements.

Detailed ways

Various implementations of the subject matter disclosed herein generally involve deploying durable sensors (eg, split ring resonators, SRRs) made of carbonaceous microstructures. The sensors may be incorporated into vehicle components, for example, within the carcass of conventional currently available pneumatic (referring to air, nitrogen, or other pneumatic) tires, next-generation airless solid tires, and in other locations, For example in the body of a vehicle. The sensors may be embedded within portions of the tire ply and/or the tire tread, for example, the rubber that contacts the road or ground. Conventional tire use can lead to degradation of the contact surface, ultimately resulting in a slick (no tread) tire not adequately adhering to the road surface, especially under adverse weather conditions (eg, snow, heavy rain, etc.). Deterioration of the tire ply containing the sensor produces a corresponding detectable change in sensor response behavior, e.g., relative to lateral tire slippage such as that encountered in "drifting" (a common practice in some enthusiast communities). Both rotation and tire strain. In this way, both conventional (e.g., forward rotating) tire degradations can be accomplished by observing shifts in the expected sensor resonant response behavior (e.g., by the concept frequency shift-keying as explained further below) by shifting the expected sensor resonant response behavior Changes and loss of tire viscosity (for example, during drifting maneuvers) are detected. As commonly understood, viscous forces may mean static friction that needs to be overcome in order to enable relative motion of contacting stationary objects, such as may be encountered during skillful driving maneuvers involving lateral movement, such as drifting. This is in contrast to kinetic and/or dynamic friction, which may mean simultaneous movement between two contacting surfaces, or the like.

Carbonaceous materials can be tuned during synthesis to achieve specific desired radio frequency (RF) signal shift (referring to frequency shift) and signal attenuation (referring to reduction in signal magnitude) behavior of the emitted RF signal. Devices capable of transmitting RF signals may include, for example, transceivers mounted on devices equipped with the disclosed system and/or inductor-capacitor (LC) circuits (also referred to (interchangeably) as tank circuits, LC circuits, or resonator) in one or more wheel wells of the vehicle. The presently disclosed implementation requires no moving parts and is therefore less prone to wear and tear from regular road use. SRRs work with pre-existing vehicle electronics. Target RF resonant frequency values for the disclosed constituent carbonaceous materials can be tuned within a reaction chamber or reactor to exhibit interactions to yield target performance characteristics. The properties can be used in any number of applications, such as knobby, low pressure off-road tires and untreaded slick tires for track only. SRRs formed from unique carbonaceous materials exhibit frequency shifts and/or signal attenuation at specified radio frequencies (RF) (eg, 0.01 GHz to 100 GHz), which can be tuned according to the desired application. With regard to tunability, carbonaceous materials can grow naturally (eg, self-nucleate) from carbon-containing gaseous species in the reactor without the need for seed particles to produce the gorgeous 3D structures.

Changes in the environment (eg, snow, rain, etc.) surrounding a vehicle equipped with the disclosed materials and systems may affect the resonance, frequency shift, and/or signal attenuation behavior of the SRR. Thus, even the slightest change in tire condition can be detected and communicated to the driver. For example, if a tire ply containing one or more SRRs contacts a road surface (eg, rotates forward) and thereby degrades over time, the resonance of the SRRs within the degraded tire ply may change. Additionally, other detectable changes may occur during a drift (e.g., lateral movement) situation such that the signal response of the affected tire ply and/or tread layer containing the SRR may indicate the presence of the tread layer or not present and the degree of wear. Thus, SRR can accurately and precisely detect sudden or gradual transitions in weather or other environmental conditions, such as skillful driving maneuvers.

Detectable changes and/or shifts in the RF range resonant frequency response of the SRRs can be detected by stimulating the RF resonant material within each SRR with an electromagnetic (EM) signal having a known frequency. In some configurations, the EM signal may initially be output via an antenna (also mounted on the vehicle) and/or further passed through a patterned resonant circuit (also referred to herein as a "resonator" herein) mounted within one or more wheel wells, so The resonant circuit described above can be 3D printed onto the tire body ply). In this way, the attenuation and/or frequency shift of the transmitted signal associated with the corresponding SRR can be observed and analyzed electronically to give an indication of the current environmental conditions. Additionally, changes in the RF resonant frequency (or frequencies) can be observed and compared to known and discrete calibration points to determine the tire pressure measured at one or more defined detection points on the vehicle body at a given moment .

Regular use of the tire (such as encountered during on-road driving with most pavement tires or off-road driving with off-road tires) may cause slight deformation of the tire section, which may result in a corresponding The natural RF resonant frequency of the SRR varies. Such natural resonant frequency changes associated with the presently disclosed carbons forming the various SRRs can be detected and compared to known calibration points to determine conditions inside the tire. A system using an antenna in conjunction with the presently disclosed SRR incorporated into the tire ply may be adapted to sense changes in tire ply properties and report to associated telemetry equipment in the vehicle.

The presently disclosed SRRs can be tuned to detect very small changes in the physical properties of the corresponding tire ply, including changes due to air pressure on the vehicle skin or due to any external force application in/on the tire. Such changes can be detected by "probing" (e.g., transmitting an RF signal and then observing and analyzing the RF signal), followed by processing a unique set of detected signals for a given tire ply, tread, or other surface or area. properties (eg "signature") as exhibited by eg frequency domain echoes. Various mechanisms for calibrating observed signal signatures and processing returned signatures are discussed. A method for manufacturing tires with passively embedded sensors interacting with elastomers in the form of tuned carbon structures is disclosed. For example, the mechanisms used to manufacture tires from multiple plies may affect the natural resonant frequency behavior of the SRR. In addition, tires may be constructed to include multiple tire plies, each tire ply incorporating a different tuned carbon with a unique tuned carbonaceous microstructure, which may be micron-scale, or alternatively nanoscale , micron, or even median particle size up to any one or more of millimeter (mm) levels.

The disclosed SRR can achieve a self-powered signature from resonance in the GHz and MHz range, which is made possible by a triboelectric generator (e.g., generating an electrical current when, for example, a vehicle tire rotates and it repeatedly rubs and/or contacts the road or ground ). Such friction components may be integrated or otherwise incorporated into a plurality of steel belts between elastomeric layers in one or more vehicle tire plies. In this way, the SRR can be charged (and/or powered) by the triboelectric generator to cause the resonator to resonate (and thus emit an RF signal) and discharge. The resonator can be configured to accommodate repeated charge-discharge cycles and take any one or more of a variety of shapes and/or patterns, including ovoids with inherent resonant values or properties based on their forming material and/or configuration .

A change in the shape or orientation of a resonator may result in a corresponding change in any associated resonance constant. Therefore, any change in the physical properties of the tire caused by deformation (e.g., under static conditions like internal tire pressure, or under dynamic conditions such as those encountered when driving over road studs) may alter the corresponding SRR's shape or orientation. Different resonator patterns can be used (e.g., in addition to or instead of SRRs) to respond with greater sensitivity to one type of deformation than another (such as a finger's lateral movement encountered when moving around a curve). deformation compared to the vertical motion encountered when driving over gravel or rough surfaces). In addition to the configuration of the SRR to change the signal response behavior based on tire deformation, the SRR can also electronically communicate with other signal attenuation detection capabilities, such as digital signal processing, DSP, computer chips and / or transducer association. DSP can function with external transceiver (semiconductor chip) for stimulus and response; when optional. SRRs can also communicate with triboelectric generators incorporated into individual tire plies and exhibit resonant behavior detectable by external receivers.

FIG. 1 is a schematic diagram of a vehicle condition detection system 1A00 intended, for example, to be equipped on a vehicle such as an automobile and/or truck. The vehicle condition detection system 1A00 may include a sensor, such as a tuned RF resonant component 108 (eg, a split ring resonator, such as that shown in FIG. 8 ). Each of the tuning RF resonant components 108 may be formed from a variety of carbon-based microstructural materials, aggregates, agglomerates, and/or the like, such as in a paper by Stowell et al., filed Feb. 7, 2020 entitled "3D Self- - Assembled Multi-Modal Carbon-Based Particle" those materials disclosed in U.S. Patent Application No. 16/785,020 (collectively "carbonaceous materials"). The tuned RF resonant component 108 may be incorporated into a belt sensor 104, hose sensor 105 on a vehicle such as a conventional driver-driven car or a fully autonomous transport pod or vehicle that is operable to move a vehicle occupant without a human driver. , tire sensor 106 and transceiver antenna 102 in any one or more of them.

The tuned RF resonant component 108 may be configured to communicate with the transceiver 114, the vehicle central processing unit 116, the vehicle sensor data receiving unit 118, the vehicle actuator control unit 120, and the actuator 122, such as by measuring signal frequency shift or attenuation. Any one or more of the actuators that communicate electronically and/or wirelessly include doors, windows, locks 125 , engine controls 126 , navigation/head-up display 128 , suspension controls 129 , and airfoil trim 130 . Tuning the RF resonant component 108 may cause a shift in the observed frequency of the transmitted RF signal (referred to as a "frequency shift," meaning a any changes). A reference to the returned RF signal 112 corresponding to the transmitted RF signal 110 may refer to one of the tuned RF resonant components 108 integrated into any one or more of the belt sensor 104 and/or the like. Electronic detection of one or more frequency shifts or attenuations of the transmitted RF signal 110 (eg, not the actual physical reflection or return of the signal from the sensor). Transmitted RF signal 110 and returned RF signal 112 may communicate with any one or more of vehicle central processing unit 116 , vehicle sensor data receiving unit 118 , vehicle actuator control unit 120 , and/or actuator 122 ( and is therefore also rated by each of the above). The vehicle condition detection system 100 may be implemented using any suitable combination of software and hardware.

Any one or more of the various depicted sensors of the vehicle condition detection system 100 may be composed of sensors that are tuned to achieve a particular RF resonance behavior when "probed" (meaning bumped or otherwise touched) by the transmitted RF signal. Carbon-based microstructures are formed. Vehicle condition detection system 100 (or any aspect thereof) may be configured to be implemented in any contemplated vehicle use application, field or environment, such as during severe weather conditions, including sleet, hail, snow, icing , frost, mud, sand, debris, uneven terrain, water and/or the like.

The tuning RF resonant component 108 may be positioned around and/or on the vehicle (such as in the cabin, engine compartment or trunk or on the vehicle body). As shown in FIG. 1A, the tuned RF resonant components may include a belt sensor 104, a hose sensor 105, a tire sensor 106, and a transceiver antenna 102, any one or more of which may be implemented in a modern vehicle during vehicle production, or ( Alternatively) retrofitting to a pre-existing vehicle, regardless of the age and/or condition of the pre-existing vehicle. Tuning RF resonant component 108 may be formed in part using readily available materials, such as fiberglass (such as for airfoils) or rubber (such as for tires) or glass (such as for windshields). These conventional materials may be combined with carbon-based materials, growths, agglomerates, aggregates, flakes, particles, and/or the like, such as in-process self-nucleation from carbon-containing gaseous species in a reaction chamber or reactor and are formulated as those substances that: (1) increase the mechanical (such as tension, compression, shear, strain, deformation, and/or the like) strength of composite materials into which they are incorporated; and/or ( 2) Resonate at a specific frequency or set of specific frequencies (in the range of 10GHz to 100GHz). The variables that dominate the RF resonant properties and behavior of a material can be controlled separately from the variables responsible for controlling the strength of the material.

Radio frequency (RF) based stimuli (such as transmitted by transceiver 114 or by a resonator) may be used to provide feedback to tuning RF resonant component 108, actuator 122 (and/or the like, such as implemented in tuning RF resonant component 108 or The sensor on the sensor) transmits an RF signal to detect its corresponding resonant frequency and the frequency shift and pattern observed in the attenuation of the transmitted signal (which may be affected by internal or external conditions). For example, if a tuned RF resonant component such as tire sensor 106 has been specially prepared (referred to as "tuned") to resonate at a frequency of about 3, then tire sensor 106 may emit sympathetic resonance when stimulated by a 3 GHz RF signal or Sympathetic vibrations (referring to harmonic phenomena in which a previously passive line or vibrating body responds to external vibrations with a harmonic similarity to it).

These sympathetic vibrations can occur at the stimulating frequency as well as in overtones or sidelobes derived from the fundamental 3GHz tone. If the tuning resonant element (of tuning RF resonant element 108 ) has been tuned to resonate at 2 GHz, then the tuned resonant element will emit the described sympathetic vibrations when stimulated by a 2 GHz RF signal. These sympathetic vibrations will occur at the stimulating frequency as well as in overtones or sidelobes (in engineering, local maxima other than the main lobe of the far-field radiation pattern of an antenna or other radiation source) originating from the fundamental 2GHz tone. A number of additional tuned resonant components can be located near the RF transmitter. The RF transmitter may be controlled to emit a 2GHz sound pulse first, then a 3GHz sound pulse, then a 4GHz sound pulse, and so on. This train of sound pulses at different and increasing frequencies may be referred to as a "chirp".

Adjacent tire plies (such as tire plies in contact with each other) within a tire body (such as generally shown in FIGS. (Referring to corresponding) The sensors within the tire body ply and/or tread resonate at different distinct frequencies that are not harmonics of each other. That is, non-harmonic plies can ensure distinct and easily identifiable detection of a particular tire body ply and/or tread layer (or other surface or material) relative to other layers, where due to harmonics ( or otherwise associated with harmonics) presents minimal risk of confusion due to signal interference.

