Reinforced carbon-containing glass material and method for manufacturing the same

Abstract

In some embodiments, a carbon-containing glass material includes a surface / air interface and an interphase region extending from the surface / air interface to a depth within the carbon-containing glass material along a direction. The surface / air interface can be exposed to ambient air, and the interphase region can include a plurality of few-layer graphene (FLG) nanoplatelets formed in response to recombination and / or self-nucleation of a plurality of carbon-containing radicals injected into the interphase region. The FLG nanoplatelets have a non-periodic orientation configured to at least partially suppress the formation or propagation of microcracks and / or microvoids in the carbon-containing glass material. The glass material can also include a compressive stress layer disposed between the interphase region and the surface / air interface of the carbon-containing glass material, the compressive stress layer being induced by ion bombardment of the carbon-containing glass material by a plurality of ionized inert gas particles.

Description

Technical Field

[0001] The present disclosure relates generally to glass materials, and specifically to producing, strengthening, and / or reinforcing glass materials with few-layer graphene (FLG) nanoplatelets dispersed throughout one or more portions of the glass material.

Background Art

[0002] Glass is an amorphous solid material that can be used in various fields including, for example, windows, digital screen displays, optical instruments, and pharmaceutical storage containers. Glass may include silicon dioxide (SiO2), also called silica, as a main constituent material. Generally, glass can be formed by heating a mixture of dry particulate silicon dioxide with other solid raw materials until the mixture reaches a softened semi-solid state, then rapidly cooling the mixture to prevent the mixture from forming a crystalline structure. Glass is relatively brittle compared to other solid materials and may be more prone to scratching, cracking, and / or breaking than other solid materials. Accordingly, there is a need for glasses and glass materials that are stronger, more resistant to breakage, and less susceptible to cracking than conventional glasses and glass materials.

Summary of the Invention

[0003] The systems, methods, and devices of the present disclosure each have several innovative aspects, and no single one of them alone serves to provide all the desirable characteristics disclosed herein.

[0004] One innovative aspect of the subject matter described herein can be implemented as a manufacturing method. In various embodiments, the method can be used to manufacture, strengthen, and / or reinforce carbon-containing glass materials. In some embodiments, the method may involve introducing hydrocarbon gases and silanes into a reactor. The method may involve providing the reactor with an additive comprising any one or more of lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), or sulfur. The method may involve generating a non-thermal equilibrium plasma based on the excitation of hydrocarbon gases and silanes by microwave energy, the non-thermal equilibrium plasma comprising multiple methyl radicals. The method may involve subjecting the surface / air contact surface of the carbon-containing glass material to ionic bombardment by at least methyl radicals, the ionic bombardment configured to create interphase regions in the carbon-containing glass material. The method may involve forming multiple multi-layer graphene (FLG) nanoplatelets within the interphase regions of the carbon-containing glass material at various concentration levels based on the recombination or autonucleation of multiple methyl radicals. Multiple FLG nanoplatelets can be dispersed throughout the interphase region in a non-periodic orientation that can at least partially suppress the formation or propagation of cracks and / or surface defects in the carbon-containing glass material. The method may include doping one or more surfaces of at least some of the FLG nanoplatelets formed in the interphase region with an additive. The method may also include intercalating the additive between adjacent graphene layers inside at least some of the FLG nanoplatelets formed within the interphase region of the carbon-containing glass material.

[0005] In various embodiments, the carbon-containing glass material may comprise any one or more of silicate glass, soda-lime glass, alkali aluminosilicate glass, or borosilicate glass. In some embodiments, the alkali aluminosilicate glass consists of about 57% to 60% SiO2, about 10% to 25% Al2O3, and about 10% alkaline earth metal. Silane may be a silane-containing liquid precursor or silane gas. In one embodiment, the FLG nanoplatelets formed in the interphase region have a total weight of less than 2% of the carbon-containing glass material. In some cases, additives may comprise alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, additives may comprise lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof.

[0006] The interphase region may extend from the surface / air contact surface of the carbon-containing glass material to a depth of approximately 1 micron within the carbon-containing glass material. In some embodiments, the upper part of the interphase region adjacent to the surface / air contact surface has a relatively high concentration of FLG nanoplatelets, while the lower part of the interphase region distal to the surface / air contact surface has a relatively low concentration of FLG nanoplatelets. In some embodiments, the FLG nanoplatelets in the upper part of the interphase region have a size of approximately 20 nanometers (nm), and the FLG nanoplatelets in the lower part of the interphase region have a size of approximately 2 nm. In some embodiments, the FLG nanoplatelets in the gradient portion of the interphase region located between the upper and lower parts of the interphase region gradually decrease in size along the direction toward the depth of the interphase region. In some embodiments, the FLG nanoplatelets in the lower part of the interphase region are uniformly distributed across the entire plane of the lower part of the interphase region. In addition, or alternatively, the density of multiple FLG nanoplatelets may gradually decrease along the direction extending from the surface / air contact surface to the depth of the interphase region.

[0007] In various embodiments, the additive may be configured to self-repair cracks formed in the carbon-containing glass material when the additive is exposed to ambient air. For example, the additive may oxidize when exposed to reactants present in the ambient air (such as gaseous oxygen, O2, and / or moisture (H2O)), and the resulting oxidized additive can spread to cracks and / or surface defects formed in the carbon-containing glass material. In some embodiments, the oxidized additive may also coat the surface of cracks and / or surface defects formed in the carbon-containing glass material. In some cases, it may be intercalated between adjacent graphene layers of the FLG nanoplatelets during post-processing operations. Post-processing operations may include constant temperature treatment in a vacuum or an inert atmosphere.

[0008] Another innovative aspect of the subject matter described herein can be implemented as a manufacturing method. In various embodiments, the method can be used to manufacture, strengthen, and / or reinforce carbon-containing glass materials. In some embodiments, the method may include supplying a non-thermal equilibrium plasma containing a plurality of positively charged gas particles and a plurality of ionized inert gas particles to a reaction chamber. The method may include accelerating at least a plurality of positively charged gas particles through the reaction chamber based on the application of an external potential to the non-thermal equilibrium plasma. The method may include impacting the surface / air contact surface of the carbon-containing glass material with the accelerated positively charged gas particles and ionized inert gas particles. The method may include forming an interphase region in the carbon-containing glass material in response to the impact with the accelerated positively charged gas particles and ionized inert gas particles. The interphase region, which may extend from the surface / air contact surface to a depth of about 1 micron in the carbon-containing glass material along a direction perpendicular to the surface / air contact surface, may have a plurality of microcracks or microvoids formed inside by the impact. In some cases, microcracks or microvoids may have a size of approximately 5 nanometers (nm) to 10 nm. The method may include forming a compressive stress layer in a carbon-containing glass material in response to impact by at least ionized inert gas particles. The compressive stress layer may be located between the interphase region of the carbon-containing glass material and the surface / air contact surface. The carbon-containing glass material may include silicate glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, or any combination thereof. In one embodiment, the alkali aluminosilicate glass consists of approximately 57% to 60% SiO2, approximately 10% to 25% Al2O3, and approximately 10% alkaline earth metal.

[0009] In some cases, a non-thermal equilibrium plasma may contain an intrinsic potential. In some embodiments, the intrinsic potential of a non-thermal equilibrium plasma may be sufficient for at least some positively charged gas particles and / or ionized inert gas particles to penetrate the surface / air contact surface of a glass material without an external potential being applied to the reaction chamber.

[0010] The method may also include impacting the surface / air contact surface with accelerated positively charged gas particles and ionized inert gas particles, while simultaneously injecting multiple carbon-based radicals separated from a non-thermal equilibrium plasma into the interphase region of a carbon-containing glass material. The method may also include forming multiple multi-layer graphene (FLG) nanoplatelets within the interphase region of the carbon-containing glass material based on the recombination and / or self-nucleation of the multiple injected carbon-based radicals. The carbon-based radicals can be injected into the interphase region at one or more different incidence angles. In some embodiments, the upper part of the interphase region adjacent to the surface / air contact surface may have a relatively high concentration of FLG nanoplatelets, while the lower part of the interphase region distal to the surface / air contact surface may have a relatively low concentration of FLG nanoplatelets. In addition, the FLG nanoplatelets in the upper part of the interphase region may have a size of approximately 20 nanometers (nm), while the FLG nanoplatelets in the lower part of the interphase region may have a size of approximately 2 nm. In one embodiment, FLG nanoplatelets formed in the sloping portion of the interphase region, located between the upper and lower parts of the interphase region, gradually decrease in size along the direction toward the depth of the interphase region. In some embodiments, the FLG nanoplatelets in the lower part of the interphase region may be uniformly distributed across the entire plane of the lower part of the interphase region.

[0011] In some embodiments, the method may also include intercalating additives between adjacent graphene layers within FLG nanoplatelets formed in the interphase region. In some cases, the additives may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additives may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof. In one embodiment, a first portion of the additive intercalated in the FLG nanoplatelets formed in the upper part of the interphase region has a mole fraction of about 50%, and a second portion of the additive intercalated in the FLG nanoplatelets formed in the lower part of the interphase region has a mole fraction of about 2%. Other portions of the additive injected into the area of ​​the interphase region between the upper and lower parts may have a mole fraction that gradually decreases along the direction toward the depth of the interphase region.

