Conductive polymers and polymer-derived ceramics

Abstract

This disclosure relates to a resin for forming a conductive polymer material or a polymer-derived ceramic (PDC) material, comprising a photopolymerizable organosilicon monomer and a conductive additive. Also disclosed are conductive polymer materials and PDC materials, polymer materials for forming conductive PDC materials, and methods for forming these materials.

Description

[Technical Field]

[0001] [Cross-reference of related applications] This application claims the interests of Australian Provisional Patent Application No. 2023902235, filed on 12 July 2023, and the entirety of that application constitutes part of this specification by reference.

[0002] This disclosure relates to a resin for forming conductive polymer materials and / or polymer-derived ceramic (PDC) materials, comprising a photopolymerizable organosilicon monomer and a conductive additive. Also disclosed are conductive polymer materials and PDC materials, polymer materials for forming conductive PDC materials, and methods for forming these materials. [Background technology]

[0003] The advent of 3D printing has facilitated the production of polymer articles by printing and shaping resin and polymerizing it to obtain polymer articles. This is due to 3D printing's ability to easily generate customized, complex, and three-dimensionally controlled shapes and article structures, which were difficult to achieve in the past using conventional casting and subtractive manufacturing techniques.

[0004] The advent of 3D printing has also accelerated the production of ceramic articles. By using pre-ceramic resins, 3D-printed and polymerized pre-ceramic polymer articles can be converted into polymer-derived ceramic (PDC) materials. A common process for producing PDC materials involves subjecting pre-ceramic polymer articles to thermal decomposition conditions at temperatures exceeding 1000°C. This induces thermally induced conversion from organic material to inorganic material (i.e., ceramic) and thermal decomposition of certain components of the pre-ceramic polymer. Decomposition tends to release gases that may include carbon dioxide, carbon monoxide, methane, and water. This tends to produce solid, non-porous PDC materials. Therefore, 3D printing allows for more efficient and precisely controlled production of ceramic materials by pre-forming and polymerizing a softer, more deformable pre-ceramic resin before converting the formed article into a hard ceramic material.

[0005] However, 3D printing is still in its early stages. Most 3D printing methods, particularly those for forming PDC materials, are limited to direct ink writing (DIW) techniques, as well as photopolymerization-based techniques such as stereolithography, digital light projection, two-photon lithography, and volumetric printing stereolithography. These techniques are limited to specific resins that form only non-conductive polymer materials and PDC materials, and may be limited to the formation of relatively simple articles manufactured with low resolution.

[0006] 3D printing of conductive electrochemical devices is limited to fused deposition modeling (FDM), direct infusion weld (DIW), and selective laser sintering / melting (SLS / M). FDM printing of electrochemical devices is typically based on a composite filament of graphene and polylactic acid (PLA). This printing method has low resolution, limited resin component selection, produces only low-conductivity articles, and PLA is unstable to hydrolysis. DIW offers greater flexibility in the resin component and produces articles with higher conductivity than FDM, but the resolution is even lower. SLS / M provides higher resolution, but is limited to a few metals (generally stainless steel, titanium, and nickel), and requires expensive printers and raw materials.

[0007] Conductive ceramic and polymer materials are widely used in a variety of socio-economically important applications, including sustainable energy production and storage, pharmaceutical development, surgical and medical devices, environmental and health monitoring, consumer products, and engineering fields. Specific applications of conductive ceramic materials include resistors, semiconductors, and superconductors in electronic circuits, as well as gas sensors and heating elements. Most of these are metallic or metalloids. These applications stem from the fact that these ceramic materials generally exhibit excellent thermal stability, chemical stability, and mechanical strength. Specific applications of conductive polymer materials include semiconductors and supercapacitors in electronic circuits, chemical sensors, electromagnetic shielding, and electrochemiluminescence. These applications stem from the fact that polymer materials generally possess elasticity, biodegradability, non-brittleness, and a soft touch.

[0008] Therefore, although conductive polymer and ceramic materials possess excellent properties that are desirable for realizing initiatives in many fields, their widespread adoption is hindered by manufacturing constraints, particularly those imposed by 3D printing technology.

[0009] Therefore, it is desirable to provide a resin that enables the production of conductive polymer materials and / or ceramic materials using, in particular, 3D printing technology to reduce or avoid one or more of the drawbacks described above and to be utilized in new and existing applications. SUMMARY OF THE INVENTION

[0010] This disclosure is based on the common knowledge that certain components used in resins result in conductive PDC materials formed using the thermal decomposition process of conductive polymer materials and / or polymer materials formed from the resins.

[0011] In one aspect, this disclosure relates to a resin for forming a conductive polymer material or a polymer-derived ceramic (PDC) material, comprising a photopolymerizable organosilicon monomer and a conductive additive.