The transceiver 114 (and/or the resonator, not shown in FIG. 1A ) may be configured to transmit the transmitted RF signal 110 to any one or more of the tuned RF resonant components 108 to digitally identify the tuned Frequency shifting and/or attenuation of the RF signal 112 returned by any one or more of the RF resonating components 108 . Such "return" signals 112 may be processed into digital information that may be transmitted electronically to a vehicle central processing unit 116 that interacts with a vehicle sensor data receiving unit 118 and/or a vehicle actuator control unit 120 , the vehicle sensor data receiving unit and/or the vehicle actuator control unit transmits other vehicle performance related signals based on the received sensor data. The returned signal 112 ₀ may at least partially control the actuator 122 . That is, the vehicle actuator control unit 120 may control the actuators 122 to operate based on feedback received from the vehicle sensor data receiving unit 118 regarding wear or degradation of vehicle components indicated by tuned RF components in communication with the transceiver 114 . Any one or more of the doors, windows, locks 124 , engine controls 126 , navigation/head-up display 128 , suspension controls 129 , and/or airfoil trim 130 are operated.

Detection of road debris and adverse weather conditions while monitoring the behavior of the returned RF signal 111 , such as frequency shift and/or attenuation, may, for example, cause the actuator 122 to trigger a corresponding change in the suspension control 129 . Such changes may include, for example, softening the suspension settings to accommodate driving over road debris, and tightening the suspension settings afterwards to accommodate enhanced vehicle responsiveness in heavy rain (and thus low traction) Driving during conditions may be necessary. There are many variations of such control by the vehicle actuator control unit 120, wherein any conceivable condition external to the vehicle can be detected by the transceiver (such as the frequency of the transmitted RF signal 110 and/or the returned RF signal 112). shift and/or attenuation).

Any of the tuned RF resonant components 108 forming the described sensor may be tuned to resonate at a particular frequency when stimulated, wherein a defined displacement of one or more frequencies (as induced by the carbon-based microstructure) may One or more signal signatures are formed indicative of the material or condition of the material into which the sensor is incorporated.

The time variance or deviation (TDEV) (TDEV) of a frequency shift (such as that shown in the signal signature) in the returned RF signal 112 (refers to the temporal stability of phase x versus the observation interval τ of the measured clock source; the time deviation thus forms The type of standard deviation measured to indicate temporal instability of the signal source) may correspond to time-varying changes in the sensor environment and/or time-varying changes in the sensor itself. Therefore, the 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.) Signals associated with the sensors (such as transmitted RF signal 110 and returned RF signal 112). The results of such analysis, such as signature analysis, may be delivered to the vehicle central processing unit 116 which (in turn) may communicate commands to the vehicle actuator control unit 120 for appropriate responsive action. In some configurations, such responsive action by the actuator 122 may involve at least some human driver input, while in other configurations, the vehicle condition detection system 100 may function entirely in a self-contained manner, allowing the so equipped Addresses component performance issues when the vehicle is in a fully driverless environment. Additionally, the vehicle central processing unit 116 may be associated with one or more upstream components (e.g., a computing device associated with a racing application housed in a stationary area) and/or be responsible for obtaining and/or processing and tuning the RF resonant component 108 All data is electronically communicated to the racing mission control unit 119.

2 shows a block diagram of a signal processing system 200, which may include surface sensors 260 and embedded sensors 270, any one or more of which may be combined with other sensors as such equipped vehicles (referred to as equipped A vehicle with surface sensors 260 and embedded sensors 270) communicates electronically changes in environment 250. The signal processing system 200 may also include a transceiver 214, a signature analysis module 254, and a vehicle central processing unit 216, any one or more of which are in electronic communication with the others.

In some implementations, embedded sensors 270 (which may be embedded within materials such as tire ply) may employ and/or be powered by self-powered telemetry including sensors that are also incorporated into the enclosure. Frictional energy generators within the material (not shown in Figure 2). Thus, the frictional energy generator may generate current and/or electricity usable to power a resonant circuit (discussed in more detail herein) by collecting static charge accumulated between, for example, a rotating tire or wheel and the road surface it is in contact with. described), the resonant circuit may then resonate to transmit an RF signal of known frequency. Thus, an externally mounted transceiver unit, such as a transceiver unit mounted in each wheel well of the vehicle, can transmit an RF signal that propagates further through a resonant circuit, which in this configuration is a friction Powered and embedded in the ply of the tire body. The frequency shift and/or magnitude attenuation of the transmitted signal is also received and analyzed, for example, by the signature analysis module 254 and/or the vehicle central processing unit 216 .

Self-powered telemetry (meaning that measurements or other data are collected at a remote or inaccessible point and automatically transmitted to a receiving device for monitoring) could be incorporated into vehicle tires. As referred to herein, self-powered telemetry involves the use of triboelectric charge generation inside the tire, the storage of this charge and the subsequent discharge of the stored charge to or through a resonant circuit to utilize the A circuit consisting of an inductor and a capacitor denoted by the letter C connected together to generate an RF signal at one or more specific frequencies) "ringing" that occurs during discharge (referring to the resonance responsible for the further emission of the RF signal circuit oscillation).

Acoustic pulse stimulation may generally be provided in one of two possible configurations of the presently disclosed vehicle component wear detection system including: relying on a signal or 'sound pulse' generated by a stimulus source, the Such stimulus sources as conventional transceivers located external to the tire (or other vehicle component intended for monitoring wear due to continued use), such as incorporated into each wheel well of a vehicle so equipped; or using internal tires (referred to as Also embedded in the tire ply, similar to sensors with carbon-based microstructures) frictional energy generating devices that collect the original Energy generated from frictional energy that would be wasted. Tribology, as commonly understood and referred to herein, means the scientific and engineering study of interacting surfaces in relative motion. Such a frictional energy generating device may provide electrical energy to an in-tire resonant device which in turn self-transmits tire property telemetry.

Either of the above two 'acoustic pulse' stimulus generators or providers may have a complex resonant frequency (CRf) component in the range of about 10 GHz to 99 GHz (e.g. due to the small size of the resonant frequency of structures such as graphene sheets) And the lower frequency resonances in the Khz range caused by said internal resonances of relatively large size. In general, CRf can be equated as a function of the natural resonant frequency of the elastomeric component, the natural resonant frequency of the carbon component, the ratio/collection of constituent components, and the geometry of the resonant device within the tire.

Once the sensor formed from the carbon-based microstructure is stimulated, the signal processing system 200 is used to analyze the signal signature (by digitally observing the frequency of any one or more of the transmitted RF signal 210 and/or the returned RF signal 212). shift and/or attenuation). By resonating at or near its corresponding tuning frequency, shifting the transmitted frequency and/or causing the transmitted signal to The amplitude decays to "response". When an environmental change (such as one that causes tire body ply and/or tread wear) occurs while the chirp/acoustic pulse is being emitted, the "returned" signal can be monitored for a modulation change - higher than the tuned frequency or low. Accordingly, the transceiver 214 may be configured to receive the returned RF signals 212 indicative of the surface they hit, or the like.

The aforementioned chirp/burst signals may be transmitted by the transceiver 214 (such as via inaudible RF signals, pulses, vibrations, and/or similar transmissions). Additionally, a “return” signal may be received by transceiver 214 . As shown, a chirp signal may occur in a repeating chirp sequence (such as transmitted RF signal 210). For example, a chirp signal sequence may be formed by a pattern comprising a 1 GHz sound pulse, followed by a 2 GHz sound pulse, followed by a 3 GHz sound pulse, and so on. The entire chirp signal sequence can be repeated continuously as a whole. There may be a brief period between each sound pulse so that the return signal from the resonant material (returned RF signal 212) may be received immediately after the sound pulse ends. Alternatively or additionally, the signal corresponding to the acoustic pulse stimulus and the observed "response" may occur simultaneously and/or along the same general path or route. The signature analysis module may employ digital signal processing techniques to distinguish the observed "responsive" signal from the acoustic pulse signal. In cases where the returned response includes energy across many different frequencies (such as overtones, side lobes, etc.), the stimulus may be filtered using a notch filter. The returned signal received by the transceiver may be sent to the signature analysis module 254 which in turn may send the processed signal to the vehicle central processing unit 216 . The preceding discussion of FIG. 2 includes a discussion of sensors formed from carbon-containing tuned resonant materials and may also refer to sensing laminates.

The disclosed sensors may be incorporated into tire layers, for example, including resin layers that may be layered with gaps between additional carbon fiber layers within the tire ply. Each carbon-containing resin layer can be tuned differently to resonate at a different intended or desired tuning frequency. The physical phenomenon of material resonance can be described with respect to the corresponding molecular composition. For example, a layer with a first defined structure (such as a first molecular structure) will resonate at a first frequency, while a layer with a second, different molecular structure may resonate at a second, different frequency.

A material having a particular molecular structure contained in a layer will resonate at a first tuned frequency when the layer is in a low energy state, and will resonate at a second, different frequency when the material in the layer is in an induced high energy state. For example, a material in a layer exhibiting a particular molecular structure can be tuned to resonate at 3 GHz when the layer is in its intrinsic, undeformed, low energy state. In contrast, the layer can resonate at 2.95 GHz when the layer is at least partially deformed relative to its intrinsic, undeformed low energy state. Thus, this phenomenon can be tuned to the need to detect with high fidelity and accuracy the slightest anomaly of eg a tire surface that is in contact with a road surface such as a pavement and experiences increased wear at some localized contact area. Cars racing on demanding tracks (high-tech, windy tracks with sharp turns and rapid altitude changes) can benefit from such localized tire wear or degradation information to make informed tire replacement decisions, even if The same is true in time-sensitive race day conditions.

The frequency shift phenomenon mentioned above (such as a transition from resonance at a frequency of 3 GHz to resonance at a frequency of 2.95 GHz) is shown and discussed with reference to FIGS. 2B1-2B2 . Figure 2B2 depicts the frequency shift phenomenon exhibited in sensing laminates containing carbon-containing tuned resonant materials. Atoms emit electromagnetic radiation at the natural frequency of a given element. That is, atoms of a particular element have natural frequencies corresponding to the properties of the atoms. For example, when a cesium atom is stimulated, valence electrons jump from a lower energy state (such as a ground state) to a higher energy state (such as an excited energy state). When the electron returns to its lower energy state, it emits electromagnetic radiation in the form of photons. For cesium, the emitted photons are in the microwave frequency range; 9.192631770 THz. Structures larger than atoms, such as molecules formed from multiple atoms, also resonate at predictable frequencies (such as by emitting electromagnetic radiation). For example, a mass of liquid water resonates at 109.6 THz. Water in tension (such as at the surface of a bulk, at various states of surface tension) resonates at 112.6 THz. Carbon atoms and carbon structures also exhibit natural frequencies that depend on the structure. For example, the natural resonance frequency of carbon nanotubes (CNTs) depends on the tube diameter and length of the CNTs. Growing CNTs under controlled conditions to control tube diameter and length results in control of the natural resonant frequency of the structure. Therefore, synthesizing or otherwise "growing" CNTs is one way to tune to a desired resonant frequency.

Other structures formed from carbon can form under controlled conditions. Such structures include, but are not limited to, carbon nano-onions (CNO), carbon lattices, graphene, carbon-containing aggregates or agglomerates, graphene-based other carbon-containing materials, engineered nanoscale structures, etc., and/or combinations thereof , according to the presently disclosed implementation, any of the structures is incorporated into a sensor of a vehicle component. Such structures can be formed to resonate at a particular tuning frequency, and/or such structures can be modified in post-processing to obtain desired characteristics or properties. For example, desired properties, such as high reinforcement values, can be achieved by selecting a combination ratio of materials and/or by adding other materials. Furthermore, the co-location of multiple such structures introduces additional resonance effects. For example, two graphene sheets may resonate between them at a frequency that depends on the length, width, pitch, pitch shape, and/or other physical properties of the sheets and/or their juxtaposition to each other.

As is known in the art, materials have specific measurable properties. This is true for naturally occurring materials as well as for engineered carbon allotropes. Such engineered carbon allotropes can be tuned to exhibit physical properties. For example, carbon allotropes can be engineered to exhibit physical properties corresponding to: (a) specific configurations of constituent primary particles; (b) aggregate formation; and (c) agglomerate formation. Each of these physical properties affects a particular resonant frequency using a material formed with a corresponding particular carbon allotrope.

In addition to tuning a particular carbon-based structure for a particular physical configuration corresponding to a particular resonant frequency, it is also possible to tune a carbon-containing compound to a particular one of the resonant frequencies (or set of resonant frequencies). A set of resonance frequencies is called a resonance characteristic curve. A carbonaceous material tuned to exhibit a particular resonant frequency when probed by an RF signal, such as a carbonaceous material comprising a carbon-based microstructure, can be tuned to exhibit a particular electrical impedance by tuning the particular compounds that make up the material to have a particular electrical impedance A specific resonance characteristic curve is obtained. Different electrical impedances in turn correspond to different frequency response characteristic curves.