[0012] The additive may be configured to self-repair cracks formed in the carbon-containing glass material when exposed to reactants present in the ambient air (such as gaseous oxygen, O2, and / or moisture (H2O)). For example, the additive may oxidize when exposed to such reactants in the ambient air, and the resulting oxidized additive can spread to cracks and / or surface defects formed in the carbon-containing glass material. In some embodiments, the oxidizing additive can also coat the surface of cracks and / or surface defects formed in the carbon-containing glass material.

[0013] Another innovative aspect of the subject matter described herein can be implemented in carbon-containing glass materials. In some embodiments, the carbon-containing glass material may include a surface / air contact surface and an interphase region. The interphase region may extend from the surface / air contact surface to a depth of about 1 micron in the carbon-containing glass material along a direction perpendicular to the surface / air contact surface. The interphase region may include a plurality of multi-layer graphene (FLG) nanoplatelets formed in response to the recombination and / or autonucleation of a plurality of carbon-containing radicals injected into the interphase region. The plurality of FLG nanoplatelets may have a non-periodic orientation configured to at least partially suppress the formation or propagation of cracks and / or surface defects in the carbon-containing glass material.

[0014] In some embodiments, FLG nanoplatelets formed in the upper part of the interphase region adjacent to the surface / air contact surface may have a size of approximately 20 nanometers (nm), and FLG nanoplatelets formed in the lower part of the interphase region distal to the surface / air contact surface may have a size of approximately 2 nm. In some embodiments, the density of FLG nanoplatelets formed in the interphase region gradually decreases along the direction extending from the surface / air contact surface toward the depth of the interphase region. In some cases, the interphase region may have a fracture toughness of less than 50 gigapascals (GPa). In addition, or alternatively, FLG nanoplatelets formed in the interphase region of the glass material may be configured to induce compressive stress (CS) greater than 150 megapascals (MPa) within the interphase region. In some embodiments, each FLG nanoplatelet formed in the interphase region contains 3 to 5 graphene layers stacked on top of each other and has a total weight of less than 2% of the carbon-containing glass material.

[0015] In various embodiments, the interphase region may also include additives intercalated between adjacent graphene layers within the FLG nanoplatelets formed in the interphase region. In some cases, the additives may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additives may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof. The additives may be configured to self-repair cracks formed in the carbon-containing glass material when the additives are exposed to ambient air. For example, the additives may oxidize when exposed to ambient air, and the resulting oxidized additives can spread to cracks and / or surface defects formed in the carbon-containing glass material. In some embodiments, the oxidizing additives may also coat the surfaces of cracks and / or surface defects formed in the carbon-containing glass material.

[0016] In some embodiments, the carbon-containing glass material may also include a compressive stress layer formed beneath the surface / air contact surface. In one embodiment, the compressive stress layer may be formed by impacting the surface / air contact surface of the carbon-containing glass material with a plurality of ionized inert gas particles. The ionized inert gas particles penetrate the surface / air contact surface of the carbon-containing glass material and can form microcracks or microvoids in one or more portions of the interphase region. In some cases, the microcracks or microvoids may have a size of about 5 nanometers (nm) to 10 nm.

[0017] Details of one or more embodiments of the subject matter described herein are given in the accompanying drawings and the following description. Other features, aspects, and advantages will become apparent from the description, drawings, and claims. Note that the relative dimensions in the following figures may not be to scale. [Brief explanation of the drawing]

[0018] [Figure 1]Examples of a carbon-containing glass material according to some embodiments are shown. [Figure 2] Examples of FLG nanoplatelets that can be formed in the carbon-containing glass material of Fig. 1 according to some embodiments are shown. [Figure 3A] Examples of a toughening mechanism that can be used in the carbon-containing glass material of Fig. 1 according to some embodiments are shown. [Figure 3B] Another example of a toughening mechanism that can be used in the carbon-containing glass material of Fig. 1 according to some embodiments is shown. [Figure 3C] Another example of a toughening mechanism that can be used in the carbon-containing glass material of Fig. 1 according to some embodiments is shown. [Figure 4] Examples of a carbon-containing glass material having two or more interphase regions according to some embodiments are shown. [Figure 5] A part of the carbon-containing glass material of Fig. 1 according to some embodiments is shown. [Figure 6] Examples of a reactor that can be used for producing, strengthening and / or reinforcing a carbon-containing glass material according to some embodiments are shown. [Figure 7] Another example of a reactor that can be used for producing, strengthening and / or reinforcing a carbon-containing glass material according to some other embodiments is shown. [Figure 8A] A flowchart showing an example of an operation for reinforcing a carbon-containing glass material according to some embodiments is shown. [Figure 8B] A flowchart showing another example of an operation for reinforcing a carbon-containing glass material according to some embodiments is shown. [Figure 8C] A flowchart showing another example of an operation for reinforcing a carbon-containing glass material according to some embodiments is shown. [Figure 9A] A flowchart showing an example of an operation for forming a carbon-containing glass material according to some other embodiments is shown. [Figure 9B] A flowchart showing an example of an operation for forming a carbon-containing glass material according to some other embodiments is shown. [Figure 10]FIG. 1 is a flowchart showing another example of an operation for forming a carbon-containing glass material according to some other embodiments. DETAILED DESCRIPTION OF EMBODIMENTS

[0019] Like reference numerals and reference signs in various drawings indicate like elements. Aspects of the present disclosure are provided in the following description and associated drawings directed to various examples provided for illustrative purposes. Alternative embodiments may be devised without departing from the scope of the present disclosure. Furthermore, well-known elements of the present disclosure are not described in detail or are omitted so as not to obscure relevant details of the present disclosure.

[0020] Toughness of a material may refer to the ability of the material to withstand an applied force without undergoing mechanical fracture, and may depend at least in part on the compressive strength, tensile strength, and fracture toughness of the material. The compressive strength of a material may refer to the ability of the material to withstand an applied force, and can be measured in units of pascals (Pa). The ultimate tensile strength (UTS) of a material may refer to the maximum stress that the material can withstand while being stretched or pulled before mechanical failure (such as before breaking). The fracture toughness of a material refers to the inherent ability of the material to resist fracture and / or cracks.

[0021] Further, glass and glass-containing materials are also susceptible to cracks generated by external forces (such as when an object collides with the glass). For example, when an external force exceeding a certain fracture energy is applied to a glass material, the external force may cause the glass-containing material to form cracks and / or propagate existing cracks throughout the glass material. Also, when a glass material is subjected to compressive stress or tensile stress, existing defects (such as scratches or surface defects) in the glass material may exacerbate the applied compressive and / or tensile stress, which in turn may result in relatively high stress concentrations at or near the existing defects. Portions of the glass material associated with relatively high stress concentrations may be more susceptible to crack formation and propagation than other portions of the glass material.

[0022] The tensile strength of conventional glass is approximately 7 megapascals (MPa), and its theoretical maximum tensile strength is approximately 17 gigapascals (GPa), which is orders of magnitude greater than typical tensile strengths. The relatively high theoretical maximum tensile strength of glass may be due to the strong chemical bond between silicon and oxygen in silicon dioxide (SiO2) molecules, which form the main component of many glass materials. However, due to defects and surface imperfections (microcracks, fissures, and scratches, etc.) introduced into the glass material during conventional manufacturing techniques, the measured tensile strength of glass materials usually decreases from the theoretical maximum tensile strength to a typical tensile strength of approximately 7 MPa.

[0023] The applicant has confirmed that relatively brittle glass can result from the introduction of impurities into the glass during conventional manufacturing processes. These impurities are often introduced into the glass as strengthening mechanisms and can reduce the compressive strength, tensile strength, and / or fracture toughness of the glass material. For example, when glass is heated, unmelted or undissolved portions of such impurities can cause the formation of one or more layers on or within the glass material, which can then introduce internal stresses into the glass material, reducing the overall strength of the glass material. These unmelted or undissolved portions of impurities can also unintentionally provide nucleation and growth fields for crack formation and / or propagation throughout the glass. Furthermore, conventional thermal and chemical strengthening processes can expose molten glass to moisture, dust, and other particles in the surrounding air, thereby further reducing the compressive strength, tensile strength, and / or fracture toughness of the glass material by exposing the glass to additional impurities.

[0024] According to various embodiments of the subject disclosed herein, the surface / air contact surface of a glass material may be impacted by carbon-based radicals, ionized inert gas particles, additives, positively charged particles, or any combination thereof. The glass material may be impacted by ionized inert gas particles and / or positively charged particles, which may penetrate the surface / air contact surface of the glass material and create microcracks and / or microvoids in the interphase region of the glass material. Carbon-based radicals can be injected into the microcracks and / or microvoids created in the interphase region by the impact. In some embodiments, carbon-based radicals can also be injected into other parts of the glass material. The injected carbon-based radicals can recombine and / or autonucleate to form multiple FLG nanoplatelets throughout the interphase region. The FLG nanoplatelets can be dispersed throughout the interphase region in a random or aperiodic orientation to suppress crack formation or propagation in the carbon-containing glass material. In some embodiments, additives can be doped onto one or more surfaces of the FLG nanoplatelets formed in the interphase region.