[0012] In another aspect, this disclosure provides a conductive polymer material or PDC material formed using a photopolymerization process from the resin described herein.

[0013] In another aspect, this disclosure provides a conductive polymer material comprising a photopolymerized photopolymerizable organosilicon monomer and a conductive substance.

[0014] In another aspect, this disclosure provides a polymer material for forming a conductive PDC material, comprising a photopolymerized photopolymerizable organosilicon monomer and a conductive additive.

[0015] In another aspect, this disclosure provides a conductive PDC material comprising a thermally decomposed pre-ceramic polymer and a conductive substance, wherein the pre-ceramic polymer comprises a photopolymerized photopolymerizable organosilicon monomer and a conductive additive.

[0016] In another aspect, the present disclosure provides a method of forming a conductive polymer material, comprising subjecting the resin described herein to photopolymerization conditions to form a conductive polymer material.

[0017] In another aspect, the present disclosure is a method of forming a conductive PDC material, comprising: a) subjecting the resin described herein to photopolymerization conditions to form a preceramic polymer, optionally having conductivity; and b) subjecting the preceramic polymer, optionally having conductivity, to pyrolysis conditions to form a conductive PDC material. The present disclosure provides a method comprising the above.

[0018] In another aspect, the present disclosure provides a polymer material, a conductive polymer material, or a conductive PDC material formed by the method described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] [Figure 1] Graph showing the electrical conductivity (S / m) versus the pyrolysis temperature (°C) of PDC materials containing graphene (uG), graphene oxide nanoplatelet (GO), and carbon nanotube (CNT) as conductive additives, prepared according to Examples 1 / 24 (uG), 2 / 23 (GO), 15 / 19 (CNT 1 wt%), 16 / 20 / 25 (CNT 2 wt%), 17 / 21 / 26 (CNT 3 wt%), and 18 / 22 / 27 (CNT 4 wt%) respectively (the pyrolysis temperatures are various). [Figure 2] Graph showing the porosity (BET surface area, m2 / g) versus the pyrolysis temperature (°C) of PDC materials containing graphene (uG), graphene oxide nanoplatelet (GO), and carbon nanotube (CNT) as conductive additives, prepared according to Examples 1 (uG), 2 / 23 (GO), 15 / 19 (CNT 1 wt%), 16 / 20 (CNT 2 wt%), 17 / 21 (CNT 3 wt%), and 18 / 22 (CNT 4 wt%) respectively (the pyrolysis temperatures are various). [Figure 3]Examples of Example 1 include a) a photograph of a carbon-enriched black glass electrode with interdigitated pillars, including an inset of an SEM image showing porosity, and b) additional SEM images showing porosity. [Figure 4] This is a photograph of a carbon-enriched black glass electrode for Example 2, including an inset of an SEM image showing porosity. [Figure 5] This is a photograph of a polymer electrode having comb-shaped pillars, including an inset of an SEM image showing porosity, for Example 3. [Figure 6] This is a photograph of a composite ceramic electrode made of silicon carbide and silicon oxycarbide, including an inset of an SEM image showing porosity, for Example 4. [Figure 7] This is a photograph of a carbon-enriched black glass electrode for Example 5, including an inset of an SEM image showing porosity. [Figure 8] This is a photograph of a carbon-enriched black glass disk, including an inset of an SEM image showing porosity, for Example 9. [Figure 9] This is a photograph of a carbon-enriched polydimethylsiloxane disk for Example 10, including an inset of an SEM image showing porosity. [Figure 10] This is a photograph of a carbon-enriched black glass electrode for Example 11, including an inset of an SEM image showing porosity. [Figure 11] This is a BET isotherm showing porosity for Example 20. [Figure 12] This is a BET isotherm showing porosity for Example 21. [Figure 13] This is an SEM image showing the porosity of Example 22. [Figure 14] For Example 2, a) an SEM image showing porosity and b) a BET isotherm showing porosity. [Figure 15] This is a BET isotherm showing the porosity of Example 18. [Modes for carrying out the invention]

[0020] Polymer materials are typically formed by processes involving the polymerization of monomers contained in a resin. In other words, polymer materials are usually formed by subjecting a monomer-containing resin to polymerization conditions. PDC materials are typically formed by processes involving the thermal decomposition of preceramic polymers. In other words, PDC materials are usually formed by subjecting a preceramic polymer to thermal decomposition conditions. A preceramic polymer is a polymer material formed when the resin is a preceramic resin containing preceramic monomers. Generally, preceramic resins are converted from organic materials to inorganic materials during thermal decomposition.

[0021] Many polymer materials are either non-conductive or have conductivity that is too low for practical use. Similarly, many PDC materials are either non-conductive or have conductivity that is too low for practical use.