Impedance describes how difficult it is for alternating (AC) current to flow through a component. In the frequency domain, since the structure behaves as an inductor, the impedance is a complex number with real and imaginary parts. The imaginary part is the inductive reactance (a circuit element resists current flow due to the inductance and capacitance of the element; a greater reactance results in a smaller current if the same voltage is applied) component X _L , which is based on the specific structure Frequency f and inductance L:

X _L ＝2πfL (equation 1)

As the received frequency increases, the reactance also increases, so that at a certain frequency threshold, the measured strength (amplitude) of the transmitted signal may attenuate. The inductance L is affected by the electrical impedance Z of the material, where Z is related to the material properties of magnetic permeability μ and permittivity ε by the following relationship:

Thus, tuning of the material properties changes the electrical impedance Z, thereby affecting the inductance L and thus the reactance X _L .

Carbon-containing structures with different inductances, such as those disclosed in U.S. Patent No. 10,428,197, entitled "Carbon and Elastomer Integration," issued October 1, 2019 to Anzelmo et al., which is incorporated by reference in its entirety methods incorporated herein) may exhibit different frequency responses (when used to create sensors for the aforementioned systems). That is, a carbon-containing structure with a high 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.

Material properties such as magnetic permeability, permittivity, and electrical conductivity can also be considered when formulating compounds to tune to a specific electrical impedance. Furthermore, it was observed that when the structure is under tension-inducing conditions, such as when the structure is slightly deformed (such as thereby slightly changing the physical properties of the structure), the first carbon-containing structure will resonate at a first frequency, while the second The carbon-containing structure will resonate at the second frequency.

An example carbon-containing structure (eg, as shown in FIGS. 19-16Y ) can resonate at a first frequency, which can be related to an equivalent circuit including capacitor C ₁ and inductor L ₁ . The frequency _f1 is given by the following equation:

Deformation of the carbon-containing structure can in turn change the inductance and/or capacitance of the structure. The variation may be related to an equivalent circuit comprising capacitor _C2 and inductor _L2 . The frequency _f2 is given by the following equation:

FIG. 3 illustrates a signature classification system 300 that processes signals received from sensors formed from carbon-containing tuned resonant materials. Signature classification system 300 may be implemented in any physical environment or weather condition. FIG. 3 relates to the incorporation of tuned resonant sensing materials into automotive components for classifying signals (such as signatures) detected by, classifying and/or received from sensors installed in the vehicle. At operation 302 a sonication signal at a selected sonication frequency is transmitted. The ping signal generating mechanism and pinging mechanism may be implemented by any known technique. For example, a transmitter module may generate a selected frequency of 3 GHz and radiate the signal using an antenna or antennas. The design and location of the tuning antenna (such as mounted on and/or within any one or more of the wheel well or the vehicle) may correspond to any tuning antenna geometry, material, and/or location such that the intensity of the acoustic pulse is sufficient to Induced (RF) resonance in the proximity sensor. Several tuned antennas are positioned on or within the structural member proximate to the corresponding sensors. Thus, when the proximal surface sensor is stimulated by an acoustic pulse, the proximal surface sensor resonates inversely through the signature. The signature may be received (operation 304 ) and stored in a database including the received signature 310 . The sequence of emitting sound pulses followed by receiving signatures may be repeated in a loop.

The acoustic pulse frequency may be varied while iterating through the loop (operation 308). Thus, when the operation 304 is performed in the loop, the operation 304 may store the signatures 312, including the first signature 312 ₁ , the second signature 312 ₂ up to the Nth signature 312 _N . The number of iterations can be controlled by decision 306 . When the "No" branch of decision 306 is taken (such as when there are no other additional sound pulses to transmit), then the received signature may be provided (operation 314) to a digital signal processing module (such as the one shown in FIG. 1B ). instance of signature analysis module 154). The digital signal processing module classifies the signature against a set of calibration points 318 (operation 316). The calibration points may be configured to correspond to specific acoustic pulse frequencies. For example, calibration points 288 may include a first calibration point 288 ₁ which may correspond to a first sound pulse near 3 GHz and a first return signature, a second calibration point which may correspond to a second sound pulse near 2 GHz and a second return signature 288 ₂ and so on for any integer value "N" calibration points.

At operation 320 , the classified signal is sent to a vehicle central processing unit (such as vehicle central processing unit 116 of FIG. 1B ). The classified signals may be relayed by the vehicle's central processing unit to an upstream repository hosting a computerized database configured to host and/or run machine learning algorithms. Thus, a large number 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," given a set of sensory measurements that may correlate with information about vehicle performance, such as tire degradation due to repeated use. condition or diagnosis. If the measured deflection (such as air pressure) of a particular portion of an airfoil component differs from the measured deflection (such as air pressure) of a different portion of the airfoil component during operation of the vehicle, a potential diagnosis may be that one tire is underinflated, thereby causing the vehicle to The ride height is non-uniform, causing airflow over, on and/or around the vehicle to exhibit proportional non-uniformity, as detected by deflection on the airfoil components. Other underlying conditions or diagnoses may also be identified by the machine learning system. The conditions and/or diagnostic and/or support data can be returned to the vehicle to complete the feedback loop. Instruments in the vehicle provide visualizations that can be acted upon, such as by the driver or engineer.

FIG. 4 illustrates various physical characteristics or aspects (tire condition parameters 400 ) related to the incorporation of tuned resonant sensing materials into automotive components, such as tires. Here, the figure is presented with respect to addressing the deployment of sustainable sensors in tires, both non-pneumatic and pneumatic. The configuration of the tire may correspond to radial tires, bias ply tires, tubeless tires, solid tires, safety tires, and the like. Tires may be used in any kind of vehicle and/or equipment and/or accessories related to the vehicle. 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, Lawn machines, tractors, trailers, trucks, wheelchairs, etc. Tires may also be used in non-motorized vehicles, equipment, and accessories, such as bicycles, tricycles, unicycles, lawn mowers, wheelchairs, carts, and the like, in addition to or instead of the presented vehicles.

The parameters shown in FIG. 4 are illustrative, and other variants may exist or otherwise be prepared to meet specific desired performance characteristics for many conceivable end-use scenarios, including those designed to provide increased life ( Truck tires that are designed to provide maximum road adhesion (potentially at the expense of service life) or soft racing tires designed to provide maximum road adhesion (potentially at the expense of service life).

Various carbon structures are used in different formulations with other non-carbon materials integrated into the tire, which are then subjected to mechanical analysis to determine their corresponding properties of the tire. Some of these properties can be determined empirically through 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 over a uniform surface such as a roller, whereas tread life is based on wear testing over a short period of time, the results of which are extrapolated to arrive at a prediction tread life value.

Many more tire properties can be measured, but some of these measurement techniques can cause physical damage to the tire and are therefore measured at critical points in the tire's life. In contrast, using survivable sensors embedded in tires allows such otherwise destructive measurements to be made throughout the life of the tire. For example, such sensing may be performed using the detection of a response signal based on an RF signal impinging on a sensor embedded in the tire. Additionally, as discussed, each body ply and/or tread layer of the tire includes durable (also referred to as "sustainable") sensors that are tuned to resonate at a particular frequency.

Plies used in tires may be formulated to combine carbonaceous structures with other materials to achieve specific material compositions that exhibit desired performance characteristics, such as handling and longevity. One or more natural resonant frequencies of a particular material composition may be subjected to spectral analysis to form a spectral characteristic curve for the particular material composition. This spectral characteristic curve can be used as a calibration baseline for this material. When the body ply and/or the tread layer of the tire undergoes deformation, the spectral characteristic curve changes, which can be used as an additional calibration point. Many such calibration points can be generated by testing, and such calibration points can in turn be used to gauge deformation.

Analysis of the spectral response leads to quantitative measurements of many tire parameters. For example, tire parameters that may be determined from signature analysis may include tread life 422, operation at a first temperature 428, operation at a second temperature 426, rolling economy at a first temperature 430, operation at a second temperature Rolling Economy 432 , Rolling Uniformity 436 , and Braking Uniformity 438 below.

Responses, such as those represented spectrally based on return acoustic pulse signals received from sensors embedded in the material in the tire ply, may be representative of the observed deformation. That is, a certain type of tire deformation will correspond to a certain type of specific response such that a mapping can be made between a response or type of response and a type of degradation. Furthermore, time-varying changes in the spectral response of a tire as it undergoes field deformation can be used to determine a number of ambient conditions. In tires constructed using multiple plies, each body ply and/or tread layer may be tuned to exhibit a particular tuning frequency or frequency range. For example, FIG. 5 shows a schematic diagram for building a tire from multiple plies, each of which has a different specific tuning frequency or frequency range.

5 depicts a schematic diagram 500 for fine-tuning or tuning multiple body plies and/or tread layers of a tire by selecting a carbon-containing tuned resonant material for incorporation into a tire component or structure, which can be performed in any environment implemented in. Figure 5 illustrates how different carbons are mixed into a tire compound formulation which in turn is assembled into a multi-ply tire. The resulting multi-ply tires exhibit various resonance sensitivity and frequency shifting characteristics.

A plurality of reactors (such as reactor 552 ₁ , reactor 552 ₂ , reactor 552 ₃ , and reactor 552 ₄ ) each produce (or otherwise deliver or provide) a particular carbon additive/filler to a network that Tuned to obtain a specific defined spectral characteristic curve. Carbon additives such as first tuning carbon 554 , second tuning carbon 556 , third tuning carbon 558 , and fourth tuning carbon 560 may be mixed with other (carbon-based or non-carbon-based) compositions 550 . Any known technique may be used to mix, heat, pre-treat, post-treat, or otherwise combine a particular carbon additive with other compositions. Mixers such as Mixer 562 ₁ , Mixer 562 ₂ , Mixer 562 ₃ , and Mixer 562 ₄ are presented to demonstrate how different tuning carbons may be introduced into various components of the tire. Other technologies for tire components may involve other construction techniques and/or include other components of the tire. Any known technique for multi-ply tires may be used. Additionally, a particular body ply and/or tread layer may be determined based on the properties of a particular body ply and/or tread layer formulation (such as set of body plies and/or tread layers 568, including body plies and/or tread layers Spectral characteristic curves of/or tread layer 568 ₁ , body ply and/or tread layer 568 ₂ , body ply and/or tread layer 568 ₃ and body ply and/or tread layer 568 ₄ ). For example, based on stimulus and response characteristics, a first host ply and/or tread layer formulation (such as host ply and/or tread layer formulation 564 1 ) may exhibit a first spectral characteristic curve, while a second host ply and/or tread layer formulation 564 ₁ may exhibit a first spectral characteristic curve, while a second host ply and/or tread layer formulation A ply and/or tread layer formulation, such as body ply and/or tread layer formulation 564 ₂ , may exhibit a second spectral characteristic curve.

The resulting different formulations (such as, body ply and/or tread layer formulation 564 ₁ , body ply and/or tread layer formulation 564 ₂ , body ply and/or tread layer formulation 564 ₃ and The body ply and/or tread layer formulation ₅₆₄₄ ) is used in the different body ply and/or tread layers formed into the tire assembly 566, each of the body ply and/or tread layers The corresponding spectral characteristic curves are shown.

FIG. 6 shows a second set of example condition signatures 600 emitted from a tire formed from a layer of carbon-tuning resonant material. Example conditional signature 600, or any aspect thereof, may be transmitted in any environment. Figure 3F1 shows multiple body plies and/or tread layers of a new tire, such as body ply and/or tread layer #1, body ply and/or tread layer #2 and body ply and/or or tread layer #3). As used in this example and elsewhere with reference to any one or more of the presented implementations, the term "ply" may refer to a ply or layer within the body of a tire, or alternatively, the The body, remote from the tire, protrudes radially outwards for the layer intended for contact with a hard surface or, for off-road tires, with the ground. In an example, the first body ply and/or tread layer is formulated (referred to as produced with a specific formulation) using tuned carbon such that the first body ply and/or tread layer is stimulated with 1.0 GHz acoustic pulses such as The first acoustic pulse 602) resonates at 1.0 GHz when stimulated. Similarly, the second body ply and/or tread layer is formulated using a tuning carbon such that the second body ply and/or tread layer when stimulated with a 2.0 GHz acoustic pulse, such as the second acoustic pulse 604 Resonant at 2.0GHz. Additionally, the third body ply and/or the tread layer is formulated using a tuned carbon such that the third body ply and/or the tread layer when stimulated with a 3.0 GHz acoustic pulse stimulus, such as the third acoustic pulse 606, at Resonant at 3.0GHz. As shown by first response 608 , second response 610 , and third response 614 , all three body plies and/or tread layers respond at their respective tuning frequencies.

The transceiver antenna may be located in and/or on the wheel well of the corresponding tire. A system that handles any such generated response signals may 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 though the right front tire mounted on the vehicle's front right wheel may respond to acoustic pulses emitted from a transceiver antenna located in the vehicle's left front wheel well, the response signal from the vehicle's left front tire is much less The response signal from the right front tire will be significantly attenuated (and thus recognized).