[0025] The additive can be intercalated between adjacent graphene layers of FLG nanoplatelets dispersed throughout the interphase region. Subsequently, when the glass material develops one or more cracks in response to an external force applied to the glass material, portions of the additive intercalated within the FLG nanoplatelets can be exposed to the ambient air in or near the cracks. Chemical reactions between the exposed additive and the ambient air can produce metal oxides that spread and / or coat the surface of the one or more cracks formed in the glass material. The expansion of the metal oxides into the cracks and the metal oxide coating formed on the exposed crack surfaces can prevent, or at least suppress, further propagation of cracks in the glass material. Thus, using the techniques disclosed herein, glass and glass materials can be manufactured, strengthened, and / or reinforced without introducing undesirable impurities that may reduce the compressive strength, tensile strength, and / or fracture toughness of glass or glass materials.

[0026] Figure 1 shows a carbon-containing glass material 100 that can be manufactured, strengthened, and / or reinforced according to one or more embodiments of the subject matter disclosed herein. The carbon-containing glass material 100 may be any suitable type of glass, glass-containing material, or carbon-containing glass material. In some embodiments, the glass material 100 may be or include alkali aluminosilicate glass having a composition of about 57-60% SiO2, about 10-25% Al2O3, and about 10% alkaline earth metal. In some embodiments, the glass material 100 may have a thickness of 9.8 × 10 -6 It may have a thermal expansion of / K. In other embodiments, the glass material 100 may be, or include, (but not limited to) borosilicate glass, silicate glass, or soda-lime glass. In some cases, the glass material 100 may be chemically strengthened using one or more conventional glass strengthening processes before applying the various glass strengthening techniques disclosed herein. For example, the glass material 100 may be chemically strengthened by heat treatment, surface crystallization, and / or by the application of other chemicals to the glass material 100. In other examples, the glass material 100 may be chemically strengthened glass such as Gorilla® glass, which is commercially available from Corning, Inc., Corning, New York. In some other examples, the glass material 100 may be Dragontrail glass, which is available from Asahi Glass Co., Tokyo, Japan.

[0027] The glass material 100 is shown to include a surface / air contact surface 110, an interphase region 120, and a substrate region 130. The surface / air contact surface 110 may be exposed to an external environment including ambient air 102 and may provide a contact surface from which carbon-based radicals, ionized inert gas particles, additives, positively charged particles, and other particles or mixtures can penetrate and / or be injected into the glass material 100 during manufacturing. The interphase region 120 extends from the surface / air contact surface 110 to a depth 122 of the glass material 100 along a direction 150 perpendicular to the surface / air contact surface 110 and may consist of one or more mechanisms that strengthen and / or reinforce the glass material 100. In some embodiments, the depth 122 of the interphase region 120 may be about 1 micron, while in other embodiments, the depth 122 of the interphase region 120 may be about 1 to 10 microns. In some embodiments, a monolayer 112 of excess carbon may be deposited and / or placed in the interphase region 120. In some embodiments, a monolayer of excess carbon may help strengthen and / or toughen the interphase region 120 by providing a reinforcing material or substance that can be used to absorb and / or dissipate energy from collisions or other sources.

[0028] In various embodiments, the interphase region 120 may be formed within the glass material 100 by impacting the surface / air contact surface 110 with carbon-based radicals, ionized inert gas particles, additives, positively charged particles, and / or other suitable particles or materials. The carbon-based radicals may (but are not limited to) methyl radicals. In some embodiments, the carbon-based radicals and ionized inert gas particles may be supplied by (or extracted from) a non-thermal equilibrium plasma within the reaction chamber. The non-thermal equilibrium plasma may be generated by exciting hydrocarbon gases and silanes with microwave energy within the reaction chamber, for example, as described in more detail with reference to Figures 6 and 7.

[0029] Ionized inert gas particles, which may be argon and / or helium (but not limited to), can penetrate the surface / air contact surface 110 and "soften" one or more portions of the glass material 100 by, for example, creating voids in the glass material 100. More specifically, ionized inert gas particles can create voids by impacting various atoms, molecules, and particles of the glass material 100 and displacing at least some of the impacted atoms, molecules, and particles. Ionized inert gas particles may have different masses and / or different sizes, which can increase the depth and / or concentration of ion penetration. In some cases, voids created by ionized inert gas particles can form a compressive stress layer 115 between the interphase region 120 and the surface / air contact surface 110. In some embodiments, the compressive stress layer 115 can be induced by ion impacts of the glass material 100 by a plurality of ionized inert gas particles (such as any of those presented and described with respect to Figures 6 and 7).

[0030] Carbon-based radicals can be injected into voids and / or small cracks created by the impact of ionized inert gas particles on the glass material 100. Upon injection into the glass material 100, the carbon-based radicals can recombine, self-nucleate, and form multiple multi-layer graphene (FLG) nanoplatelets 140 dispersed throughout the interphase region 120. The fracture toughness of the glass material 100 is increased by the formation of the FLG nanoplatelets 140, which can reduce the Young's modulus of the interphase region 120. In some embodiments, the FLG nanoplatelets 140 can reduce the Young's modulus to approximately 50 GPa to approximately 150 MPa.

[0031] The FLG nanoplatelets 140 can be dispersed throughout the interphase region 120 in a random or non-periodic orientation, at least partially suppressing the formation or propagation of cracks and / or surface defects in the glass material 100. The FLG nanoplatelets 140 can also function as energy storage units that can absorb and / or dissipate external forces (such as fracture energy) that occur at or near cracks and crack tips in the glass material 100. In some embodiments, the FLG nanoplatelets 140 formed in the upper part 120A of the interphase region 120 adjacent to the surface / air contact surface 110 may have a size of about 20 nanometers (nm), and the FLG nanoplatelets 140 formed in the lower part 120B of the interphase region 120 distal to the surface / air contact surface 110 may have a size of about 2 nm. In some embodiments, the FLG nanoplatelets in the gradient portion 120C of the interphase region 120, located between the upper 120A and lower 120B of the interphase region 120, gradually decrease in size along the direction 150 toward the depth 122 of the interphase region 120. In some cases, the FLG nanoplatelets 140 formed inside the interphase region 120 may have a total weight of less than 2% of the glass material 100.

[0032] The density of the multiple FLG nanoplatelets 140 formed in the interphase region 120 may gradually decrease along the direction 150 from the surface / air contact surface 110 to the depth 122 of the glass material 100. For example, the density of the FLG nanoplatelets 140 may decrease by approximately 0-5%, 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45%, 45-50%, 50-55%, 55-60%, 60-65%, 65-70%, 70-75%, 75-80%, 80-85%, 85-90%, 90-95%, and 95-100% per unit depth. In some embodiments, the depth per unit area may be approximately 10 nm to 50 nm. In other embodiments, the depth per unit area may be approximately 50 nm to 100 nm.

[0033] In various embodiments, the density of FLG nanoplatelets 140 formed within the interphase region 120 of the glass material 100 can be controlled and fine-tuned by adjusting one or more aspects of the process in which carbon-based radicals are injected into the glass material 100. The compressive residual stress of the interphase region 120 may be positively correlated with the density of FLG nanoplatelets 140 formed within the interphase region 120. Thus, the compressive residual stress of the interphase region 120 can be increased (or set to a relatively high value) by increasing the density of FLG nanoplatelets 140 formed within it, and the compressive residual stress of the interphase region 120 can be decreased (or set to a relatively low value) by decreasing the density of FLG nanoplatelets 140 formed within it. In this way, the compressive residual stress of the interphase region 110 can be adjusted to discrete levels. For example, in some embodiments, the compressive residual stress in the interphase region 110 can be adjusted to levels of approximately 0-25 MPa, approximately 25-50 MPa, approximately 50-75 MPa, approximately 75-100 MPa, approximately 100-125 MPa, or approximately 125 MPa.

[0034] The additive may be any suitable material, particle, or mixture that can be injected into the glass material 100 and configured to self-repair cracks or surface defects formed in the glass material 100. In some cases, the additive may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additive may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof. The additive may be injected into one or more portions of the glass material 100 in any suitable manner. For example, in some embodiments, the additive may be injected into the glass material 100 simultaneously with the injection of carbon-based radicals into the interphase region 120, while in other embodiments, the additive may be injected into the glass material 100 independently of carbon-based radicals. In one embodiment, the additive may be doped onto one or more surfaces of FLG nanoplatelets 140 formed in the glass material 100. When injected into the glass material 100, the additive can be intercalated between adjacent graphene layers of the FLG nanoplatelet 140.