[0022] This disclosure relates to photopolymerizable monomers containing preceramic monomers, photopolymerized polymer materials containing preceramic polymers, PDC materials formed from preceramic polymers, and PDC materials formed from photopolymerized preceramic monomers. This disclosure relates to resins for forming conductive polymer materials and / or PDC materials, comprising at least a photopolymerizable organosilicon monomer and a conductive additive, which are certain components detailed herein. This disclosure also relates to conductive polymer materials and conductive PDC materials. Conductive polymer materials or PDC materials can typically comprise a polymer material or ceramic material and a conductive substance, which is a substance that imparts conductivity to the polymer material or PDC material. This disclosure also relates to resins for forming conductive polymer materials or PDC materials using at least a photopolymerization step, and polymer materials for forming conductive PDC materials using at least a photopolymerization step. Resins for forming conductive polymer materials or PDC materials by photopolymerization can typically comprise at least one photopolymerizable monomer and a conductive additive, which is a substance that imparts conductivity to the polymer material or PDC material formed from the resin. In other words, the resins of this disclosure are particularly useful for forming conductive polymer materials or PDC materials using a photopolymerization process. The photopolymerization process is preferably carried out as part of a 3D printing process. Therefore, this disclosure provides 3D printed conductive polymer materials or conductive PDC materials formed using a photopolymerization process. This disclosure also provides porous conductive polymer materials and conductive PDC materials, as well as microstructures of conductive polymer materials and conductive PDC materials.

[0023] definition Unless otherwise specified, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. Methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this disclosure, but preferred methods and materials are described. Many terms are defined throughout this disclosure for the purposes of this disclosure.

[0024] The term "conductivity" refers to a material's ability to conduct electric current. Whether a material is conductive or not can be determined by its "electrical conductivity." "Electrical resistivity" is the reciprocal of electrical conductivity and refers to a measure of a material's ability to resist the conduction of electric current. A "conductive additive" is a substance that imparts conductivity to a material. The term "imparts conductivity" refers to the ability of a substance contained in a material to increase its electrical conductivity. A conductive additive in a resin may be conductive in the resin itself and in the polymer or PDC material formed from the resin, or it may not be conductive in the resin itself but be conductive in the polymer or PDC material formed from the resin, or it may be converted into a conductive substance in the polymer or PDC material during the process of the resin being converted into that material. A conductive additive that is conductive in the resin and the polymer or PDC material formed therefrom may be called a "conductive substance." A conductive additive that is not conductive in the resin but is converted into a conductive substance during the process of the resin being converted into a polymer or PDC material may be called a "pre-conductive substance." Electrical conductivity and resistivity can be determined experimentally using methods known in the art. One known method is the four-point probe measurement, which measures the conductivity and resistivity of a material layer. This typically uses four probes placed linearly and equally spaced in contact with the material, with a current flowing between the outer probes. The inner probes measure the voltage drop as the current passes through the material. Electrical conductivity and resistivity can be calculated from the measured values ​​of the applied current and voltage. Resistivity obtained by the four-point probe method is typically expressed as sheet resistance in ohms / square and / or electrical resistivity in ohms / meter. Electrical conductivity obtained by the four-point probe method is typically expressed as conductivity in siemens / meter.

[0025] A "polymer material" is a material that is formed or can be formed by the polymerization of at least one monomer. A "monomer" is a chemical species that can polymerize to form a polymer material. A "photopolymerized" polymer material is a polymer material that is formed by using a photopolymerization process alone or in combination with other steps of the method. "Photopolymerization" is polymerization that is induced by light (directly or by the use of a photoinitiator). Monomers that can participate in photopolymerization are "photopolymerizable".

[0026] This disclosure uses photopolymerizable organosilicon monomers. "Organosilicon" refers to a chemical compound having a chemical structure that includes a silicon atom covalently bonded to a carbon atom. A photopolymerizable organosilicon monomer is a monomer that contains a photopolymerizable functional group.

[0027] The term "preceramic" refers to the ability of a material to be converted into a ceramic material by a pyrolysis process, either alone or in combination with other steps in the method. Therefore, a "preceramic polymer" is a polymer material that can be converted into a ceramic material using a method that includes a pyrolysis process. On the other hand, a "preceramic resin" is a material containing at least one monomer that can be converted into a preceramic polymer using a method that includes a polymerization process. Such monomers in a preceramic resin may be called "preceramic monomers." "Polymer-derived ceramic" (PDC) materials are ceramic materials manufactured by the pyrolysis of preceramic polymers.