When the transceiver antenna is located in the wheel well of the corresponding tire, the response from the corresponding tire will be attenuated relative to the acoustic pulse stimulus. For example, the response from the corresponding tire may be attenuated by 9 decibels (-9 dB) or more relative to the sonic pulse stimulus, or may be attenuated by 18 decibels (-18 dB) or more relative to the sonic pulse stimulus, or may be attenuated relative to the sonic pulse stimulus 36 decibels (-36dB) or more, or can attenuate 72 decibels (-72dB) or more relative to the acoustic pulse stimulus. In some cases, the acoustic impulse signal generator is designed in combination with the transceiver antenna located in the wheel well so as to attenuate the acoustic impulse response of the corresponding tire by no more than 75 dB (-75 dB).

FIG. 7 depicts a third set of example condition signatures 700 emitted from a tire after some carbon-containing tuning resonant material wears out. Optionally, one or more variations of the example conditional signature 700 or any aspect thereof may be implemented within the context of the architecture and functionality of the implementations described herein. Example conditional signature 700, or any aspect thereof, may be transmitted in any environment.

In this example, the tires are worn. More specifically, the outermost body plies and/or tread layers have been completely worn away. Therefore, acoustic pulse stimulation at 1.0 GHz will produce no response from the outermost ply. This is shown as first response decay 702 in the graph. As the tire continues to experience tread wear, the acoustic impulse response from the next body ply and/or tread layer and the acoustic impulse response from the next successive body ply and/or tread layer etc. will decay, the attenuation Can be used to measure the total tread wear of a tire. Alternatively, the same tuning carbon can be used in all plies. The tire's tread wear, as well as other indications, may be determined based on the return signal signature from the tire.

FIG. 8 is a top view of two layers, where each layer houses a split ring resonator (SRR), eg, forming an example split ring resonator (SRR) configuration including two concentric SRRs. As used herein, a split ring resonator (SRR) consists of a pair of concentric rings disposed on a dielectric substrate, where each ring has a slit (eg, due to a printed pattern). When the SRR array is excited with a time-varying magnetic field, the structure behaves as an effective medium with negative effective permeability in a narrow frequency band around the SRR resonance point. Many geometries are possible, eg, such that the dimensions and/or spacing between each SRR, including dimensions "a", "r" and/or "c", are selected to achieve a particular corresponding spectral response. For example, "a" may be approximately 1 mm, "r" may be 2 mm, and "c" may be approximately 0.6 mm. These dimensions may correspond to producing a desired and/or anticipated spectral response, for example, resulting in a relatively broad and/or broad signal response rather than a narrow and/or notched response, thereby facilitating improved spectral analysis, resulting in Improve cost efficiency when using tools such as spectrum analyzers. Additionally or alternatively, any of the dimensions may be further tuned to achieve a particular desired end-result goal, such as in race track applications, as compared to off-road applications and the like. One particular geometry involves gaps between concentric rings. Such gaps create capacitances that, in combination with the inductance inherent in the pair of concentric rings, introduce variations in the resonance of the ensemble.

Printable, sheet-oriented, cylinder-type, split-ring resonator designs can be constructed from any conductive material, including metals, conductive non-metals, dielectric materials, semiconductor materials, and more. In addition to tuning based on the choice and/or processing of the conductive material, split ring resonators can also be tuned by changing the geometry such that the effective permittivity is adjusted accordingly. The effective permittivity as a function of the shape of the split-ring resonator is given in Equation 1.

where a is the spacing of the cylinders, ω is the angular frequency, μ0 is the magnetic permeability of free space, r is the radius, d is the spacing of the concentric conductive sheets, l is the stack length, c is the ring thickness, and σ is measured around the circumference The resistance per unit length of the sheet.

In some cases, the value of a (eg, the pitch of the cylinders of a cylindrical split ring resonator) can be made relatively small so that the concentric rings absorb EM radiation over a relatively narrow frequency range. In other cases, the value of a can be made relatively large so that the concentric rings each absorb EM radiation at frequencies separated by a large interval. In some cases, different sized SRRs may be placed on different surfaces of the tire. In some cases, different sized SRRs placed on different surfaces of the tire may be used to measure tire condition (eg, temperature, age, wear, etc.).

In some embodiments, the material forming the split ring resonator is a composite material. Each SRR can be configured to have any particular desired tuned response to EM stimuli. SRRs larger than the atomic scale allow for a greater degree of control over the resonant response, at least because SRRs are designed to mimic the resonant response of atoms (albeit on a much larger scale and at lower frequencies). Furthermore, SRRs are much more reactive than ferromagnetic materials found in nature. The pronounced magnetic response of SRRs is accompanied by significant advantages over heavier, naturally occurring materials.

Figure 9 shows a schematic diagram showing a complete tire diagnostic system and apparatus for tire wear sensing by impedance-based spectroscopy. Tire 900, such as a pneumatic rubber tire filled with air or nitrogen ( _N2 ), may comprise conventional tire components including a body 920, an inner liner 912, a bead filler region 922, beads 916, one or more belts Layers 904, 906, 908, and 910, tread 902, and impedance-based spectral wear sensing printed electronics 918 (alternatively, sensors comprising carbon-based microstructures for The resonators within any one or more of layers 904-910 perform signal frequency shift and attenuation monitoring).

As shown here, wireless strain sensors can be placed on the surface or sides of the innerliner (or embedded in it) to monitor tire conditions for vehicle safety (such as detecting damaged tires). Tire deformation or strain monitoring can (indirectly) provide information indicative of the degree of friction between the tire and the contacting road surface, which can then be used to optimize the car's tire control system. The tire information may be wirelessly transmitted to a receiver located in the hub of the tire based on the resonant sensor platform.

Figure 10 shows a system 1000 for providing tire wear related information via telemetry to a navigation system or to an apparatus for manufacturing printed carbon-based materials. System 1000 may function with any one or more of the presently disclosed systems, methods, and materials, such as sensors including carbon-based microstructures, such that a repeated description thereof is omitted. Impedance spectroscopy, also known as electrochemical impedance spectroscopy (EIS), refers to the measurement of a sample, such as a sensor comprising a carbon-based microstructure incorporated into one or more tire belts of a tire 1002, that involves Impedance transduction method for applying a sinusoidal electrochemical perturbation (potential or current) over a wide range of frequencies. Printed carbon-based resonators 1004 may be incorporated within one or more tire components, such as tire belts, where each of printed carbon-based resonators 1004 has the generally elliptical configuration shown, or is adapted to realize a suitable There is a particular desire to efficiently and accurately detect wear of vehicle components by monitoring frequency shifts and/or attenuation, such as first response attenuation indicating wear of the tire body ply and/or tread layer having a natural resonant frequency of about 1.0 GHz Some other shape or configuration of resonant properties.

Components of the roll 1010 capable of forming the printed carbon-based resonator 1004 include a carbon-based microstructure and/or a reservoir 1012 of a microstructural material (such as graphene), such as a groove, an anilox roll 1014 (referring to a core typically made of steel or aluminum). A rigid cylinder consisting of a steel or aluminum core coated with technical ceramics whose surface contains millions of extremely fine dimples (called cells), plate cylinder 1016 and impression cylinder 1018 . In operation, graphene extracted from repository 1012 may be rolled, pressed, stretched, or otherwise fabricated into printed carbon-based resonator 1004 by rollers in assembly of rollers 1010 . For system 1000 to function, alignment (finger alignment) of printed carbon-based resonators 1004 may not be required.

Thus, any combination of the aforementioned features can be used to make tires having resonators (referring to actual or "equivalent" grooves, LCs, and/or resonant circuits) in which the carbonaceous microstructure itself can respond to all signals from the transceiver. Transmitting RF signals and/or resonating with energy supplied by an advanced energy source such that other sensors disposed in or on any one or more components (such as the tread, one or more plies, innerliner, etc. of a tire) can Exhibits frequency shifting or signal attenuation properties or behavior. The described resonators do not necessarily need to embody actual electronics and/or integrated circuits (ICs). The described resonators can be implemented simply as tuned carbonaceous microstructures, thus avoiding common degradation problems that can arise when implementing traditional discrete circuits in decomposable materials such as tire tread layers. Such resonators may resonate in response to externally supplied 'acoustic pulses', such as supplied by transceivers located in the wheel wells of the vehicle, or the resonators may be resonant by using any variation or number of power or charge generators ( co-located (meaning within the same tire tread layer, but possibly at different locations within that tire tread layer), self-powered, Self-probe capability to charge and respond.

Any of the described resonators (and other resonators and/or resonant circuits) may be configured to transmit and/or further transmit an oscillating RF signal (or other form of electromagnetic emissions, depending on the overall configuration). As vehicle tires experience wear from use (such as on-road or off-road driving), the tire tread layers that come into contact with the road or ground (earth) may undergo deformation, either immediately or over time, such as from "flattening" recognized that flattening refers to the at least partial flattening of a segment of the tread layer of a vehicle tire exposed during rotation or rolling, and/or as observed from lateral motion experienced during cornering, etc.), the resulting signal frequency shifts and/or Or the attenuation behavior can change according to such "squeezing" because the associated signal can oscillate within one or more known amplitude ranges. Additionally or alternatively, as the tire undergoes deformation, the observed signal may oscillate within a known frequency range corresponding to a particular resonator, allowing precise and accurate identification of the type of degradation that occurs when the oscillation occurs, Rather than requiring the driver, passengers and/or other vehicle occupants to leave the vehicle while the vehicle is stationary to observe tire tread conditions. Such frequency-shifted oscillations may be observed as a back-and-forth frequency shift between two or more frequencies within the known frequency range.

Wirelessly capable strain (such as a geometric measure of deformation representing relative displacement between particles in a body of material caused by external constraints or loads) sensors located on the side of the innerliner can monitor tire conditions to ensure automotive safety ( such as by detecting damaged tires). In addition, tire deformation or strain monitoring can indirectly provide information on the degree of friction between the tire and the road surface, which can then be used to optimize automotive tire control systems. Such tire information may be wirelessly transmitted to a receiver (and/or transceiver) located in the hub of the wheel based on a resonant sensor (such as an impedance spectroscopy IS sensor) platform.

11 is a schematic diagram 1100 relating to a resonant serial number based digital encoding system for determining vehicle tire wear via ply printed encoding. The resonant serial number based digital encoding system may be combined and/or function with any of the presently disclosed systems, methods and sensors. A digital encoding system based on a resonant serial number provides digital encoding of tires via ply-printed encoding, thus providing cradle-to-grave (referring to complete service life) tracking (and associated performance metrics) of the tire and usage profile without the need for Legacy electronics sensitive to normal wear and tear in tires.

In some implementations, digitally encoding a tire's resonant serial number through tire tread layer printing can facilitate cradle-to-grave tire tracking and use of the tire without necessarily requiring the presence of electronics within the tire. For example, along with tire wear sensing accomplished by impedance spectroscopy, additional resonators may be digitally encoded onto one or more printed patterns such as a serial number for telemetry tracking. Accordingly, a vehicle so equipped can track tread wear, miles driven (eg, total), and tire age without the need for radio frequency identification (RFID) technology.

Along with tire wear sensing via Impedance Spectroscopy (IS) and/or Electrochemical Impedance Spectroscopy (EIS), additional resonators can be digitally encoded onto the printed pattern to provide a recognizable sequence for telemetry-based tire performance tracking Number. Tires incorporating the discussed printed carbon-based resonators may be inherently serializable by printing progressively onto the body ply and/or tread layer.

Figure 12 shows a schematic 1200 for resonant serial number encoding in a tire. Serial number "6E" as shown is encoded in a specially prepared array of printed carbon resonators configured to resonate according to the 'acoustic pulse' stimulus-response graph 1212, allowing easy and reliable identification of such equipment This specific body ply and/or tread layer of a vehicle tire.

Figure 13 is presented to illustrate the use of a split ring resonator (SRR) as a resonant device that facilitates the aggregation phenomenon produced by the different proximal presence resonator types. This figure shows the inner surface 1301 of a tire, wherein the inner surface has two split ring resonators (e.g., split ring resonator 1303A and split ring resonator 1303B), each of the split ring resonators A circuit configuration 1902 is formed that can be tuned to attenuate a signal at a particular frequency and/or attenuate within a particular frequency range. In this embodiment, the circuit configuration 1902 is shown as corresponding to a geometric pattern of a substantially circular split ring resonator; however, alternative circuit configurations may have different geometric patterns (e.g., cylindrical, elliptical, Rectangular, oval, square, etc.), therefore, any conceivable geometric configuration is possible. Variations of geometric configurations may be selected based on the effect on the resonant ability of the geometric pattern. Specifically and as shown, the geometric patterns can include self-assembled carbon-based particles having various coalescence patterns (e.g., coalescence pattern 1306, coalescence pattern 1308, and coalescence pattern 1310) that Any one or more of these may constitute a concentrated region 1304 that may affect the resonant properties of the material into which the carbon-based microstructure is incorporated. A coalescence pattern and/or a series of coalescence patterns may also affect the resonance properties of materials incorporating carbon-based microstructures.

In various configurations, the carbon-based microstructure is formed at least in part from graphene. In this context, graphene refers to an allotrope of carbon in the form of an atomic monolayer in a two-dimensional hexagonal lattice in which one atom forms each vertex. Co-location and/or juxtaposition of multiple such hexagonal lattices into more complex structures introduces additional resonance effects. For example, the juxtaposition 1302 of two graphene sheets or platelets may resonate between them at a frequency that depends on the length, width, pitch, thickness, pitch shape, and/or other physical characteristics of the flakes and/or platelets. properties and/or their relative juxtaposition with each other.