[0035] Subsequently, when the additive is exposed to ambient air, it can be oxidized by a chemical reaction between the additive and certain components of the ambient air (such as H2O molecules and O2 molecules). The oxidizing additive can spread to and / or coat cracks, fissures, and surface defects adjacent to the intercalated FLG nanoplatelet 140. For example, when the glass material 100 generates one or more cracks in response to an external force applied to the glass material 100, the cracks, fissures, and surface defects, or portions of the additive intercalated inside the FLG nanoplatelet 140 near them, can be exposed to ambient air 102. The chemical reaction between the exposed additive and the ambient air 102 can produce metal oxides that spread to and / or coat the surface of the cracks, fissures, and surface defects formed in the glass material 100. The spread of metal oxides to cracks, fissures, and surface defects, as well as the metal oxide coating on exposed surfaces of cracks, fissures, and surface defects, can prevent, or at least suppress, the further propagation of cracks, fissures, and surface defects in the glass material 100. Thus, using the techniques disclosed herein, glass and glass materials can be manufactured, strengthened, and / or reinforced without introducing undesirable impurities that may reduce the compressive strength, tensile strength, and / or fracture toughness of glass or glass materials.

[0036] In some embodiments, the non-thermal equilibrium plasma may also include a plurality of positively charged particles that can be separated from the carbon-based radicals and ionized inert gas particles in the reaction chamber. An external electric field or potential may be used to accelerate the positively charged particles passing through the reaction chamber, thereby increasing the velocity and energy at which the positively charged particles can collide with the surface / air contact surface 110 of the glass material 100. In this way, the accelerated particles can penetrate the glass material 100 with greater energy and further soften one or more portions of the glass material 100 that define the interphase region 120.

[0037] In one embodiment, the formation of FLG nanoplatelets 140 within the interphase region 120 can be controlled to adjust the temporal and spatial aspects of the intrinsic strain field within the interphase region 120. For example, carbon-based radicals injected into the glass material 100 recombine and, below the surface / air contact surface 110, are aligned 2D sp having a density and size distribution defined within the interphase region 120 of less than approximately 1 mm. 2 FLG nanoplatelets can be formed. In some embodiments, the intrinsic strain field undergoes autonucleation and 2D sp in the reaction chamber before being injected into the interphase region 120 of the glass material 100. 2 This can result from controlled growth of graphene nanoparticles. 2D sp in the reaction chamber. 2 The control of graphene nanoparticle self-nucleation and growth may arise from the presence of supersaturated levels of excited carbon-based radicals in a non-equilibrium plasma where carbon-based radicals are generated.

[0038] In some other embodiments, additional carbon-based particles may be introduced into the reaction chamber and subsequently injected into the interphase region 120 of the glass material 100. These additional carbon-based particles may further increase the fracture toughness of the interphase region 120 and / or further suppress crack formation and propagation throughout the glass material 100. In some embodiments, these additional carbon-based particles, which may be called secondary carbon particles, may be injected into the upper part 120A of the interphase region 120.

[0039] In some embodiments, different hydrocarbon precursor feed gases (methane, ethanol with different C / H ratios, ethanol with different oxygen content, etc.) are used to perform specific plasma chemical reactions (C+, C2, CH3, O -(etc.) can be created, from which carbon-based radicals are generated and subsequently injected into the interphase region 120 of the glass material 100. In some embodiments, the size of the FLG nanoplatelets 140 can be selected or adjusted based on the specific purpose of the resulting graphene formation. For example, FLG nanoplatelets used to adjust various quantum effects of the glass material 100 may have a size of less than 5 nm, while FLG nanoplatelets used to adjust the light transmission or light absorption properties of the glass material 100 may have a size of about 5 to 50 nm.

[0040] The FLG nanoplatelets 140 cause the interphase region 120 to have a different refractive index than the substrate portion 130 of the glass material 100. In one embodiment, the FLG nanoplatelets 140 formed in the interphase region 120 may be configured such that the change in light transmittance due to scattering at the surface / air contact surface 110 of the glass material 100 is less than about 0.5%.

[0041] The formation of FLG nanoplatelets 140 within the interphase region 120 and the penetration of excited ions into it can result in an interphase region 120 having a processing gradient ranging from linear to Gaussian. In some embodiments, one or more mechanical, chemical, electrical, and / or optical properties can be tuned based on the concentration of FLG nanoplatelets 140 formed within the interphase region 120. The FLG nanoplatelets 140 formed within the interphase region 120 can also increase the fracture toughness of the glass material 100 by dissipating fracture energy and other external forces applied to the glass material 100. Thus, forming FLG nanoplatelets 140 within the interphase region 120 based on the techniques disclosed herein can reinforce the glass material 100 without introducing undesirable impurities into the glass material 100.

[0042] Figure 2 shows examples of FLG nanoplatelets 200 that can be formed in the carbon-containing glass material 100 of Figure 1, according to several embodiments. An example of an FLG nanoplatelet 200, which may be an FLG nanoplatelet 140 formed in the glass material 100 of Figure 1, may have a twisted or wrinkled structure, and the group of carbon-carbon bonded atoms may bend or fold in response to an external force, pressure, or load. For example, when an external force is applied to the glass material 100, the presence of the FLG nanoplatelets 140 in the interphase region 120 may cause the glass material 100 to bend, fold, or fold in response to the applied force (such as a force that is not due to cracking or fracturing). Thus, glass and glass materials manufactured, strengthened, and / or reinforced using the techniques disclosed herein can absorb and / or dissipate the energy and stress associated with the applied force, pressure, and load, thereby reducing the overall compressive stress experienced by the glass material 100.

[0043] In the example shown in Figure 2, the FLG nanoplatelet 200 is shown to include four graphene layers 201-204 stacked on top of each other (vertically or substantially vertically, etc.). In other embodiments, the FLG nanoplatelet 200 may include a different number of graphene layers. The number of graphene layers in the FLG nanoplatelet 200 may affect one or more properties of the FLG nanoplatelet 200. These properties may include, but are not limited to, the ability to absorb or dissipate energy, the ability to conduct electricity, and the ability to self-heal cracks formed in glass and glass materials. For example, increasing the number of graphene layers in the FLG nanoplatelet 200 may improve the ability of the glass material 100 to absorb or dissipate energy, improve the ability of the glass material 100 to conduct electricity, and improve the ability of the glass material 100 to self-heal cracks and other surface defects. Therefore, in at least some embodiments, the FLG nanoplatelets 140 formed on the glass material 100 in Figure 1 may have a relatively large number of graphene layers (e.g., 10 or more graphene layers) to maximize the glass material 100's ability to absorb energy, dissipate energy, conduct electricity, and self-repair cracks.

[0044] However, increasing the number of graphene layers in the FLG nanoplatelet 200 increases the thickness of the FLG nanoplatelet 200, which in turn increases the opacity of the FLG nanoplatelet 200. Generally, opacity is a measure of impermeability to electromagnetic radiation and light. For example, an opaque material is neither transparent (allowing all received light to pass through the material) nor semi-transparent (allowing only a portion of received light to pass through the material), but rather reflects, scatters, and / or absorbs all received light. Furthermore, when light strikes a contact surface between two layers, materials, components, and / or materials, some of the light may not travel through the contact surface. That is, some of the light may be absorbed by the contact surface, some of the light may be absorbed by the contact surface, and some of the light may be scattered by the contact surface (the rest of the light travels through the material). As a result, when the FLG nanoplatelets 200 contain more than a certain number of graphene layers or exceed a certain thickness, the opacity of the FLG nanoplatelets 200 may exceed a threshold, and thereafter, the glass material in which the network of FLG nanoplatelets 200 is formed is unsuitable for some optical applications. For example, thereafter, the tempered glass material 100 may not be suitable for optical applications.

[0045] The applicant has confirmed that when formed in a glass material (such as the carbon-containing glass material 100 in Figure 1), the FLG nanoplatelets 200 having 3 to 5 layers of graphene bring about a desired harmony of the glass material's ability to absorb energy, dissipate energy, conduct electricity, and self-repair cracks and light transmittance (such as the ability to pass light below the threshold of loss and / or refraction). The applicant has also confirmed that the FLG nanoplatelets 200 formed inside the interphase region 120 of the glass material 100 have a thickness of about 1 nm to 3 nm and lateral dimensions (length and width, etc.) of about 100 nm to 100 μm. In one embodiment, the FLG nanoplatelets 200 formed in the upper part 120A of the interphase region 120 have a lateral dimension of about 20 nm, and the FLG nanoplatelets 200 formed in the lower part 120B of the interphase region 120 have a lateral dimension of about 2 nm.

[0046] Figure 3A shows examples of mechanisms 300A for toughening a glass material according to several embodiments. The glass material includes a surface / air contact surface 302 and an interphase region 304. The surface / air contact surface 302, which may be an example of the surface / air contact surface 110 in Figure 1, can provide a contact surface from which various particles and materials can be impacted, injected, and / or doped into the glass material. The interphase region 304, which may be an example of the interphase region 120 in Figure 1, includes a plurality of FLG nanoplatelets 200 formed within it, for example, as described above with reference to Figures 1 and 2. As shown in Figure 3A, the glass material also includes a crack 310 having a width W1 across the surface / air contact surface 302 and a depth D1 extending into the glass material. The crack 310 is also shown to include a crack tip 312.