[0028] A “green body” is a formed article containing a polymer material, which may undergo additional processing steps such as cleaning and / or thermal decomposition (if the polymer material is a preceramic polymer). Green bodies can be formed by forming processes known in the art. Forming processes particularly applicable to this disclosure include stereolithography, digital light projection, two-photon lithography, continuous liquid interface methods, direct ink writing, and 3D printing methods such as inkjet printing. These methods are widely known in the art.

[0029] A "microstructure" refers to a physical feature or structure characterized by dimensions less than 1 mm, particularly dimensions between approximately 1 micron and less than 1 mm. For example, a microstructure can be characterized by one or more of the three principal axes of three-dimensional space (i.e., generally represented by the X, Y, and Z axes) being less than 1 mm. As an example, a cylindrical projection from a surface with a height of 50 microns and a diameter of 50 microns can be described as a microstructure, or a structure with dimensions within the microstructure range. A structure may also be a feature characterized by the absence of material (i.e., a "negative feature"), such as a cylindrical hole with a depth of 50 microns and a diameter of 50 microns. What distinguishes a microstructure from microscopic irregularities on a surface is the controlled formation or arrangement of the microstructure, which is different from random or irregular microscopic features. A microstructure may also be the structure of a larger article, i.e., a macrostructure.

[0030] A "macrostructure" generally refers to a structure characterized by dimensions of 1 mm or more. For example, articles made of polymer or PDC material can be characterized by one or more of the three principal axes of three-dimensional space (i.e., generally represented by the X, Y, and Z axes) being 1 mm or more. Dimensions can range from 1 mm to 100 mm, but are preferably 1 mm to 50 mm, and more preferably 1 mm to 10 mm. In the case of preceramic polymers, the dimensions of the green body may be larger than those of PDC material formed by the thermal decomposition of the green body by a coefficient that takes shrinkage into account.

[0031] Having "porous" properties means that it contains pores. A "pore" is a space that does not contain solid material. Pores can be considered hierarchically in terms of pore size, such as micropores, mesopores, and macropores. A "micropore" refers to a pore with a diameter of less than 2 nm. A "mesopore" refers to a pore with a diameter of 2 nm to 50 nm. A "macropore" refers to a pore with a diameter of 50 nm to 100 micrometers. Macropores can be further considered as submacropores, intermacropores, and supermacropores, which refer to macropores with diameters of 50 nm to 1 micrometer, 1 micrometer to 10 micrometers, and 10 micrometers to 100 micrometers, respectively. "Diameter" does not limit the shape of the pore, but refers to the maximum axial dimension. Similarly, "microporous" refers to the inclusion of micropores, while "mesoporous" refers to the inclusion of mesopores, and "macroporous" refers to the inclusion of macropores. Pore ​​size can be experimentally determined using methods known in the art. Known methods include gas adsorption (including the use of BET surface analyzers), scanning electron microscopy, and immersion methods (including mercury porosimetry). Similarly, porosity is directly related to specific surface area; greater porosity results in a larger specific surface area. Specific surface area can be experimentally determined using methods known in the art, including gas adsorption (including the use of BET surface analyzers) and immersion methods (including mercury porosimetry).

[0032] Resins, polymer materials, and PDC materials It is surprising that the resins of this disclosure are applicable to the formation of conductive polymer materials and PDC materials. Because additives tend to degrade the integrity of the polymer materials and PDC materials formed from them, it has conventionally been difficult to form polymer articles and PDC articles, particularly 3D printable articles, based on resins containing non-polymerizable additives beyond trace amounts. Furthermore, photopolymerization has not been utilized in the production of conductive polymer materials and PDC materials, particularly in production using 3D printing technology. This disclosure finds that by combining resin components containing the photopolymerizable organosilicon monomers and conductive additives described herein, conductive polymer materials and PDC materials can be formed without loss of material integrity, with reduced risk of material integrity impairment, or with less degree of integrity degradation.

[0033] In preferred embodiments, the conductive polymer material has an electrical conductivity of at least 0.1 μS / m, preferably at least 1 μS / m, preferably at least 10 μS / m, preferably at least 30 μS / m, and may have an electrical conductivity of at least 40 μS / m, at least 70 μS / m, or at least 100 μS / m. The electrical conductivity may be as high as 1 S / m, 900 mS / m, 800 mS / m, 700 mS / m, 600 mS / m, or 500 mS / m. Any minimum and maximum values ​​can be combined without limitation. For example, when expressed as a range, electrical conductivity can be given as 0.1 μS / m to 1 S / m, 1 μS / m to 800 mS / m, 10 μS / m to 700 mS / m, 30 μS / m to 500 mS / m, 70 μS / m to 500 mS / m, or 100 μS / m to 500 mS / m. Generally speaking, the more conductive additives there are, the higher the electrical conductivity of the conductive polymer material. Also, the higher the electrical conductivity of the conductive additive itself, or the conductive substance formed from it (in the case of a conductive substance precursor), the higher the electrical conductivity of the conductive polymer material.