Table 1 depicts a range of possible attenuations due to aggregation effects. As shown in the table, each of the structures has a different resonant frequency domain corresponding to its scale label.

Table 1: Example of Aggregate Effects

Any number of different split ring resonators can be printed onto the surface of the tire. Furthermore, any number of different sized split ring resonators can be printed onto any surface of the tire. Selection of the material and/or size and/or other structural or dimensional characteristics of a particular split ring resonator may be used to control the resonant frequency of the split ring of that particular resonator. A series of split ring resonators of different sizes can be printed such that the pattern corresponds to a digitally encoded value. Stimulating a series of split ring resonators of different sizes via electromagnetic signal communication (eg sweeping through 8GHz to 9GHz or similar range) and measuring the decay response through the return range yields a identifiable coded sequence number. Many different encoding schemes are possible, therefore, the non-limiting examples of Table 2 are for illustration only.

Table 2: Example Encoding Schemes

FIG. 14 shows a schematic diagram of a tire sensor 1400 according to some implementations. In one implementation, tire sensor 1400 may include a section 1402 of a tire body having a plurality of tire plies (eg, as shown in FIG. 9 ). The tire sensor 1400 may detect the temperature of a tire ply 1408 into which, for example, the tire sensor 1400 is incorporated. In one implementation, a tire sensor may include a ceramic material 1404 (eg, organized as a matrix) and one or more SRRs 1406, such as shown in FIG. 8 and elsewhere in this disclosure. Each of the one or more SRRs 1406 may have a natural resonant frequency that may shift (eg, as shown in FIG. 16 ) in response to one or more of changes in the elastomeric properties of the corresponding tire or changes in temperature. . Conductive layer 1410 may be dielectrically separated from corresponding ones of one or more SRRs 1406 . In some implementations, the tire sensor 1400 can be produced and shipped without being incorporated into a tire so that it can be later incorporated into the tire and/or tire ply.

Additionally or alternatively, tire sensor 1400 may be incorporated into a system (not shown in FIG. 14 ) configured to detect tire strain in a vehicle (eg, as shown in FIG. 16 ). The system may include an antenna disposed on one or more of the vehicle or vehicle components (eg, as discussed in this disclosure with respect to the transmission and/or propagation of electromagnetic signals). The antenna is configured to output electromagnetic acoustic pulses. The system may also include a tire including a body formed from one or more tire plies (eg, as shown in FIG. 9 ). Any one or more of the tire plies may include a split ring resonator (SRR), for example, as discussed in this disclosure. In one implementation, each SRR has a configuration configured to proportionally deflect (e.g., , as shown in Figure 16) natural resonant frequency.

In some implementations, the described systems can be used to detect changes in physical properties of materials associated with tires and/or vehicles (eg, cars and trucks) outside of the configuration. For example, the system may detect changes in surface temperature of aircraft wings and/or other types of airfoils (eg, associated with spacecraft and/or the like). Additionally, the system may permit one or more SRRs 1406 to be removably adhered to a patient in a hospital setting such that temperature readings of the corresponding patient may be obtained without the use of conventional thermal sensors (e.g., rely on radiative heat transfer techniques, etc.). In any of these examples, as well as other examples, such systems can detect physical properties associated with a surface.

In one implementation, the system may include a single antenna and one or more flexible substrates configured to output electromagnetic acoustic pulses. Each of the flexible substrates may include a first side including a plurality of split ring resonators (SRRs) (eg, one or more SRRs 1406 ) disposed on the flexible substrate. Each SRR may have a natural resonant frequency that may shift proportionally (eg, as shown in FIG. 16 ) in response to changes in the elastomeric properties of the corresponding one or more tire plies. The elastomeric properties may include one or more of reversible deformation, stress, strain or temperature. In this way, the system can generate an absorption profile (eg, referring to a unique variation in the absorption phenomenon of an electromagnetic acoustic pulse output by an antenna). The system may include a second side positioned opposite the first side. The second side is attachable to the surface. A single antenna can analyze data associated with an absorption profile and output a configuration of physical properties.

15 depicts a graph 1500 of measured resonance signature signal strength (in decibels dB) versus height of tire tread layer loss (in millimeters mm), according to some implementations. As shown herein, carbon-containing microstructures and/or microstructural materials may be incorporated into the sensor, or in some configurations, at a given concentration level or at a plurality of different concentration levels (in one or more tire tread layers each) are incorporated into all layers of one or more tire treads to achieve the unique degradation profile shown. That is, the measured resonance signature (referring to the identifying "signature" of the particular tire tread layer in question) can be "probed" by one or more RF signals as described herein to reveal the attenuation of that transmitted signal as shown .

A new tire tread layer may be configured to indicate a signal strength (measured in decibels dB) of about 0. The strength may vary in proportion to the degree of degradation of the tire tread layer. For example, a 2 mm height loss of a tire tread layer (assumed to be in contact with the road surface) may correspond to the measured resonance signature signal strength profile as shown. A 'burst' signal at 6.7GHz can be measured at a strength level of about 9dB, and so on.

Thus, carbonaceous microstructures of unique concentration levels, chemistries, dispersions, distributions, and/or the like may be embedded in (or in some cases, placed on one or more of the tire tread layers) ostensibly) to achieve a unique and easily identifiable measured resonance signature signal strength as shown. As a result, users of such systems are immediately informed of the exact extent and location of tire tread wear when it occurs while driving, rather than being limited to viewing the tires while the vehicle is stationary, which can be time consuming And cumbersome.

16 depicts measured resonance signature signal strength (in decibels in dB) relative to a split ring resonator incorporated into a tire tread and/or tire ply (eg, as discussed in this disclosure), according to some implementations ( Graph 1600 of the natural resonant frequency of SRR). As shown herein, carbon-containing and/or carbonaceous microstructures and/or microstructural materials may be incorporated into sensors, or in some configurations, at a given concentration level or at a plurality of different concentration levels (in one or more tires in each of the tread layers) into all layers of one or more tire treads to achieve the unique degradation profile shown. That is, the measured resonance signature (referring to the identifying "signature" of the particular tire tread layer in question) can be "probed" by one or more RF signals as described herein to reveal the deviation of that transmitted signal as shown. The drift is representative of and/or proportional to the extent of reversible tire deformation (eg, stress and/or strain) such as may be encountered in a drifting situation. In this way, the behavior of the SRR "response" signal can be modeled in terms of tire deformation, such as strain (associated with drift), such that the graph of FIG. tire wear, etc.) to get a complete picture of tire condition and performance.

Real-world scenarios that produce lateral tire stiction losses can include drifting and/or skidding, for example meaning phenomena that occur when a layer of water forms between the vehicle's wheels and the road surface, resulting in a loss of traction that prevents the vehicle from responding to control inputs . If all contacting wheels slip simultaneously, the vehicle effectively becomes an uncontrollable skateboard. Use of the presently disclosed SRRs and/or resonators in conjunction with antennas and/or signal processing devices can effectively eliminate the need to rely on conventional slip detection techniques, such as by using a vibration detection unit coupled to the surface of a tire that may be damaged due to Deteriorated and damaged by prolonged use. Additionally, Figure 16 shows the spectral response (in decibels of signal) associated with lateral tire movement encountered during a loss of stiction while drifting. In a real world situation, something like a temporary loss of stiction might be heard as a high-pitched "squeal", unlike other sounds that are only heard during rapid forward rotation. Such periodic stiction losses (before the drifting vehicle regains stiction and/or traction) may manifest (not shown in FIG. 16 ) as a regular and/or periodic shift in the natural resonant frequency of the corresponding SRR. Referring back to FIG. 16, a "screaming" type situation may be visually depicted by small regular and/or periodic shifts in the frequency of the various valleys and/or peaks of the curve.

As can be seen, real-time multi-modal resonators support methods for measuring stiction using resonant material-containing sensors for elastomer property change detection. In one arrangement, one or more sensors comprising a resonant material for detection of changes in the properties of the elastomer are positioned near the transducer. A stimulus signal is emitted to excite one or more resonant material-containing sensors for detection of changes in the properties of the elastomer. The emissions include electromagnetic energy spanning a known frequency range. Calibration signals are captured under known stiction conditions. After receiving a return signal comprising at least in part frequencies responsive to the stimulus signal, various signal processing techniques are applied to the return signal. For example, various signal processing techniques are applied to the return signal for comparison with the stimulus signal. Whenever the frequency and/or amplitude of the return signal differs from the calibration signal, a corresponding interfacial indirect permittivity (eg, at the interface between the tire and the running surface) is calculated. Correlate absolute and/or relative values of interfacial indirect permittivity to stiction values (eg, using a calibration table). Changes in static friction values over time are in turn related to road and/or tire conditions.

The static and/or dynamic values making up the aforementioned calibration signal and/or calibration table may be based at least in part on an analysis of the stimulus signal and/or an analysis of the environment in the vicinity of the transducer. Furthermore, the aforementioned calibration signals and/or calibration tables may cover permittivity calibration signals, magnetic permeability calibration signals, temperature calibration signals, vibration calibration signals, doping calibration signals, and the like. In one implementation, a calibration procedure may be performed under known and/or controlled environmental conditions (e.g., dry pavement and clear weather) to generate baseline data at various forward-facing angular velocities (such that the test vehicle is only directly forward movement without side-slip and/or sliding movement). This baseline data then serves as one or more calibration curves from which deformation values can then be compared and/or calculated. In this way, a significant change in performance relative to the initial unstretched (baseline) calibration curve (eg, as shown in Figure 16) can be observed.

Whenever the return signal differs from the calibration signal, further analysis of the return signal relative to the stimulus signal can be used to identify which frequencies of the return signal differ from the calibration signal. The difference may be observed and/or measured as an attenuation of one or more frequencies relative to the calibration signal. Additionally or alternatively, the difference may be observed/measured as a frequency shift of the peak relative to the peak of the calibration signal (as shown in Figure 16, relative to correspondingly stretching the data by 0.5%, etc.).

Figure 17 illustrates the use of a split ring resonant structure configured to resonate in a manner corresponding to an encoded serial number. Such patterns of split ring resonant structures can be printed on tires or other elastomers. As shown, the coded serial number "E1" is shown by the presence of four differently sized split ring resonators. Stimulus-response graph 1700 shows EM stimulation in the range of about 8 GHz to about 9 GHz, while the response is shown as an attenuation in the range of about -8 dB to about -18 dB. Stimulating a series of split-ring resonators of different sizes via electromagnetic signal communication across the range and measuring the returned S-parameters across the range yields a convenient and reliable identification of the particular printed pattern. Subsequently, if a unique pattern is printed onto each of a series of tires, and if the pattern is associated with a coded serial number, the particular tire can be determined based on the pattern's response to the EM interrogation.

More specifically, if a unique pattern is printed onto each of a series of tires, and if the pattern is associated with a coded serial number, then EM responses to EM stimuli within the range corresponding to the coding scheme can be The query determines a particular tire based on the measured S-parameters (eg, S-parameter ratios corresponding to decay). In the example of FIG. 17, the attenuation falls within the range of about -8 dB to about -18 dB, however, in other measurements the attenuation falls within the range of about -1 dB to about -9 dB. In other measurements, the attenuation fell within the range of about -10 dB to about -19 dB. In other measurements, the attenuation fell within the range of about -20dB to about -35dB. In empirical experiments, the attenuation was substantially independent of the number of differently configured resonators proximally co-located on the tire surface. More specifically, in some experiments, the attenuation was particularly pronounced when the resonators were co-located proximally on the tire surface on the tread side of the steel belt (eg, in a steel belt radial tire).

The aforementioned coding and printing techniques can be used in tires and other elastomer-containing parts. In some cases, printing the resonator is performed at a relatively high temperature and/or under a chemical agent (eg, a catalyst) such that chemical bonds are formed between the carbon atoms of the resonator and the elastomer. The chemical bonds formed between the carbon atoms of the resonator and the elastomer contribute to the ensemble effect, therefore, the calibration curve may take into account the type and extent of the aforementioned chemical bonds.

Elastomers may contain any one or more types of rubber. Pentadiene is, for example, a common rubber formulation. Isoprene has its own C-C single and double bonds between other molecular elements in the ligand. The additional carbon double bonds formed by high temperature printing of split ring resonators have a conductivity-enhancing effect that can be exploited to form larger, lower frequency resonators. Additionally or alternatively, the agglomerate can be tuned to a specific size, which will produce overtones that contribute to the collective effect, which in turn yields very high sensitivity given EM interrogation within a certain tuning range. In some cases, the material's response to EM interrogation is sufficiently discernible that the age or other aspect of the condition of the elastomer can be determined (eg, by comparison to one or more calibration curves).

More specifically, as the elastomer ages, the molecular spacing changes and the coupling and/or percolation of energy correspondingly decreases, so the response frequency shifts as the conductive regions become more and more isolated from adjacent regions. In some cases, the attenuation and/or return signal strength will change at certain frequencies. Such changes can be determined over time and used to construct a calibration curve.

The design of the tire supports many possible locations for printing the split ring resonator. For example, a split ring resonator may be located on any interior surface of the tire, including but not limited to the cap ply, and/or on or near the steel belt (e.g., on the tread side of the steel belt), and/or On or near the radial ply, and/or on the sidewall, and/or on the chafer, and/or on the bead, etc.