[0047] One of the FLG nanoplatelets 200, shown as FLG nanoplatelet 200A in Figure 3A, is shown to "bridge" the crack 310. That is, the first end of FLG nanoplatelet 200A is bonded to the right-hand portion of the glass material of the crack 310, and the second end of FLG nanoplatelet 200A is bonded to the left-hand portion of the glass material of the crack 310. As a result of this bridging, FLG nanoplatelet 200A can absorb and / or dissipate forces, stresses, and loads applied to the portion of the glass material near the crack 310. Furthermore, since the crack 310 is most likely to propagate vertically downward 305 in response to tensile stress that pulls the opposite sides of the crack 310 apart, the position and orientation of FLG nanoplatelet 200A relative to the crack 310 can direct the direction of crack propagation in the transverse direction 315, which is perpendicular to the vertical direction 305 and parallel to the surface / air contact surface 302 of the glass material.

[0048] In various embodiments, additives can be intercalated between adjacent graphene layers of FLG nanoplatelets 200 formed in a glass material (for simplicity, the additives are not shown in Figure 3A). In some cases, the additives can be doped onto one or more surfaces of at least a portion of the FLG nanoplatelets 200. When exposed to ambient air, the additives may oxidize and form an oxidized material that spreads over and / or covers the surface of cracks 310 formed in the glass material. In some cases, the additives may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additives may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof. Thus, the presence of such additives intercalated within the FLG nanoplatelets 200 allows for self-healing of cracks 310 (and other cracks not shown for simplicity) formed in the glass material.

[0049] In some embodiments, due to the surface energy effect, the intercalated additives may form spheres on or near the surface of each FLG nanoplatelet 200. In some cases, the metallic spheres may have a diameter of about 1–5 nm. The metallic spheres may diffuse when an external force is applied, creating voids between the FLG nanoplatelets 200 (resulting from the Kirkendall effect, etc.). At least a portion of the voids may absorb and / or dissipate the fracture energy present at the crack tip 312, thereby preventing further propagation of the crack 310 into or across the glass material.

[0050] Figure 3B shows an example of a mechanism 300B for toughening a glass material according to another embodiment. The glass material includes a surface / air contact surface 302 and an interphase region 304. The surface / air contact surface 302, which may be an example of the surface / air contact surface 110 in Figure 1, can provide a contact surface from which various particles and materials can be impacted, injected, and / or doped into the glass material. The interphase region 304, which may be an example of the interphase region 120 in Figure 1, includes a plurality of FLG nanoplatelets 200 formed within it, for example, as described above with reference to Figures 1 and 2. As shown in Figure 3B, the glass material also includes a crack 320 having a width W2 across the surface / air contact surface 302 and a depth D2 extending into the glass material. The crack 320 is also shown to include a crack tip 322.

[0051] One of the FLG nanoplatelets 200, shown as FLG nanoplatelet 200B in Figure 3B, is positioned below the crack tip 322 and oriented substantially orthogonal to the depth D2 of the crack 320. When the crack 320 is subjected to an applied force, causing the crack 320 to begin propagating vertically downward 305, the FLG nanoplatelet 200B positioned below the crack tip 322 may absorb and / or diffuse some or all of the applied force, resulting in the crack not propagating further than the FLG nanoplatelet 200B. In some cases, the orthogonal orientation of the FLG nanoplatelet 200B relative to the crack 320 may cause the crack 320 to "branch," forming one or more microcracks at or near the crack tip 322. Because the microcracks are relatively small and have relatively low energy compared to crack 320, they may not propagate laterally in direction 315 beyond FLG nanoplatelets 201, or laterally in direction 316 beyond FLG nanoplatelets 202. More specifically, because FLG nanoplatelets 201 and 202 are oriented orthogonal to the laterally moving microcracks, the laterally moving microcracks may not have enough energy to penetrate or fracture FLG nanoplatelets 201 and 202. Thus, FLG nanoplatelets 200B can suppress the vertical propagation of crack 320 (and other cracks not shown for simplification) through the glass material, and FLG nanoplatelets 201 and 202 can suppress the laterally moving microcracks through the glass material.

[0052] Figure 3C shows examples of mechanisms 300C for toughening a glass material according to several embodiments. The glass material includes a surface / air contact surface 302 and an interphase region 304. The surface / air contact surface 302, which may be an example of the surface / air contact surface 110 in Figure 1, can provide a contact surface from which various particles and materials can be impacted, injected, and / or doped into the glass material. The interphase region 304, which may be an example of the interphase region 120 in Figure 1, includes a plurality of FLG nanoplatelets 200 formed within it, for example, as described above with reference to Figures 1 and 2. As shown in Figure 3C, the glass material also includes a crack 330 having a width W3 across the surface / air contact surface 302 and a depth D3 extending into the glass material. The crack 330 is also shown to include a crack tip 332.

[0053] One of the FLG nanoplatelets 200, shown as FLG nanoplatelets 200C in Figure 3C, is adjacent to the crack tip 332 and oriented substantially parallel to the crack 330. When the crack 330 is subjected to an applied force, and the crack 330 begins to propagate laterally 315 toward the FLG nanoplatelets 200C, the graphene layers inside the FLG nanoplatelets 200C exhibit sliding motion toward each other, for example, which can absorb and / or dissipate at least a portion of the applied force, thereby suppressing further propagation of the crack 330 through the glass material.

[0054] Figure 4 shows examples of carbon-containing glass material 400 having two or more interphase regions according to several other embodiments. As shown, the glass material 400 may include a first interphase region 420(1), a second interphase region 420(2), and a third region 430. Each of the first interphase region 420(1) and the second interphase region 420(2) may contain a plurality of FLG nanoplatelets (e.g., formed by recombination or autonucleation of carbon-based radicals injected into or impacted in the glass material). In some embodiments, each of the first interphase region 420(1) and the second interphase region 420(2) may be an example of the interphase region 120 of the glass material 100 in Figure 1. That is, each of the first interphase region 420(1) and the second interphase region 420(2) may have a plurality of FLG nanoplatelets 402, 404 formed inside them to strengthen and / or reinforce the glass material 400. The alignment of the FLG nanoplatelets 402 and 404 can, in some embodiments, reduce potential surface defects or damage to the first interphase region 420(1) and the second interphase region 420(2). In some embodiments, the FLG nanoplatelets 402 and 404 inside the first interphase region 420(1) and the second interphase region 420(2) may be formed in different orientations. For example, the first FLG nanoplatelet 402 may have a first orientation, and the second FLG nanoplatelet 404 may have a second orientation different from the first orientation. The first interphase region 420(1) may also include other FLG nanoplatelets (not shown for simplicity) having one or more orientations different from the first and second orientations.

[0055] FLG nanoplatelets 402, 404 formed within various parts of the glass material 400 can form graphene networks integrated within the various molecular structures of the glass material 400. In some embodiments, the graphene networks, which may be analogous to grain boundaries observed in nanocrystalline matrix structures, can extend laterally across the glass material 400 (e.g., along width and length), forming a toughening or strengthening mechanism that can increase the compressive strength, tensile strength, and fracture toughness of the glass material 400.

[0056] Figure 5 shows a portion of the carbon-containing glass material 500 according to several other embodiments. The glass material 500, which may be an example of the glass material 100 in Figure 1, is shown to include a surface / air contact surface 510, an interphase region 520, a self-healing layer 530, cracks 540 formed in the glass material 500, and a plurality of FLG nanoplatelets 550 formed in the glass material 500. For simplicity, the portion of the glass material 500 below the interphase region 520 is not shown in Figure 5.

[0057] As shown, the self-healing layer 530 may be located within the interphase region 520 of the glass material and may extend to the surface / air contact surface 510 of the glass material 500. One or more additives 560 may be intercalated between adjacent graphene layers 552 of at least some of the FLG nanoplatelets 550 formed in the glass material (for simplicity, Figure 5 shows only one graphene layer 552 of the FLG nanoplatelets 550). In some cases, the additives may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additives may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof.

[0058] As a crack 540 propagates vertically downward 501 from the surface / air contact surface 510 of the glass material 500 to the self-healing layer 530, the crack 540 exposes a group of FLG nanoplatelets 550 to the ambient air at or near the crack tip 542. Chemical reactions between the intercalated additives within the group of FLG nanoplatelets 550 and certain components of the ambient air (such as oxygen (O2) molecules 570 and water (H2O) molecules 572) generate oxides (metal oxides 580 and / or metal oxide-hydroxides 582) that spread into and / or coat the exposed surface 541 of the crack 540. The spread of oxides 580 and / or oxides 582 into the crack 540, and the resulting coating on the exposed surface 541 of the crack 540, prevent, or at least suppress, further propagation of the crack 540 through the glass material 500. Thus, using the techniques disclosed herein, the glass material 500 can be manufactured, strengthened, and / or reinforced without introducing undesirable impurities that may reduce the compressive strength, tensile strength, and / or fracture toughness of the glass material 500.

[0059] In some embodiments, thermal or microwave energy may be applied to the glass material 500 during manufacturing (e.g., in a reaction chamber) to increase the diffusion of the additive 560 to the crack tip 542, thereby increasing the rate at which the metal oxide 580 and metal hydroxide 582 are produced.