[0034] In a preferred embodiment, the conductive PDC material has an electrical conductivity of at least 0.1 μS / m, preferably at least 1 μS / m, preferably at least 10 μS / m, preferably at least 40 μS / m, preferably at least 70 μS / m, and preferably at least 100 μS / m. The electrical conductivity may be as high as 600 S / m, 500 S / m, 400 S / m, 300 S / m, 200 S / m, 150 S / m, or 100 S / m. Any minimum and maximum values ​​can be combined without limitation. For example, when expressed as a range, the electrical conductivity can be 0.1 μS / m to 600 S / m, 1 μS / m to 500 S / m, 10 μS / m to 500 S / m, 40 μS / m to 300 S / m, 70 μS / m to 200 S / m, or 100 μS / m to 150 S / m. Similar to conductive polymer materials, generally speaking, the greater the amount of conductive additive, the higher the electrical conductivity of the conductive PDC material. Also, the higher the electrical conductivity of the conductive additive itself, or the conductive substance formed from it (in the case of a conductive substance precursor), the higher the electrical conductivity of the conductive PDC material.

[0035] The resins of this disclosure are applicable to the formation of microstructures and macrostructures of polymers and PDCs, including microstructures of larger articles. Key findings regarding microstructure formation in PDC material formation are described in the specifications of Australian Provisional Patent Application No. 2022901435, filed on 27 May 2022, and PCT Patent Application No. PCT / AU2023 / 050159, filed on 8 March 2023, the respective disclosures of which are incorporated herein by reference in whole. The resins described herein are suitable for forming microstructures of polymers and PDCs, particularly PDC articles containing microstructures, because the resins undergo linear and volume contraction when thermally decomposed from a green material, forming a smaller PDC material than the green material before thermal decomposition. This is because, during thermal decomposition, the material undergoes a thermally induced conversion from organic to inorganic, and as liquid and gaseous material is released, preceramic polymers typically undergo a certain degree of linear and volume contraction. The degree of shrinkage can be controlled, in one way, by using resins characterized by different degrees of polymerization, and by using resins that are porous or that form porosity during post-polymerization processing. Generally speaking, the lower the degree of polymerization, the greater the degree of shrinkage during thermal decomposition, as unpolymerized monomers are released as liquid and gas. Similarly, the greater the porosity, the greater the degree of shrinkage, as more liquid and gas are released from the porous structure during thermal decomposition, and the porous structure subsequently collapses into smaller volumes. This makes it possible to manufacture PDC articles containing microstructures with dimensions below resolution, i.e., smaller than the minimum practical resolution obtained by the method used to form the green body. For example, many desktop 3D printers have a minimum practical resolution of about 500 microns (determined by the properties of the resin being printed, e.g., viscosity). By utilizing the shrinking ability of preceramic resins formulated according to this disclosure, it is possible to form microstructures with lower resolution. The primary use of shrinkage in the formation of PDC materials is described in the specifications of Australian Provisional Patent Application No. 2022901435 and PCT Patent Application No. PCT / AU2023 / 050159, mentioned above.Generally speaking, for similar reasons, the electrical conductivity of conductive PDC materials tends to be higher than that of conductive polymer materials containing the same amount of conductive additives. One reason for this is thought to be that, under the same conditions, conductive PDC materials contain conductive additives at a higher density (per volume of material) than conductive polymer materials.

[0036] The resins of this disclosure can be used to form porous polymer materials and PDC materials. Key findings in the formation of porous PDC materials are described in the specifications of Australian Provisional Patent Application No. 2022900557, filed March 8, 2022, and PCT Patent Application No. PCT / AU2023 / 050161, filed March 8, 2023, the respective disclosures of which are incorporated herein by reference. Porous polymer materials and PDC materials can be formed from resins that are porous and maintain their porosity during polymerization and thermal decomposition, or from resins that can introduce porosity during polymerization and / or thermal decomposition. Resins can be porous by containing porous materials, such as porous particles, which can maintain porosity within polymer materials or PDC materials formed from porous resins. Porosity can be introduced into polymer materials during the polymerization of resins containing particulate materials, such as porous particles or particulate conductive additives. During polymerization, crosslinks may be forced to form around particulate matter, creating pores. The degree of porosity can be controlled by the porosity of the porous material and the amount of porous material included. Porosity can be introduced into the PDC material during the thermal decomposition of the preceramic polymer. The degree of porosity of the PDC material can be controlled by the porosity of the porous material, controlling the maximum temperature during thermal decomposition to below the temperature at which the porosity of the material collapses, using resins characterized by different degrees of polymerization for the purpose of burning and removing unpolymerized monomers, using two or more monomers characterized by different ceramic yields, and / or adding pologens to the resin that are burned and removed during thermal decomposition.