The use of split ring resonator technology is not limited to tires. The technique is applicable to any elastomeric component such as belts and hoses. Furthermore, the use of split-ring resonator technology is not limited to vehicles. That is, since consumables are found in organic powertrain and/or drivetrain components in a wide range of powerplants (eg, in industrial machinery systems), split ring resonator technology can also be applied to those consumables. Some aspects of wear phenomena are the result of friction, heat, thermal cycling, and corrosion, any of which can cause and/or accelerate changes in the molecular structure of a material. Changes in the molecular structure of materials can be detected under EM interrogation. More specifically, by calculating the frequency shift, the response of a particular sample (eg, the response of an aged sample) under a particular EM interrogation regime relative to a calibration curve, the age or condition of a material can be assessed based on the magnitude of the frequency shift.

18A-18Y depict carbon-based materials, growths, agglomerates, aggregates, flakes, particles, and/or the like, such as formed from a carbon-containing gaseous species such as methane (CH ₄ ) in a reaction chamber or reactor. )) those materials that self-nucleate in operation, such as disclosed in U.S. Patent Application No. 16/785,020, filed February 7, 2020, by Stowell et al., entitled "3D Self-Assembled Multi-Modal Carbon-Based Particle" .

The illustrated carbon-based nanoparticles and aggregates can be characterized by a high degree of "uniformity" (such as desired high mass fraction of carbon allotropes), high "order" (such as low concentration of defects), and/or high "purity" (such as low concentration of elemental impurities).

Nanoparticles produced using the methods described herein can contain multi-walled spherical fullerenes (MWSF) or linked MWSF and have high uniformity (such as a graphene to MWSF ratio of 20% to 80%), high order High degree (such as a Raman signature with an _ID / _IG ratio of 0.95 to 1.05) and high purity (such as a ratio of carbon to other elements (except hydrogen) greater than 99.9%). Nanoparticles produced using the methods described herein contain MWSF or linked MWSF, and the MWSF does not contain a core composed of impurity elements other than carbon. Particles produced using the methods described herein may be aggregates comprising nanoparticles described above having larger diameters, such as greater than 10 μm.

Conventional methods have been used to produce particles containing highly ordered multi-walled spherical fullerenes, but may result in final products with various disadvantages. For example, high temperature synthesis techniques produce mixtures with many carbon allotropes and thus have low homogeneity (such as less than 20% fullerenes relative to other carbon allotropes) and/or small particle sizes (such as less than 1 μm , in some cases smaller than 100 nm) particles. Processes using catalysts can produce products that include catalyst elements and are therefore also of relatively low purity (meaning less than 95% carbon and other elements). These undesired properties also often lead to undesired electrical properties of the resulting carbon particles (such as electrical conductivity of less than 1,000 S/m).

The carbon nanoparticles and aggregates described herein can be characterized by Raman spectroscopy indicative of a high degree of order and uniformity of structure. The uniformly ordered and/or pure carbon nanoparticles and aggregates described herein can be produced using relatively high speed, low cost improved thermal reactors and methods, as described below.

As commonly understood and referred to herein, the term "graphene" means an allotrope of carbon in the form of a two-dimensional, atomic-scale, hexagonal lattice in which one atom forms each vertex. The carbon atoms in graphene are sp ² -bonded. Additionally, graphene has a Raman spectrum with two main peaks: a G-mode at about 1580 cm ⁻¹ and a D-mode at about 1350 cm ⁻¹ (when using a 532 nm excitation laser).

As commonly understood and referred to herein, the term "fullerene" means a carbon molecule in the form of a hollow sphere, spheroid, tube or other shape. Spherical fullerenes may also be called buckminsterfullerenes or buckyballs. Cylindrical fullerenes may also be referred to as carbon nanotubes. Fullerenes are structurally similar to graphite, which is made up of stacked graphene sheets linked by hexagonal rings. Fullerenes can also contain pentagonal (or sometimes heptagonal) rings.

As commonly understood and as referred to herein, the term "multi-walled fullerene" means a fullerene having multiple concentric layers. For example, multi-walled nanotubes (MWNTs) contain multiple rolled layers of graphene (concentric tubes). Multi-walled spherical fullerenes (MWSFs) contain multiple concentric fullerene spheres.

As commonly understood and as referred to herein, the term "nanoparticle" means a particle measuring from 1 nm to 989 nm. Nanoparticles may include one or more structural properties (such as crystal structure, defect concentration, etc.) and one or more types of atoms. Nanoparticles can be of any shape including, but not limited to, spherical shapes, spheroidal shapes, dumbbell shapes, cylindrical shapes, elongated cylindrical-type shapes, rectangular and/or prismatic shapes, disc shapes, wire shapes, irregular shapes, A dense shape (such as having few voids), a porous shape (such as having many voids), and the like.

As commonly understood and as referred to herein, the term "aggregate" means a plurality of nanoparticles formed by van der Waals forces, by covalent bonds, by ionic bonds, by metallic bonds, or by other physical or chemical Interacting together. Aggregate sizes can vary considerably, but are generally greater than about 500 nm.

The carbon nanoparticles may include two (2) or more linked multi-walled spherical fullerenes (MWSF) and a graphene layer coating the linked MWSF, and may be formed independently of being composed of impurity elements other than carbon core. As described herein, the carbon nanoparticles may comprise two (2) or more linked multi-walled spherical fullerenes (MWSF) and a graphene layer coating the linked MWSF. In such configurations, where the MWSF is void-free at the center (meaning a space free of carbon atoms greater than about 0.5 nm or greater than about 1 nm). Linked MWSFs can be formed from concentric, ordered spheres of ^sp hybridized carbon atoms (this contrasts favorably with conventional spheres of disordered, non-uniform, amorphous carbon particles, which otherwise might not be able to achieve the any one or more of the unexpected and advantageous properties).

The nanoparticles comprising linked MWSF have an average diameter 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 in the range of 40 to 500nm, or 40 to 250nm, or 40 to 100nm, or 50 to 500nm, or 50 to 250nm, or 50 to 100nm.

The carbon nanoparticles described herein form aggregates in which many nanoparticles come together to form larger units. The carbon aggregates may be a plurality of carbon nanoparticles. The diameter of the carbon aggregates may be in the range of 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. As defined above, aggregates may be formed from a plurality of carbon nanoparticles. Aggregates may contain linked MWSF, such as Raman signatures with high homogeneity measures (such as graphene to MWSF ratios of 20% to 80%), high degrees of order (such as _ID / _IG ratios of 0.95 to 1.05) ) and high purity (such as greater than 99.9% carbon) those linked MWSF.

Aggregates of carbon nanoparticles (mainly referring to those having diameters in the ranges described above, especially particles larger than 10 μm) are generally easier to collect than particles or particle aggregates smaller than 500 nm. Ease of collection reduces the cost of manufacturing equipment used in the production of carbon nanoparticles and increases the yield of carbon nanoparticles. Particles sized greater than 10 μm also pose fewer safety concerns than the risks of handling smaller nanoparticles, such as the potential health and safety risks posed by inhaling smaller nanoparticles. Therefore, lower health and safety risks further reduce manufacturing costs.

With reference to the carbon nanoparticles disclosed herein, the ratio of graphene to MWSF of the carbon nanoparticles may be from 10% to 90%, or from 10% to 80%, or from 10% to 60%, or from 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 graphene to MWSF ratio of the carbon aggregate 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 to linked MWSF of carbon nanoparticles 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 to linked MWSF of the carbon aggregate 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%.

Carbon allotropes can be characterized using Raman spectroscopy to distinguish their molecular structures. For example, Raman spectroscopy can be used to characterize graphene to determine information such as order/disorder, edges and grain boundaries, thickness, number of layers, doping, strain, and thermal conductivity. The MWSFs were also characterized using Raman spectroscopy to determine the degree of order of the MWSFs.

Raman spectroscopy was used to characterize the structure of the reference MWSF or connected MWSF used within various tire-related plies incorporated into tires as discussed herein. The main peaks in the Raman spectrum are G-mode and D-mode. The G-mode is due to the vibration of the carbon atoms in the sp ² -hybridized carbon network, and the D-mode is about the breathing of the hexagonal carbon rings with defects. In some cases, defects may be present but not detectable in Raman spectroscopy. For example, if the presented crystalline structure is orthogonal with respect to the basal plane, the D-peak will exhibit an increase. Alternatively, the D-peak value will be zero if the surface presents an absolutely planar surface parallel to the base plane.

When using 532 nm incident light, the Raman G-mode is typically at 1582 cm ⁻¹ for planar graphite, but can be shifted down (such as down to 1565 cm ⁻¹ or down to 1580 cm ⁻¹ ) for MWSF or connected MWSF. The D-mode is observed at about 1350 cm ⁻¹ in the Raman spectrum of MWSF or connected MWSF. The ratio of the intensity of the D-mode peak to the G-mode peak, such as I _D / _IG , is related to the degree of order of the MWSF, with a lower _ID /I _G indicating a higher degree of order. _ID / _IG near or below 1 indicates a relatively high degree of order, and _ID / _IG greater than 1.1 indicates a lower degree of order.

As described herein, carbon nanoparticles or carbon aggregates containing MWSF or linked MWSF can have and/or exhibit a Raman spectrum with a first Raman peak at about 1350 ^cm when using 532 nm incident light And the second Raman peak is at about 1580 cm ⁻¹ . The ratio of the intensity of the first Raman peak to the intensity of the second Raman peak (such as _ID / _IG ) of the nanoparticles or aggregates described herein may 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.

As defined above, the carbon aggregates containing MWSF or linked MWSF are of high purity. The carbon to metal ratio of the carbon aggregates comprising MWSF or linked MWSF 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%. Carbon aggregates having a ratio of carbon to other elements 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%. Carbon aggregates having a ratio of carbon to other elements (other than hydrogen) 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%.

As defined above, carbon aggregates comprising MWSF or linked MWSF have a high specific surface area. The Buert (BET) specific surface area of the carbon aggregate is 10 to 200m ² /g, or 10 to 100m ² /g, or 10 to 50m ² /g, or 50 to 200m ² /g, or 50 to 100m ^{2 /} g g, or 10 to 1000 m ² /g.

As defined above, carbon aggregates containing MWSF or linked MWSF have high electrical conductivity. As defined herein, carbon aggregates comprising MWSF or linked MWSF are compressed into agglomerates and the agglomerates have an electrical conductivity 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 4,000S/m, or greater than 5,000S/m, or greater than 10,000S/m, or greater than 20,000S/m, or greater than 30,000S/m, or greater than 40,000S/m, or greater than 50,000S/m, Or greater than 60,000S/m, or greater than 70,000S/m, or 500S/m to 100,000S/m, or 500S/m to 1,000S/m, or 500S/m to 10,000S/m, or 500S/m to 20,000 S/m, or 500S/m to 100,000S/m, or 1000S/m to 10,000S/m, or 1,000S/m to 20,000S/m, or 10,000 to 100,000S/m, or 10,000S/m to 80,000 S/m, or 500S/m to 10,000S/m. In some cases, the aggregated particles have a density of about 1 g/cm ³ , or about 1.2 g/cm ³ , or about 1.5 g/cm ³ , or about 2 g/cm ³ , or about 2.2 g/cm ³ , or about 2.5 g/cm ³ , or about 3 g/cm ³ . Additionally, tests have been performed in which compressed agglomerates of carbon aggregate material have been formed at compressions of 2,000 psi and 12,000 psi and annealing temperatures of 800°C and 1,000°C. Higher compression and/or higher annealing temperatures generally produced aggregated grains with higher electrical conductivity (comprising in the range of 12,410.0 S/m to 13,173.3 S/m).

The carbon nanoparticles and aggregates described herein can be produced using thermal reactors and methods. Additional details regarding thermal reactors and/or methods of use can be found in U.S. Patent No. 9,862,602, entitled "CRACKING OF A PROCESSGAS," issued January 9, 2018, which is hereby incorporated by reference in its entirety . Additionally, carbon-containing and/or hydrocarbon precursors (referring to at least methane, ethane, propane, butane, and natural gas) can be used with the thermal reactor to produce the carbon nanoparticles and carbon aggregates described herein.

The carbon nanoparticles and aggregates described herein are produced using a thermal reactor at 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 use a thermal reactor at 0.1 second (s) to 30 seconds, or 0.1 second to 10 seconds, or 1 second to 10 seconds, or 1 second to 5 seconds, 5 seconds to 10 seconds second, or greater than 0.1 second, or greater than 1 second, or greater than 5 seconds, or less than 30 seconds of gas resonance time generation.

The carbon nanoparticles and aggregates described herein can be produced at 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 using a thermal reactor. 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 production rate.

Thermal reactors (or other cracking equipment) and thermal reactor processes (or other cracking methods) can be used to refine, pyrolyze, dissociate, or crack feedstock process gases into their components to produce the carbon nanoparticles and carbon nanoparticles described herein. aggregates and other solid and/or gaseous products (such as hydrogen and/or lower hydrocarbon gases). Raw process gases typically include, for example, hydrogen (H ² ), carbon dioxide (CO ² ), C ¹ to C ¹⁰ hydrocarbons, aromatic hydrocarbons, and/or other hydrocarbon gases such as natural gas, methane, ethane, propane, butane, Isobutane, saturated/unsaturated hydrocarbon gases, ethylene, propylene, etc., and mixtures thereof. Carbon nanoparticles and carbon aggregates can include, for example, multi-walled spherical fullerenes (MWSF), linked MWSF, 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.