[0060] Figure 6 shows examples of reactors 600 that can be used to manufacture, strengthen, and / or reinforce carbon-containing glass materials according to several embodiments. In some cases, glass materials strengthened and / or reinforced using the techniques described herein may have greater resilience against the propagation of existing cracks and / or the formation of new cracks when an external force is applied to the glass material 650. In addition, or alternatively, the reactor 600 may be implemented as a plasma torch.

[0061] The reactor 600 may include a microwave energy source 610, an input gas inlet 615, a reaction vessel 620, a potential source 630, and a metal substrate 640. The reaction vessel 620 may include a reaction chamber 622, a downstream region 624, and a collector 626. The reaction chamber 622 has a length L along a direction 602 parallel to the reaction chamber 622. The input gas inlet 615 is coupled between the reaction vessel 620 and a material source (not shown for simplicity) and may be used to introduce or otherwise supply material 605 (one or more gases, liquids, particles, etc.) into the reaction chamber 622. For example, in some cases, material 605 may include (but not limited to) various structured carbons such as CNTs and fullerenes.

[0062] The microwave energy source 610 can generate microwave energy 612 that can excite material 605 to produce a plasma capable of separating or extracting carbon-based radicals. In some cases, the microwave energy source 610 can generate pulsed microwave energy, for example, as described in jointly held U.S. Patents 9,767,992 and 10,314,512. In other examples, the microwave energy source 610 can generate continuous microwave energy. The microwave energy source 610 may include a control circuit that can adjust various characteristics of the microwave energy 612 based on one or more control signals (CTRLs). For example, the CTRL signals may determine one or more of the pulse duration, pulse frequency, duty cycle, instantaneous power level, or average power level of the microwave energy 612. Thus, the reactor 600 can configure the size, number, and concentration of the graphene layer of FLG nanoplatelets formed in the glass material 650 by adjusting the pulse duration, pulse frequency, duty cycle, instantaneous power level, and / or average power level of the microwave energy 612 generated to create a non-thermal equilibrium plasma in the reaction chamber 622. The ability to control the energy applied to the non-thermal equilibrium plasma allows the target reaction to occur and promotes the distribution of FLG nanoplatelets and other particles throughout the glass material 650.

[0063] In some embodiments, a mixture of hydrocarbon gas and silane may be introduced into the reaction chamber 622 through the input gas inlet 615 at an appropriate flow rate. The hydrocarbon gas may be any suitable carbon-containing gas, such as methane gas (but not limited to). The silane may be any suitable silane gas or silane-containing liquid precursor. In some embodiments, the silane may be introduced into the reaction chamber 622 at a flow rate of about 1 standard liter / min (slm) to 10 slm / min. In some embodiments, additives may be introduced into the reaction chamber 622 at the same time as the mixture is introduced. In some cases, the additives may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additives may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof. The additives may be introduced into the reactor at a flow rate of about 1% to 75% of the hydrocarbon gas flow rate.

[0064] The microwave energy 612 generated by the microwave energy source 610 can be directed to a portion of the reaction chamber 622 containing a mixture of hydrocarbon gas and silane. The microwave energy 612, which may have a power level of approximately 300 watts (W) to 25 kilowatts (kW), can excite the mixture of hydrocarbon gas and silane to generate a non-thermal equilibrium plasma. In some embodiments, the microwave energy source 610 may be a klystron or a traveling wave tube amplifier (TWTA). The non-thermal equilibrium plasma may contain carbon-based radicals (such as methyl radicals), positively charged particles, ionized inert gas particles, or any combination thereof. In various embodiments, the carbon-based radicals, positively charged particles, and / or ionized inert gas particles 660 output from the reaction chamber 622 via the collector 626 can be directed to the surface / air contact surface of the glass material 650 by impact and / or injection. The glass material 650 may be subjected to impact by carbon-based radicals, positively charged particles, and / or ionized inert gas particles to form, strengthen, and / or reinforce one or more portions of the glass material 650. Portions of the glass material 650 formed, strengthened, or reinforced according to the techniques disclosed herein may have improved compressive strength, tensile strength, and fracture toughness, and therefore greater resilience against cracks and surface defects than conventional glass materials.

[0065] More specifically, the surface / air contact surface of the glass material 650 may be subjected to impact by carbon-based radicals and ionized inert gas particles separated from the non-thermal equilibrium plasma of the reaction chamber 622. The ionized inert gas particles penetrate the surface / air contact surface of the glass material 650, and microcracks, microvoids, and / or surface defects may be formed in the portion of the glass material 650 beneath the surface / air contact surface. In some embodiments, the microcracks, microvoids, and / or surface defects formed by the ion impact of the glass material 650 may define the interphase region of the glass material 650. The carbon-based radicals that penetrate the surface / air contact surface of the glass material 650 may be injected into the interphase region.

[0066] In some embodiments, an external electric field may be applied to the reaction chamber 622 to accelerate positively charged particles through the reaction chamber 622 toward the glass material 650 along direction 604, thereby increasing the velocity and energy at which the positively charged particles can collide with the surface / air contact surface 110 of the glass material 650. For example, a potential source 630 may generate a negative electric field or potential that can accelerate positively charged particles toward the glass material 650 located on the metal substrate 640 along direction 604. In some embodiments, the negative potential generated by the potential source 630 may be configured to extract or separate positively charged gas particles from the non-thermal equilibrium plasma based on its electrical polarity. Thus, the negative electric field or potential may allow positively charged particles, as well as ionized inert gas particles and carbon-based radicals, to penetrate more deeply into the interphase region of the glass material 650.

[0067] Carbon-based radicals injected into the interphase region of the glass material 650 can recombine and self-nucleate to form multiple FLG nanoplatelets. These FLG nanoplatelets can be dispersed throughout the interphase region of the glass material 650 in a non-periodic orientation that at least partially suppresses crack formation or propagation in the glass material 650. In some embodiments, the FLG nanoplatelets formed in the interphase region can increase the fracture toughness of the glass material 650 by reducing the Young's modulus of the interphase region (but not limited to) approximately 50 GPa to approximately 150 MPa. The FLG nanoplatelets formed in the interphase region can also function as energy reservoirs that absorb and / or dissipate external forces applied to existing cracks and / or crack tips in the glass material 650.

[0068] As described, the concentration and size of FLG nanoplatelets formed in the glass material 650 may decrease along direction 604 to the depth of the interphase region. For example, in some embodiments, FLG nanoplatelets formed in the upper part of the interphase region of the glass material 650 may have a size of about 20 nanometers (nm), and FLG nanoplatelets formed in the lower part of the interphase region of the glass material 650 may have a size of about 2 nm. In some cases, the size of FLG nanoplatelets formed between the upper and lower parts of the interphase region may gradually decrease along direction 604.

[0069] In some embodiments, as described above, additives may be doped onto one or more surfaces of FLG nanoplatelets formed in the interphase region of the glass material 650. For example, as described above with reference to Figures 1, 2, 3A-3C, 4, and 5, additives that can be intercalated between at least some adjacent graphene layers of FLG nanoplatelets formed in the interphase region of the glass material 650 can self-repair cracks and other surface defects in the glass material 650 when exposed to ambient air.

[0070] In various embodiments, the reactor 600 may be cylindrical in shape and have a diameter of up to 1 inch. In some embodiments, the reactor 600 may be configured as a Gaussian reactor, while in other embodiments, the reactor 600 may be configured as a non-Gaussian reactor (for example, plasma produced in a non-Gaussian reactor typically exhibits better energy dissipation and energy distribution than plasma produced in a Gaussian reactor).

[0071] Figure 7 shows another example of a reactor 700 that can be used to manufacture, strengthen, and / or reinforce carbon-containing glass materials according to several other embodiments. In some embodiments, the reactor 700 may be similar to the reactor 600 in Figure 6, and in other embodiments, it may differ from the reactor 600 in Figure 6. For example, the reactor 700 may include a microwave energy source 610, an input gas inlet 615, a reaction vessel 720, a potential source 730, a metal substrate 640, and a collector 626. In one embodiment in which the reactor 700 differs from the reactor 600, the reactor 700 includes a plurality of electrodes 728 located on the opposite side of one or more parts of the reaction chamber 720, rather than having the potential source 630 for generating an electric field inside one or more parts of the reaction chamber 720. Electrode 728 may be configured to generate an internal electric field (for example, based on a current and / or voltage provided by the power supply unit 732) that can accelerate multiple positively charged particles, resulting in increased velocity and energy when the accelerated positively charged particles are struck within the glass material 650. In addition, or alternatively, reactor 700 may also include an additional potential source (not shown for simplicity) positioned to generate a negative potential across the reaction chamber 722 along direction 704 and induce a current flow 732 along the wall facing the inside of the reaction chamber 722. The current flow 732 induced within the reaction chamber 722 may create a magnetic field that can attract and accelerate at least positively charged gas particles output from the collector 626 towards the glass material 650 through the reaction chamber 722.