[0037] It is surprising that the resin of the present disclosure is applicable to the formation of porous and conductive polymer materials and PDC materials. As described above, additives such as porous substances in the resin tend to reduce the integrity of the polymer materials and PDC materials formed therefrom. Similarly, porosity reduces the density of the material and intuitively has an impact on reducing the integrity of the polymer material or PDC material. However, in the present disclosure, it has been found that certain components of the resin described herein enable the formation of porous and conductive polymer materials and PDC materials. This is provided by a photopolymerizable organosilicon monomer, which tends to have one or both of high reactivity and stability, and forms a polymer material characterized by one or both of a high degree of polymerization and stability that weakens the destabilizing effects of conductive additives and porosity.

[0038] However, generally speaking, the porosity of the conductive polymer materials that can be formed from the resins disclosed herein is characterized by an upper limit value before the destabilizing effects of the conductive additives and porosity may exceed the stabilizing effects of the photopolymerizable organosilicon monomers and the polymerized materials they form. Thus, generally speaking, the porosity of the conductive polymer materials is characterized by an upper limit of about 150 m 2 / g. This is about 5 m 2 / g, 10 m 2 / g, 20 m 2 / g, 30 m 2 / g, 40 m 2 / g, 50 m 2 / g, 60 m 2 / g, 70 m 2 / g, 80 m 2 / g, 90 m 2 / g, 100 m 2 / g, 110 m 2 / g, 120 m 2 / g, 130 m 2 / g, 140 m 2 / g, and 150 m 2 / g, including about 5 m 2 / g to 150 m 2It may also have a porosity of / g. This includes cases where it is analyzed by BET surface area analysis, sometimes called BET specific surface area. This is 100m 2 This does not necessarily apply to conductive PDC materials, which may be characterized by porosity exceeding / g.

[0039] Porosity can be imparted to polymer materials and PDC materials as micropores, mesopores, and / or macropores. Micropores can be imparted by porous substances in the resin. Mesopores can similarly be imparted by porous substances in the resin and can also be formed during polymerization and / or thermal decomposition. Macropores can be formed by pologens in the resin that are removed by combustion during thermal decomposition. However, macropores tend to have a greater destabilizing effect than micropores and mesopores. Therefore, in preferred embodiments, porosity is substantially imparted by micropores and / or mesopores. Accordingly, in preferred embodiments, the PDC materials described herein are formed from preceramic polymers that contain little or no pologens, or substantially or virtually no pologens, as will be described in more detail below.

[0040] The manufactured materials are useful in many engineering and scientific fields where conductive materials are used, such as electrodes including microelectrodes, catalyst supports, bipolar plates, electrocatalytic reactors, and electrochemical devices.

[0041] Photopolymerizable organosilicon monomers This disclosure uses a photopolymerizable organosilicon monomer, which is an organosilicon compound containing a photopolymerizable functional group.

[0042] organosilicon compounds To begin with, organosilicon compounds that form the basis of photopolymerizable organosilicon monomers are generally based on a main chain structure of repeating motifs containing silicon atoms, and in that sense, they are generally oligomeric or polymeric compounds. Examples applicable to this disclosure include polysiloxanes, polycarbosiloxanes, polysilsesquioxanes, polycarbosilanes, polysilylcarbodiimides, polysilsesquicarbodiimides, polysilazanes, polysilsesquiazanes, polyborosilanes, polyborosiloxanes, and polyborosilazanes. Since silicon and carbon atoms are generally tetravalent, organosilicon, including the main chain structure of polymeric organosilicon, is generally substituted with carbon-containing organic chemical groups. With respect to organosilicon, "substitution" means that any one or more hydrogen atoms bonded to the atom in question are replaced, as long as the valency of the atom is not exceeded and a stable compound is obtained. Non-limiting examples of suitable substituents include substituents of the R group as defined below.

[0043] In preferred embodiments, the organosilicon compound forming the basis of the photopolymerizable organosilicon monomer is selected from one or more of polysiloxanes, polycarbosiloxanes, polycarbosilanes, polysilylcarbodiimides, and polysilazanes. Preferably, these organosilicon compounds have the chemical structures of the following formulas 1, 2, 3, 4, and 5: [ka] (In the formula, n represents the main chain structure of repeating motifs containing silicon atoms, and is an independent integer between 2 and 15, and R1, R2, R3, and R4 are independent of each integer n, H, C1~C 18 Substituted or unsubstituted alkyl, C1-C 18The R1 and R2 pairs and the R3 and R4 pairs are independently selected from the group consisting of substituted or unsubstituted alkyl ethers, phenyls, and halides, provided that for all integers of n, neither R1 nor R2 is a H, alkyl ether, or halide. Preferably, for all integers of n, neither R1 nor R2 nor R3 nor R4 is a H, alkyl ether, or halide. Preferably, each of the R1 and R2 pairs and the R3 and R4 pairs is identical for all integers of n.