Methods for producing the carbon nanoparticles and carbon aggregates described herein may include thermal cracking processes using, for example, fine carbon dioxide, optionally enclosed within an elongated housing, housing, or body of a thermal cracking apparatus. Long longitudinal heating elements. The body may comprise one or more tubes or other suitable enclosures, eg made of stainless steel, titanium, graphite, quartz or the like. The body of the thermal cracking apparatus is generally cylindrical in shape with a central elongated longitudinal axis disposed vertically and a raw process gas inlet at or near the top of said body. Raw process gas may flow longitudinally downward through the body or portions thereof. In a vertical configuration, both air flow and gravity facilitate the removal of solid products from the body of the thermal cracking apparatus.

The heating element may comprise any one of a heat lamp, one or more resistive wires or filaments (or stranded wire), metal filaments, metal strips or rods, and/or other suitable thermal radical generators or elements or Alternatively, the thermal radical generator or element may be heated to a specific temperature sufficient to thermally crack molecules of the feedstock process gas, such as a molecular cracking temperature. The heating element may be positioned, positioned or arranged to extend centrally within the body of the pyrolysis apparatus along the central longitudinal axis of the pyrolysis apparatus. In configurations with only one heating element, the heating element can be placed at or concentrically with the central longitudinal axis; alternatively, for configurations with multiple heating elements, the heating element can be positioned at Spaced or offset generally symmetrically or concentrically about and around the central longitudinal axis and parallel to the central longitudinal axis.

The thermal cracking used to produce the carbon nanoparticles and aggregates described herein can be accomplished by flowing a feedstock process gas over or in contact with or in the vicinity of a heating element within a longitudinally elongated reaction zone , the longitudinally elongated reaction zone is generated by heat from a heating element and is defined by and housed inside the body of the thermal cracking plant to heat the raw process gas to a specific molecular cracking temperature or at a specific molecular at the cracking temperature.

The reaction zone can be considered as a region that surrounds the heating element and is close enough to the heating element that the feedstock process gas receives sufficient heat to thermally crack its molecules. The reaction zone is thus generally axially aligned or concentric with the central longitudinal axis of the body. Pyrolysis is carried out under specific pressure. The raw process gas is circulated around or across the outer surfaces of the vessel or heated chamber of the reaction zone to cool the vessel or chamber and to preheat the raw process gas before it flows into the reaction zone.

The carbon nanoparticles and aggregates and/or hydrogen gas described herein are produced without the use of catalysts. Thus, the process can be completely catalyst-free.

The disclosed methods and systems can advantageously be rapidly scaled up or scaled down for different production levels as needed, such as being scalable to provide stand-alone hydrogen and/or carbon nanoparticle production stations, hydrocarbon sources or fuel cell stations, To provide higher capacity systems such as for refineries and/or the like.

A thermal cracking apparatus for cracking a feedstock process gas to produce the carbon nanoparticles and aggregates described herein includes a main body, a feedstock process gas inlet, and an elongated heating element. The interior volume of the body has a longitudinal axis. The interior volume has a reaction zone concentric with the longitudinal axis. Raw process gas may flow into the interior volume via the raw process gas inlet during thermal cracking operations. An elongated heating element may be disposed within the interior volume along the longitudinal axis and surrounded by the reaction zone. During thermal cracking operations, the elongated heating element is heated by electrical energy to a molecular cracking temperature to create a reaction zone, heat from the elongated heating element is used to heat the feedstock process gas, and the heat converts the feedstock process gas in the reaction zone to Thermal cracking of molecules into their constituents.

A method for cracking a feedstock process gas to produce the carbon nanoparticles and aggregates described herein may include at least any one or more of: (1) providing a thermal cracking apparatus having an internal volume that having a longitudinal axis and an elongate heating element disposed within said interior volume along said longitudinal axis; (2) heating the elongate heating element by electrical energy to a molecular cracking temperature to create a longitudinally elongate reaction zone within the interior volume; (3) flowing the raw process gas into the interior volume and through a longitudinally elongated reaction zone (such as where the raw process gas is heated by heat from an elongated heating element); The elongated reaction zone thermally cracks molecules of the feed process gas within the longitudinally elongated reaction zone into its components such as hydrogen and one or more solid products.

The feedstock process gas used to produce the carbon nanoparticles and aggregates described herein can include hydrocarbon gases. The results of the cracking may in turn also include hydrogen in gaseous form, such as H ² , and various forms of the carbon nanoparticles and aggregates described herein. Carbon nanoparticles and aggregates include two or more MWSFs and MWSF-coated graphene layers, and/or linked MWSFs and linked MWSF-coated graphene layers. Preheat the raw process gas (such as preheating to 100°C to 500°C) by letting the raw process gas flow through the gas preheating zone between the heating chamber and the shell of the thermal cracking equipment, and then let the raw process gas flow into the interior volume. A gas with nanoparticles therein flows into the interior volume and through the longitudinally elongated reaction zone to mix with the feedstock process gas to form a coating of solid product, such as a graphene layer, around the nanoparticles.

The multi-walled spherical fullerene (MWSF) or linked MWSF-containing carbon nanoparticles and aggregates described herein can be produced and collected without the need to perform any post-processing treatments or manipulations. Alternatively, some post-processing may be performed on one or more of the presently disclosed MWSFs. Some examples of post-processing involved in the manufacture and use of resonant materials include mechanical treatments such as ball milling, grinding, sanding, microfluidization, and other techniques to reduce particle size without damaging the MWSF. Some other examples of post-processing include exfoliation processes (referring to the complete separation of carbonaceous material layers, such as the generation or extraction of graphene layers from graphite, etc.), including shear mixing, chemical etching, oxidation (such as the Hummer method), thermal annealing , doping by adding elements such as sulfur and/or nitrogen during annealing, vaporization, filtration and lyophilization, and other processes. 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 under high pressure and temperature in an inert gas. Multiple post-processing methods can be used together or in succession. Post-processing yields functionalized carbon nanoparticles or aggregates containing multi-walled spherical fullerenes (MWSF) or linked MWSF.

The materials can be mixed together in different combinations, amounts and/or ratios. The different carbon nanoparticles and aggregates described herein containing MWSF or linked MWSF can be mixed together prior to one or more post-processing operations, if present. For example, different carbon nanoparticles and aggregates containing MWSF or linked MWSF of different properties (such as different sizes, different compositions, different purities, from different processing batches, etc.) can be mixed together. The carbon nanoparticles and aggregates containing MWSF or linked MWSF described herein can be mixed with graphene to vary the ratio of linked MWSF to graphene in the mixture. The different carbon nanoparticles and aggregates described herein containing MWSF or linked MWSF can be mixed together after post-processing. Different carbon nanoparticles and aggregates with different properties and/or different post-treatment methods (such as different sizes, different compositions, different functionalities, different surface properties, different surface areas) can be in any number, ratio and/or mix together.

The carbon nanoparticles and aggregates described herein are generated and collected, and subsequently processed by mechanical grinding, milling, and/or exfoliation. Treatment (such as by mechanical grinding, milling, exfoliation, etc.) can reduce the average size of the particles. Treatment (such as by mechanical grinding, milling, exfoliation, etc.) can increase the average surface area of the particles. Processing by mechanical grinding, grinding and/or exfoliation shears away portions of the carbon layer, resulting in graphite flakes mixed with carbon nanoparticles.

Mechanical grinding or grinding is the use of ball mills, planetary mills, rod mills, shear mixers, high shear granulators, autogenous mills or to break down solid materials into smaller parts by grinding, crushing or cutting. Other types of machining of small pieces are performed. Mechanical grinding, lapping and/or stripping are performed wet or dry. Mechanical grinding is performed by grinding for a period of time, followed by a period of idle time, and repeating the grinding and idle period for several cycles. The grinding period is 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 idle period is 1 min to 10 min, or about 5 min, or about 6 min. The several grinding and idle cycles are 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 amount of grinding and idle time is 10 min to 1,200 min, or 10 min to 600 min, or 10 min to 240 min, or 10 min to 120 min, or 100 min to 90 min, or 10 min to 60 min, or about 90 min, or about several minutes.

The grinding step in the cycle is performed by rotating the grinder in one direction, such as clockwise, for a first cycle and then rotating the grinder in the opposite direction, such as counterclockwise, for the next cycle. Mechanical grinding or milling is performed using a ball mill, and the grinding step is performed using a rotational speed of 100 to 1000 rpm, or 100 to 500 rpm, or about 400 rpm. Mechanical grinding or milling is performed using a ball mill using grinding media with 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 grinding or milling is performed using a ball mill using metals such as steel, oxides such as zirconia (zirconia), yttria stabilized zirconia, silica, alumina, magnesia, or Grinding media of other hard materials such as silicon carbide or tungsten carbide.

The carbon nanoparticles and aggregates described herein are produced and collected, and subsequently processed using high temperatures such as thermal annealing or sintering. Treatments using elevated temperatures are performed in an inert atmosphere such as nitrogen or argon. Treatments using elevated temperatures are carried out at atmospheric pressure or under vacuum or under reduced pressure. The treatment using high temperature is at 500°C to 2,500°C, or 500°C to 1,500°C, or 800°C to 1,500°C, or 800°C to 1,200°C, or 800°C to 1,000°C, or 2,000°C to 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.

The carbon nanoparticles and aggregates described herein are produced and collected, and then in post-processing operations, additional elements or compounds are added to the carbon nanoparticles, thereby combining the unique properties of the carbon nanoparticles and aggregates in other in the material mixture.

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

The carbon nanoparticles and aggregates described herein are used in a variety of applications beyond those pertaining to making and using resonant materials, either before or after post-processing. Such applications include, but are not limited to, transportation applications (such as automobile and truck tires, couplings, mounts, elastomeric "o-rings", hoses, sealants, grommets, etc.) functional additives for materials, additives for epoxy resins, etc.).

18A and 18B show transmission electron microscope (TEM) images of carbon nanoparticles during synthesis. The carbon nanoparticles of Figure 18A (at a first magnification) and Figure 18B (at a second magnification) contain linked multi-walled spherical fullerenes (MWSF), where a graphene layer coats the linked MWSF. In this example, the ratio of MWSF to graphene allotrope is about 80% due to the relatively short resonance time. The diameter of the MWSF in FIG. 18B is approximately 5 nm to 10 nm, and using the conditions described above, the diameter may be 5 nm to 500 nm. MWSF has an average diameter of 5nm to 500nm, or 5nm to 250nm, or 5nm to 100nm, or 5nm to 50nm, or 10nm to 500nm, or 10nm to 250nm, or 10nm to 100nm, or 10nm to 50nm, or 40nm to 500nm, or 40nm to 250nm, or 40nm to 100nm, or 50nm to 500nm, or 50nm to 250nm, or 50nm to 100nm. No catalyst is used in this process, so there is no central seed containing contaminants. The aggregate particles produced in this example have a particle size of about 10 μm to 100 μm, or about 10 μm to 500 μm.

Figure 18C shows the Raman spectrum obtained for the as-synthesized aggregates in this example with incident light at 532 nm. The _ID / _IG of the aggregates produced in this example was about 0.99 to 1.03, indicating that the aggregates were composed of carbon allotropes with a high degree of order.

18D and 18E show example TEM images of carbon nanoparticles after size reduction by grinding in a ball mill. The ball milling was performed cyclically, with a 3 minute (min) counterclockwise grinding operation, followed by a 6 minute idle operation, followed by a 3 minute clockwise grinding operation, followed by a 6 minute idle operation. The grinding operation was performed using a rotational speed of 400 rpm. The grinding media was zirconia and ranged in size from 0.1mm to 10mm. The total size reduction process time was 60 min to 120 min. After size reduction, the aggregate particles produced in this example had a particle size of about 1 μm to 5 μm. The size-reduced carbon nanoparticles are linked MWSF, where the graphene layer coats the linked MWSF.

Figure 18F shows Raman spectra obtained from these aggregates after size reduction with 532 nm incident light. The _ID /I _G of the aggregate particles in this example after size reduction is about 1.04. In addition, the particles after size reduction have a Buert (BET) specific surface area of about 40 to ⁵⁰ m ² /g.

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

In this example, carbon nanoparticles are produced using a hot wire processing system using heat. The precursor material was methane, which was flowed at a flow rate of 1 slm to 5 slm. With these flow rates and tool geometries, the resonance time of the gas in the reaction chamber was about 20 to 30 seconds, and the carbon particle generation rate was about 20 g/hr.

Additional details regarding this processing system can be found in the previously mentioned US Patent 9,862,602 entitled "CRACKING OF APROCESS GAS".