[0072] In addition to the methane gas added to reactors 600 and 700 to generate carbon-based radicals, the carbon-containing precursor may include any known carbon particles or particulate structures, such as those disclosed in ISO / TS80004-13:2017(en) entitled "Nanotechnologies-Vocabulary-Part 13:Graphene and related two-dimensional (2D) materials".

[0073] In some embodiments, the hydrocarbon gas flowing into reactor 700 may be a short-chain hydrocarbon gas, while in other embodiments, the hydrocarbon gas flowing into reactor 700 may be a long-chain hydrocarbon gas. In some cases, the hydrocarbon gas may be methane (CH4) and / or butane (C4H4). 10 ) may include. In various embodiments, the generation of suitable carbon-based radicals from a non-thermal equilibrium plasma may be based on one or more of the following: Input carbon-containing gas flow rate of 100 standard cubic centimeters / min (sccm) - 5 standard liters / min (slm). • Lower flow rates typically result in improved fidelity and controllability, and thus can contribute to accelerating carbon-based species through reaction chambers 622 and 710. This can lead to a reduction in the doping rates of several additives 604 and 704. • Higher flow rates typically result in higher power output, but can reduce the fidelity and / or directivity of FLG nanoplatelets. Silanes and / or silane-containing liquid precursors such as hexamethyldisiloxane (HMDSO) or hexamethyldisilazane (HMDSN), as well as pure silanes, flow into reactors 600 and 700, providing a variety of suitable silicon source flow rates. In some embodiments, the silicon source flow rate may be one of 1–10 liters / min, 11–20 liters / min, 21–30 liters / min, 31–40 liters / min, 41–50 liters / min, 51–60 liters, 61–70 liters / min, 71–80 liters / min, 81–90 liters / min, 91–100 liters / min, 101–200 liters / min, or 201–530 liters / min, and higher flow rates may allow coating of additional additives corresponding to the accelerated ionized particles 616 and 716. Gas species including lithium (Li), nickel (Ni), manganese (Mn), copper (Cu), trimethylaluminum (TMA), trimethylgallium (TMG), and sulfur (S) flow into reactors 600 and 700, providing one of the following silicon source flow rates: 1–10 liters / min, 11–20 liters / min, 21–30 liters / min, 31–40 liters / min, 41–50 liters / min, 51–60 liters / min, 61–70 liters / min, 71–80 liters / min, 81–90 liters / min, 91–100 liters / min, 101–200 liters / min, or 201–530 liters / min. Higher flow rates may allow for thicker coating of additives to the FLG nanoplatelets 316A and 316B. • Additives containing silica may be introduced into reactors 600 and 700 at a rate of approximately 1% to 75% of the methane gas flow rate, and / or dispersed in particulate form. The additive may be configured to coat and / or decorate the accelerated ionized particles 660. The preferred chemical properties of carbon-containing glass material 650 are due to the presence of approximately 0.1% to 5% additives and approximately 65% ​​to 99% silica, with the remainder being attributable to the carbon-containing material (FLG nanoplatelets, etc.). Reactors 600 and 700 may be adjusted to achieve a light transmittance of at least 96% of the portion of the carbon-containing glass material 650 across the visible frequency spectrum, and / or to adjust the refractive index of the carbon-containing glass material 650. Considering that graphene generally exhibits a neutral light transmission density, uniform coloration of the carbon-containing glass material 650 is provided.

[0074] Figure 8A shows a flowchart illustrating examples of operation 800 for reinforcing a glass material according to several embodiments. In various embodiments, operation 800 may be carried out in a reaction chamber such as reactor 600 in Figure 6 or reactor 700 in Figure 7 (but not limited to). In other embodiments, operation 800 may be carried out in another suitable reaction chamber or chemical apparatus. In some embodiments, operation 800 may be used to inject particles into a carbon-containing glass material including a surface / air contact surface and an interphase region extending from the surface / air contact surface along a direction perpendicular to the surface / air contact surface to the depth of the carbon-containing glass material, as described, for example, with reference to one or more of Figures 1 to 7. In some embodiments, operation 800 begins in block 802, supplying a non-thermal equilibrium plasma containing a plurality of positively charged gas particles and a plurality of ionized inert gas particles to the reaction chamber. Operation 800 proceeds to block 804, accelerating at least a plurality of positively charged gas particles through the reaction chamber based on the application of an external potential to the non-thermal equilibrium plasma. Operation 800 proceeds to block 806, where the surface / air contact surface of the carbon-containing glass material is subjected to an impact with accelerated positively charged gas particles and ionized inert gas particles. Operation 800 proceeds to block 808, where, in response to the impact with the accelerated positively charged gas particles and ionized inert gas particles, an interphase region is formed in the carbon-containing glass material, the interphase region having multiple voids, extending from the surface / air contact surface along a direction perpendicular to the surface / air contact surface to the depth of the carbon-containing glass material. Operation 800 proceeds to block 810, where, in response to at least the impact with ionized inert gas particles, a compressive stress layer is formed in the carbon-containing glass material, the compressive stress layer is located between the interphase region and the surface / air contact surface of the carbon-containing glass material.

[0075] In various embodiments, the carbon-containing glass material may include silicate glass, soda-lime glass, alkali aluminosilicate glass, borosilicate glass, or any combination thereof. In some embodiments, the alkali aluminosilicate glass consists of about 57% to 60% SiO2, about 10% to 25% Al2O3, and about 10% alkaline earth metal.

[0076] In some embodiments, the external potential may be configured to accelerate positively charged gas particles. In addition, or alternatively, the non-thermal equilibrium plasma may also include an intrinsic potential. In some embodiments, the intrinsic potential of the non-thermal equilibrium plasma may be sufficient to inject at least a portion of the FLG nanoplatelets into the interphase region without the application of an external potential to the reaction chamber. In various embodiments, impact may cause multiple microcracks or microvoids to form in one or more portions of the carbon-containing glass material.

[0077] Figure 8B shows a flowchart illustrating an exemplary process 820 for reinforcing a glass material according to several embodiments. In various embodiments, operation 820 may be performed after impacting the surface / air contact surface with accelerated positively charged gas particles and ionized inert gas particles in block 806 of Figure 8A. In other embodiments, operation 820 may be performed simultaneously with the formation of a compressive stress layer in block 810 of Figure 8A. For example, operation 820 begins in block 822, simultaneously impacting the surface / air contact surface with accelerated positively charged gas particles and ionized inert gas particles, and injecting multiple carbon-based radicals separated from a non-thermal equilibrium plasma into the interphase region of the carbon-containing glass material. Operation 820 proceeds to block 824, where multiple multi-layer graphene (FLG) nanoplatelets are formed within the interphase region of the carbon-containing glass material based on the recombination and / or self-nucleation of the multiple carbon-based radicals. In some embodiments, the carbon-based radicals may be injected into the interphase region at one or more different incidence angles.

[0078] In various embodiments, the upper part of the interphase region adjacent to the surface / air contact surface has a relatively high concentration of FLG nanoplatelets, while the lower part of the interphase region distal to the surface / air contact surface has a relatively low concentration of FLG nanoplatelets. In some embodiments, the FLG nanoplatelets in the upper part of the interphase region adjacent to the surface / air contact surface have a size of approximately 20 nanometers (nm), while the FLG nanoplatelets in the lower part of the interphase region distal to the surface / air contact surface have a size of approximately 2 nm. The FLG nanoplatelets in the lower part of the interphase region can be uniformly distributed across the entire plane of the lower part of the interphase region. In one embodiment, the FLG nanoplatelets formed in the gradient portion of the interphase region located between the upper and lower parts of the interphase region gradually decrease in size along the direction toward the depth of the interphase region. In some embodiments, each FLG nanoplatelet may contain 3 to 5 layers of graphene. In other embodiments, the FLG nanoplatelets may have a total weight of less than 2% of the carbon-containing glass material.

[0079] Figure 8C shows a flowchart illustrating an exemplary process 830 for reinforcing a glass material according to several embodiments. In various embodiments, operation 830 may be performed after impacting the surface / air contact surface with accelerated positively charged gas particles and ionized inert gas particles in block 806 of Figure 8A. In other embodiments, operation 830 may be performed simultaneously with the formation of a compressive stress layer in block 810 of Figure 8A. For example, operation 830 begins in block 832 and intercalates additives between adjacent graphene layers within each FLG nanoplatelet. In some cases, the additives may include alkali metals (such as lithium, sodium, potassium, calcium, fluorine, or bromine), transition metals (such as copper or iron), or any combination thereof. In other examples, the additives may include lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), sulfur, or any combination thereof.

[0080] In various embodiments, a first portion of the additive intercalated into the FLG nanoplatelets located in the upper part of the interphase region has a mole fraction of approximately 50%, and a second portion of the additive intercalated into the FLG nanoplatelets located in the lower part of the interphase region has a mole fraction of approximately 2%. In some embodiments, the remaining portion of the additive injected into the area of ​​the interphase region between the first and second portions has a mole fraction that gradually decreases along the direction toward the depth of the interphase region.