[0044] In formulas 2, 3, and 5, the hydrogen atoms of the CH2 and NH groups may be substituted with one or more groups defined for R1. As described above, organosilicon is a chemical compound having a chemical structure containing a silicon atom covalently bonded to a carbon atom, and this includes the organosilicon monomers of formulas 1 to 5, where n is an integer equal to 1. That is, in formulas 1 to 5, n may be an integer of 1 or more independently, or an integer from 1 to 15.

[0045] The organosilicon compound that forms the basis of the photopolymerizable organosilicon monomer may be a polyoctahedralsilsesquioxane, preferably one or more of polysilsesquioxanes, polysilsesquicarbodiimides, and polysilsesquiazanes substituted with one or more groups defined for R1. In other words, the polyoctahedralsilsesquioxane is C1-C 18 Substituted or unsubstituted alkyl groups, C1-C 18 It may be substituted with one or more groups selected from the group consisting of substituted or unsubstituted alkyl ethers, phenyls, and halides.

[0046] The organosilicon compounds that form the basis of photopolymerizable organosilicon monomers have the following chemical structures: Formulas 6, 7, and 8: [ka] (In the formula, n represents the main chain structure of repeating motifs containing silicon atoms, and is an independent integer between 2 and 15. R1, R2, R3, and R4 are as defined above, and, R5 and R6 are independent of each integer n, and are H, OH, C1~C 18 Substituted or unsubstituted alkyl, C1-C 18 You can also choose one or more from polyborosilanes, polyborosiloxanes, and polyborosilazanes having (independently selected from the group consisting of substituted or unsubstituted alkyl ethers and phenyl). Preferably, R5 and R6 are the same for all integers of n, such as R1, R2, R3, and R4.

[0047] As described above, organosilicon is a chemical compound having a chemical structure that includes a silicon atom covalently bonded to a carbon atom, and this includes organosilicon compounds of formulas 6 to 8 (where n is an integer equal to 1). That is, in formulas 6 to 8, n may be an integer of 1 or greater, or an integer from 1 to 15.

[0048] In a preferred embodiment, the organosilicon compound is selected from one or more polysiloxanes, polycarbosiloxanes, and polycarbosilanes, where n is independently an integer between 2 and 5, and R1, R2, R3, and R4 are identical for all integers of n and are independently selected from the group consisting of H, methyl, and isobutyl, provided that the pairs R1 and R2 and R3 and R4 are not both H and are polysilsesquioxanes substituted with the group defined for R1, preferably isobutyl.

[0049] In the most preferred embodiment, the organosilicon compound is a polysiloxane, where n is independently an integer between 2 and 5, and R1, R2, R3, and R4 are identical for all integers of n and are independently selected from the group consisting of H, methyl, and isobutyl, except that the pair of R1 and R2 and the pair of R3 and R4 are not both H.

[0050] Photopolymerizable organosilicon monomers Photopolymerizable organosilicon monomers are the aforementioned organosilicon compounds that have been substituted to include a photopolymerizable functional group, i.e., the aforementioned organosilicon compounds containing a photopolymerizable functional group.

[0051] The photopolymerizable functional group may be substituted at one or more positions in the organosilicon compound, and in the case of oligomeric or polymeric organosilicon compounds, it may be substituted at any position (possibly multiple positions) along the main chain structure. Alternatively, or in addition, particularly in the case of oligomeric or polymeric organosilicon compounds, the photopolymerizable functional group may be substituted at the terminal, i.e., at one or more terminal groups of the main chain structure. With respect to photopolymerizable organosilicon monomers, "substitution" means that any one or more nonpolymerizable chemical groups of the organosilicon compound bonded to the atom in consideration are replaced by a photopolymerizable functional group, provided that the valence does not exceed and a stable compound is obtained. Non-limiting examples of suitable substituents include those of the photopolymerizable functional groups defined below.

[0052] Therefore, photopolymerizable organosilicon monomers can be obtained by substituting one or more of the R1, R2, R3, and R4 terminal groups of the above organosilicon compounds, or terminal groups (or more), with one or more photopolymerizable functional groups of one or more types. Different “types” of photopolymerizable functional groups are those having different chemical structures. The type of photopolymerizable functional group (or more) used is not particularly important, as long as it enables the photopolymerization of the organosilicon monomer (or more). One type of photopolymerizable reactive group selected to react with itself may be used, or two or more photopolymerizable functional groups selected to react with each other (i.e., complementary) may be used. Alternatively, or in addition, the photopolymerizable functional groups may be selected to react with a crosslinking agent added to the resin.