Example 1

18G (shown enlarged according to FIG. 15 ), FIG. 18H (shown enlarged according to FIG. 16 ) and FIG. 18I (shown enlarged according to FIG. 17 ) show TEM images of carbon nanoparticles during synthesis of this example. The carbon nanoparticles contain linked multi-walled spherical fullerenes (MWSF) with graphene layers coating the linked MWSF. The ratio of multi-walled fullerenes to graphene allotropes in this example is about 30%, since the relatively long resonance time allows thicker or more graphene layers to coat the MWSF. No catalyst is used in this process, so there is no central seed containing contaminants. The as-synthesized aggregate particles produced in this example had a particle size of approximately 10 μm to 500 μm. - Figure 18J shows the Raman spectrum of aggregates from this example. The Raman signature of the as-synthesized particles in this example indicates a thicker graphene layer coating the MWSF in the as-synthesized material. In addition, the particles as synthesized have a Buert (BET) specific surface area of about 90 m ² /g to 100 m ² /g. -

Example 2

18K and 18L show TEM images of the carbon nanoparticles of this example. In particular, the image depicts carbon nanoparticles after size reduction by grinding in a ball mill. The size reduction process conditions are the same as those described above with respect to FIGS. 18G-18J . After size reduction, the aggregate particles produced in this example had a particle size of about 1 μm to 5 μm. TEM images show that connected MWSFs embedded in the graphene coating can be observed after size reduction. Figure 18M shows the Raman spectrum obtained for aggregates of this example after size reduction with 532 nm incident light. After size reduction, the _ID / _IG of aggregated particles in this example is around 1, indicating that linked MWSFs embedded in the as-synthesized graphene coating become detectable in Raman after size reduction , and very well organized. The particles after size reduction have a Buert (BET) specific surface area of about 90 to ¹⁰⁰ m ² /g.

Example 3

18N is a scanning electron microscope (SEM) image showing carbon aggregates of graphite and graphene allotropes at a first magnification. Figure 18O is a SEM image showing carbon aggregates of graphite and graphene allotropes at a second magnification. Layered graphene is clearly shown within deformations (wrinkles) of the carbon. The 3D structure of the carbon allotrope is also visible.

The particle size distributions of the carbon particles of Figures 18N and 18O are shown in Figure 18P. Mass basis cumulative particle size distribution 1806 corresponds to the left y-axis ( ^Q3 (x)[%]) of the graph. The histogram of the mass particle size distribution 1808 corresponds to the right axis (dQ ³ (x)[%]) in the graph. The median particle size is about 33 μm. The 10th percentile particle size is about 9 μm, and the 90th percentile particle size is about 103 μm. The mass density of the particles is about 10g/L.

Example 4

The particle size distribution of carbon particles captured from the multistage reactor is shown in Figure 18Q. Mass basis cumulative particle size distribution 1814 corresponds to the left y-axis ( ^Q3 (x)[%]) of the graph. The histogram of mass particle size distribution 1816 corresponds to the right axis (dQ ³ (x)[%]) in the graph. The median particle size captured was about 11 μm. The 10th percentile particle size is about 3.5 μm, and the 90th percentile particle size is about 21 μm. The graph in FIG. 18Q also shows the number-based cumulative particle size distribution 1818 corresponding to the left y-axis (Q ⁰ (x)[%]) of the graph. The median particle size on a number basis is from about 0.1 μm to about 0.2 μm.

Returning to the discussion of Figure 18P, the graph also shows a second set of example results. Specifically, in this example, the particles were reduced in size by mechanical grinding, and the size-reduced particles were then processed using a cyclone. The mass-based cumulative particle size distribution 410 of the trapped size-reduced carbon particles in this example corresponds to the left y-axis ( ^Q3 (x)[%]) of the graph. The histogram of the mass reference particle size distribution 412 corresponds to the right axis (dQ ³ (x)[%]) in the graph. The median diameter of the trapped size-reduced carbon particles in this example was about 6 μm. The 10th percentile particle size is 1 μm to 2 μm, and the 90th percentile particle size is 10 μm to 20 μm.

Additional details regarding the manufacture and use of cyclone separators can be found in U.S. Patent Application 15/725,928, entitled "MICROWAVE REACTOR SYSTEM WITH GAS-SOLIDS SEPARATION," filed October 5, 2017, which is hereby incorporated by reference in its entirety incorporated.

In some cases, microwave plasma reactor systems can be used to produce graphite, graphene, and amorphous Carbon particles and aggregates of carbon. In some other examples, the carbon-containing precursor is optionally mixed with a supply gas such as argon. The particles produced in this example contain graphite, graphene, amorphous carbon, and no seed particles. The particles in this example have a ratio of carbon to other elements (other than hydrogen) of about 99.5% or greater.

In one particular example, hydrocarbons are the input material to a microwave plasma reactor, and the separated output of the reactor contains hydrogen gas and carbon particles including graphite, graphene, and amorphous carbon. Carbon particles are separated from hydrogen in a multi-stage gas-solid separation system. The separated output from the reactor had a solids content of 0.001 g/L to 2.5 g/L.

Example 5

18R, 18S, and 18T are TEM images of carbon nanoparticles during synthesis. The images show examples of graphite, graphene, and amorphous carbon allotropes. Layers of graphene and other carbon materials are clearly visible in the image.

The particle size distribution of the trapped carbon particles is shown in Figure 18U. Mass basis cumulative particle size distribution 1820 corresponds to the left y-axis ( ^Q3 (x)[%]) of the graph. The histogram of the mass particle size distribution 1822 corresponds to the right axis (dQ ³ (x)[%]) in the graph. The median particle size captured in the cyclone in this example is about 14 μm. The 10th percentile particle size is about 5 μm, and the 90th percentile particle size is about 28 μm. The graph in FIG. 18U also shows the number-based cumulative particle size distribution 424 corresponding to the left y-axis (Q ⁰ (x)[%]) of the graph. The median particle size on a number basis in this example is from about 0.1 μm to about 0.2 μm.

18V, 18W and 18X and 18X are images showing three-dimensional carbonaceous structures grown onto other three-dimensional structures. Figure 18V is a 100X magnification of a three-dimensional carbon structure grown on carbon fibers, and Figure 18W is a 200X magnification of a three-dimensional carbon structure grown on carbon fibers. Figure 18X is a 1601X magnification of a three-dimensional carbon structure grown onto carbon fibers. Three-dimensional carbon growth over the fiber surface is shown. Figure 18Y is a 10,000X magnification of a three-dimensional carbon structure grown onto carbon fibers. Images depict growth on basal as well as marginal planes.

More specifically, FIGS. 18V-18Y show example SEM images of 3D carbon materials grown onto fibers using plasma energy from a microwave plasma reactor and thermal energy from a thermal reactor. Figure 18V shows a SEM image of intersecting fiber 1831 and fiber 1832 with 3D carbon material 1830 grown on the fiber surface. FIG. 18W is a higher magnification image showing 3D carbon material 1830 on fibers 1832 (scale bar is 300 μm, as opposed to 500 μm in FIG. 18V ). FIG. 18X is another enlarged view (scale bar is 40 μm) showing the 3D carbon material 1830 on the fiber surface 1835, where the 3D nature of the 3D carbon material 1830 can be clearly seen. Figure 18Y shows only a close-up view of the carbon (scale bar is 500nm), showing the interconnection between the basal plane of the fiber 1832 and the multiple sub-particle edge planes 1834 of the 3D carbon material grown on the fiber. 18V-18Y illustrate the ability to grow 3D carbon on 3D fiber structures, such as 3D carbon growth grown on 3D carbon fibers.

3D carbon growth on fibers can be achieved by introducing a plurality of fibers into a microwave plasma reactor and using plasma to etch the fibers in the microwave reactor. Etching creates nucleation sites at which the growth of the 3D carbon structure begins when carbon particles and daughter particles are produced by dissociation of the hydrocarbon in the reactor. The 3D carbon structure in itself provides a highly integrated 3D structure with pores into which the resin is permeable for direct growth on fibers in three dimensions. This 3D-reinforced matrix for resin composites, comprising a 3D carbon structure integrated with high-aspect-ratio reinforcing fibers, yields enhanced material properties, such as tensile strength and shear, compared to composites with conventional fibers, the Conventional fibers have a smooth surface, and the smooth surface is usually layered with a resin matrix.

A carbon material, such as any one or more of the 3D carbon materials described herein, can have one or more exposed surfaces that provide for functionalization, such as promoting adhesion and / or adding elements such as oxygen, nitrogen, carbon, silicon or hardeners. Functionalization refers to the addition of functional groups to compounds by chemical synthesis. In materials science, functionalization can be employed to achieve desired surface properties; for example, functional groups can also be used to covalently attach functional molecules to the surface of chemical devices. The carbon material can be functionalized in situ, that is, in situ within the same reactor in which the carbon material was produced. Carbon materials can be functionalized in post-processing. For example, the surface of fullerene or graphene can be functionalized with oxygen- or nitrogen-containing species that form bonds with the polymers of the resin matrix, thus improving adhesion and providing a strong bond to enhance the strength of the composite.

Any of the disclosed carbon-based materials (such as CNT, CNO, graphene, 3D carbon materials such as 3D graphene) or Most of them carry out functionalized surface treatment. Such treatments may include in-situ surface treatments during the generation of carbon materials, which may be combined with binders or polymers in composite materials; or after carbon material generation while the carbon materials are still within the reactor. surface treatment.

Some of the foregoing embodiments include a resonator comprising a plurality of three-dimensional (3D) aggregates formed of carbonaceous material embedded within one or more carcass plies of a tire. However, some embodiments include resonators that are printed or otherwise disposed on the inner surface of the tire (eg, on the innerliner of the tire). In the foregoing specification, the disclosure has been described with reference to specific implementations of the disclosure. It will, however, be evident that various modifications and changes can be made thereto without departing from the broader spirit and scope of the disclosure. For example, the program flow described above is described with reference to the ordering of program actions. However, the ordering of many of the described program actions may be changed without affecting the scope or operation of the present disclosure. The specification and drawings are to be regarded in an illustrative rather than a restrictive sense.

Claims (22)

CLAIMS 1. A system configured to detect tire strain in a vehicle, the system comprising: an antenna disposed on or in the vehicle and configured to emit electromagnetic acoustic pulses; and A tire comprising a body formed from one or more tire plies, at least one of which includes a plurality of split ring resonators (SRRs) having A natural resonant frequency in response to changes in the elastomeric properties of a tire ply, including one or more of reversible deformation, stress, or strain. 2. The system of claim 1, wherein the plurality of SRRs further comprises a first SRR comprising a plurality of first carbon particles configured to be based at least in part on the The concentration level of the first carbon particles within the first SRR is uniquely resonant in response to the electromagnetic acoustic pulse. 3. The system of claim 2, wherein the plurality of SRRs further comprises a second SRR adjacent to the first SRR and comprising a second plurality of carbon particles, the second carbon Particles are configured to uniquely resonate in response to the electromagnetic acoustic pulse based at least in part on a concentration level of the second carbon particles within the second SRR. 4. The system of claim 3, wherein the first carbon particles comprise first aggregates forming a first porous structure, and the second carbon particles comprise second aggregates forming a second porous structure . 5. The system of claim 4, wherein the first porous structure and the second porous structure comprise mesoscale structures. 6. The system of claim 3, wherein each of the first SRR and the second SRR includes a three-dimensional (3D) layer printed onto a surface of the tire ply. 7. The system of claim 3, wherein the first SRR is configured to resonate at a first frequency in response to the electromagnetic acoustic pulses, and the second SRR is configured to resonate in response to the electromagnetic acoustic pulses. pulses to resonate at a second frequency, the first frequency being different from the second frequency. 8. The system of claim 7, wherein each of the first frequency and the second frequency is associated with an encoded serial number. 9. The system of claim 7, wherein a resonant amplitude of the first SRR or the second SRR is indicative of a degree of wear of the tire ply. 10. The system of claim 3, wherein an amount or magnitude of a change in the natural resonant frequency of the SRR caused by the electromagnetic acoustic pulse is indicative of an amount of deformation of the tire ply. 11. The system of claim 3, wherein each of the first SRR and the second SRR has a decay point. 12. The system of claim 11, wherein the decay point of each of the first SRR and the second SRR is associated with a frequency response to the electromagnetic acoustic pulse. 13. The system of claim 3, wherein each of the first carbon particles and the second carbon particles are chemically bonded to the tire ply. 14. The system of claim 3, wherein each of the first SRR and the second SRR has a value associated with one or more of an S-parameter or a frequency of the electromagnetic acoustic pulse. Main dimensions. 15. The system of claim 3, wherein at least one of the first SRR or the second SRR has an oval shape, an elliptical shape, a rectangular shape, a square shape, a circular shape, or a curved shape. one. 16. The tire of claim 3, wherein one or more of the first SRR or the second SRR comprises a cylindrical SRR. 17. The tire of claim 3, wherein said first SRR is located outside said second SRR. 18. The system of claim 3, wherein the first SRR and the second SRR are disposed within an innerliner of the tire. 19. The tire of claim 3, further comprising a tread side, one or more of the plurality of SRRs disposed adjacent to the tread side. 20. The system of claim 3, wherein each of the first SRR and the second SRR has a negative effective permeability. 21. The system of claim 3, wherein each of the first SRR and the second SRR comprises one or more of a conductive material, a metal, a conductive non-metal, a dielectric material, or a semiconductor material By. 22. The system of claim 3, wherein the first SRR and the second SRR are configured as a pair of concentric rings.

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