[0081] In various embodiments, the additive is configured to self-repair the carbon-containing glass material based on the additive's exposure to ambient air. For example, the additive may oxidize upon exposure to ambient air, forming an oxidizing additive (such as a metal oxide) based on the exposure to ambient air. The oxidizing additive may spread into microcracks and / or microvoids formed in the carbon-containing glass material. The oxidizing additive may also coat the surface of microcracks and / or microvoids formed in the carbon-containing glass material.

[0082] Figures 9A and 9B show flowcharts illustrating examples of operation 900 for forming a carbon-containing glass material according to several embodiments. In various embodiments, operation 900 may be carried out in a reaction chamber such as reactor 600 in Figure 6 or reactor 700 in Figure 7 (but not limited to). In other embodiments, operation 900 may be carried out in another suitable reaction chamber or chemical apparatus. In some embodiments, operation 900 may be used to inject particles into a carbon-containing glass material including a surface / air contact surface, for example, as described with reference to one or more of Figures 1 to 7. In various embodiments, operation 900 begins in block 902, during which hydrocarbon gas and silane are introduced into the reactor. Operation 900 proceeds to block 904, during which an additive containing any one or more of lithium, nickel, manganese, copper, trimethylaluminum (TMA), trimethylgallium (TMG), or sulfur is introduced into the reactor. Operation 900 proceeds to block 906, generating a non-thermal equilibrium plasma based on the excitation of hydrocarbon gases and silanes by microwave energy, the non-thermal equilibrium plasma containing multiple methyl radicals. Operation 900 proceeds to block 908, applying ionic bombardment by at least methyl radicals to the surface / air contact surface of the carbon-containing glass material, the ionic bombardment configured to create an interphase region within the carbon-containing glass material. Operation 900 proceeds to block 910, forming multiple multi-layer graphene (FLG) nanoplatelets within the interphase region of the carbon-containing glass material at various concentration levels based on the recombination or autonucleation of multiple methyl radicals, the multiple FLG nanoplatelets dispersed throughout the interphase region in a non-periodic orientation configured to at least partially suppress the formation or propagation of cracks and / or surface defects in the carbon-containing glass material. Operation 900 proceeds to block 912, doping an additive onto one or more surfaces of at least a portion of the FLG nanoplatelets. Operation 900 proceeds to block 914, in which an additive is intercalated between adjacent graphene layers inside at least a portion of the FLG nanoplatelets formed within the interphase region of the carbon-containing glass material.

[0083] In various embodiments, the glass material may comprise any one or more of silicate glass, soda-lime glass, alkali aluminosilicate glass, or borosilicate glass. In some embodiments, the alkali aluminosilicate glass consists of about 57% to 60% SiO2, about 10% to 25% Al2O3, and about 10% alkaline earth metal. In some other embodiments, the silane may be a silane-containing liquid precursor or silane gas. In one embodiment, the FLG nanoplatelets formed in the interphase region have a total weight of less than 2% of the carbon-containing glass material.

[0084] In various embodiments, the interphase region extends from the surface / air contact surface to a depth of approximately 1 micron in the carbon-containing glass material. In some embodiments, the density of multiple FLG nanoplatelets gradually decreases along the direction extending from the surface / air contact surface to the depth of the interphase region.

[0085] In various embodiments, the upper part of the interphase region adjacent to the surface / air contact surface has a relatively high concentration of FLG nanoplatelets, while the lower part of the interphase region distal to the surface / air contact surface has a relatively low concentration of FLG nanoplatelets. In some embodiments, the FLG nanoplatelets in the gradient portion of the interphase region located between the upper and lower parts of the interphase region gradually decrease in size along the direction toward the depth of the interphase region. In some embodiments, the FLG nanoplatelets in the lower part of the interphase region are uniformly distributed across the entire plane of the lower part of the interphase region.

[0086] In some embodiments, the additive may be intercalated between adjacent graphene layers of the FLG nanoplatelets during post-manufacturing constant temperature treatment in a vacuum or inert atmosphere. The additive may be configured to self-repair the carbon-containing glass material based on exposure of the additive to ambient air. For example, the additive may oxidize based on exposure of the additive to ambient air, forming an oxidizing additive. The oxidizing additive may spread into one or more cracks and / or surface defects in the carbon-containing glass material, and may also coat one or more surfaces of cracks and / or surface defects in the carbon-containing glass material.

[0087] Figure 10 shows a flowchart illustrating an example of operation 1000 for forming a carbon-containing glass material according to several embodiments. In various embodiments, operation 1000 may be performed concurrently with one or more processes of the example of operation 900 in Figures 9A and 9B. For example, operation 1000 begins at block 1002 and induces the formation of microcracks and / or microvoids in the carbon-containing glass material before FLG nanoplatelets are formed in the interphase region. In some embodiments, microcracks and / or microvoids may be formed in the glass material by impacting the surface / air contact surface of the glass material with accelerated charged particles and / or ionized inert gas particles, which can penetrate and / or impact the surface / air contact surface with sufficient force to create small cracks, microcracks, or voids in the glass material without reducing the strength or fracture toughness of the glass material.

[0088] When used herein, the phrase “at least one of” in a list of elements refers to any combination of those elements, including a single component. For example, “at least one of a, b, or c” is intended to include a, b, c, ab, ac, bc, and abc. Various exemplary logic, logic blocks, modules, circuits, and algorithmic processes described in relation to the embodiments disclosed herein may be implemented as electronic hardware, computer software, or a combination of both. Hardware and software compatibility is generally described in terms of functionality and is described for the various exemplary components, blocks, modules, circuits, and processes described above. Whether such functionality is implemented as hardware or software depends on the specific application and the design constraints imposed on the overall system.

[0089] Various modifications to the embodiments described herein may be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments without departing from the spirit or scope of this disclosure. Accordingly, the claims are not intended to be limited to the embodiments shown herein, but the broadest scope that is consistent with this disclosure, the principles disclosed herein, and novel features is permitted.

Claims

1. A carbon-containing glass material, Surfaces exposed to ambient air / air contact surfaces, The interphase region includes an interphase region extending in a certain direction from the surface / air contact surface to a depth in the carbon-containing glass material, The interphase region includes a plurality of multi-layer graphene (FLG) nanoplatelets, The plurality of FLG nanoplatelets have a non-periodic orientation configured to at least partially suppress the formation or propagation of microcracks and / or microvoids in the carbon-containing glass material. A carbon-containing glass material further comprising a compressive stress layer disposed between the interphase region and the surface / air contact surface of the carbon-containing glass material.

2. A carbon-containing glass material, Surfaces exposed to ambient air / air contact surfaces, The interphase region includes an interphase region extending in a certain direction from the surface / air contact surface to a depth in the carbon-containing glass material, The interphase region includes a plurality of multi-layer graphene (FLG) nanoplatelets, The plurality of FLG nanoplatelets have a non-periodic orientation configured to at least partially suppress the formation or propagation of microcracks and / or microvoids in the carbon-containing glass material. The present invention further comprises an additive intercalated between adjacent graphene layers in the FLG nanoplatelet formed within the interphase region, The additive is a carbon-containing glass material comprising any one or more of lithium, sodium, potassium, calcium, or other alkali metals.

3. A carbon-containing glass material, Surfaces exposed to ambient air / air contact surfaces, The interphase region includes an interphase region extending in a certain direction from the surface / air contact surface to a depth in the carbon-containing glass material, The interphase region includes a plurality of multi-layer graphene (FLG) nanoplatelets, The plurality of FLG nanoplatelets have a non-periodic orientation configured to at least partially suppress the formation or propagation of microcracks and / or microvoids in the carbon-containing glass material. The plurality of FLG nanoplatelets are configured to induce compressive residual stress greater than 150 megapascals (MPa) within the interphase region, and are made of a carbon-containing glass material.

4. A surface exposed to ambient air / an air contact surface, The interphase region includes an interphase region extending in a certain direction from the surface / air contact surface to a depth in the carbon-containing glass material, The interphase region includes a plurality of multi-layer graphene (FLG) nanoplatelets, A method for manufacturing a carbon-containing glass material, wherein the plurality of FLG nanoplatelets have a non-periodic orientation configured to at least partially suppress the formation or propagation of microcracks and / or microvoids in the carbon-containing glass material, A method for producing a carbon-containing glass material, comprising forming the plurality of multi-layer graphene (FLG) nanoplatelets in response to the recombination and / or self-nucleation of a plurality of carbon-containing radicals injected into the interphase region.

5. A surface exposed to ambient air / an air contact surface, The interphase region includes an interphase region extending in a certain direction from the surface / air contact surface to a depth in the carbon-containing glass material, The interphase region includes a plurality of multi-layer graphene (FLG) nanoplatelets, A method for manufacturing a carbon-containing glass material, wherein the plurality of FLG nanoplatelets have a non-periodic orientation configured to at least partially suppress the formation or propagation of microcracks and / or microvoids in the carbon-containing glass material, and further comprises a compressive stress layer disposed between the interphase region of the carbon-containing glass material and the surface / air contact surface, A method for manufacturing a carbon-containing glass material, wherein the compressive stress layer is induced by ionic impact of the carbon-containing glass material by a plurality of ionized inert gas particles.

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