[0053] As described above, photopolymerizable organosilicon monomers tend to possess either high reactivity or stability, or both, forming polymer materials characterized by either high degree of polymerization or stability. For example, photopolymerizable organosilicon monomers, through their high reactivity (optionally via crosslinking agents) either themselves or with other photopolymerizable monomers, can form polymer materials characterized by a high degree of polymerization, or polymer materials characterized by high stability, or, through their high reactivity, can form polymer materials characterized by both a high degree of polymerization and high stability. Photopolymerizable organosilicon monomers can be selected based on the degree of polymerization and / or stability obtained during polymerization. In other words, they can be selected to form polymer materials characterized by a specific degree of polymerization and / or stability.

[0054] "Degree of polymerization" refers to the polymerization yield and is the ratio of reacted (polymerized / crosslinked) polymerizable functional groups or monomers in the polymer material to unreacted (unpolymerized / uncrosslinked) polymerizable functional groups or monomers (i.e., those intended to polymerize with themselves and / or other monomers (which may be multiple) (optionally including polymerization via crosslinking groups)). Photopolymerizable organosilicon monomers can be selected to have a high degree of polymerization with a polymerization yield of over 80%, and even "very high degrees of polymerization" of over 90%, even over 95%, or over 98%, and also include "complete polymerization" of over 99%, or 100% to a substantially detectable extent. Photopolymerizable organosilicon monomers may also be selected to have a "moderate degree of polymerization" with a polymerization yield of 60% to 80%. Moderate degrees of polymerization are particularly applicable to polymer materials with high stability, but are less suitable for other applications. Photopolymerizable organosilicon monomers tend not to form polymer materials characterized by a "low degree of polymerization," which is a polymerization yield of 60% or less.

[0055] "Stability" refers to a material's ability to resist degradation. Photopolymerizable organosilicon monomers can be selected based on the high stability of the photopolymerized polymer materials formed using them and / or themselves.

[0056] High degrees of polymerization are particularly suitable for forming relatively high-density polymer and PDC materials, although these materials may be characterized by relatively low porosity. Moderate degrees of polymerization are particularly suitable for forming porous polymer and PDC materials. High stability is suitable as an aid to counteract the destabilizing effects of conductive additives and / or porosity.

[0057] The selection of photopolymerizable organosilicon monomers based on their degree of polymerization and stability can usually be achieved by selecting photopolymerizable functional groups.

[0058] The photopolymerizable functional group(s) may be selected from the group consisting of hydroxyl, epoxide, vinyl, allyl, ethynyl, thiol, glycidyl, acrylate, and thiocyanate (or the group including the motif).

[0059] In preferred embodiments, the photopolymerizable functional group(s) are selected based on their ability to participate in the photopolymerization chemistry of thiol-ene, thiol-acrylate, or acrylate. Resins containing certain components described herein, including photopolymerizable monomer(s) involved in thiol-ene chemistry, tend to form polymer materials that are highly reactive and characterized by a high degree of polymerization, but are relatively unstable. On the other hand, photopolymerizable monomer(s) involved in acrylate chemistry tend to be relatively stable, but may form polymer materials that are less reactive and characterized by a relatively low degree of polymerization. On the other hand, photopolymerizable monomer(s) involved in thiol-acrylate chemistry tend to be relatively stable and can form polymer materials characterized by a high degree of polymerization. Therefore, in preferred embodiments, the photopolymerizable organosilicon monomer(s) include one or two photopolymerizable functional groups, preferably selected from allyl, vinyl, thiol, and acrylate, more preferably selected from thiol and acrylate, to participate in thiol-acrylate photopolymerization chemistry. In a preferred embodiment, if the resin contains another photopolymerizable monomer, the photopolymerizable organosilicon monomer comprises one type of photopolymerizable functional group, preferably a photopolymerizable functional group selected as described above, more preferably a thiol or an acrylate, while the other photopolymerizable organosilicon monomer comprises one type of complementary photopolymerizable functional group, preferably the other of a thiol or an acrylate.

[0060] Examples of optional crosslinking agents applicable to these embodiments include diacrylates and dithiols.

[0061] Photopolymerizable organosilicon monomers, which are preceramic monomers, are characterized by their ceramic yield. "Ceramic yield" refers to the mass of PDC material obtained by thermal decomposition (i.e., the mass of converted PDC material as a percentage of the mass of preceramic monomer), expressed as a percentage of the mass of the preceramic monomer. For example, if 10 g of PDC material is formed by the thermal decomposition of 11 g of preceramic monomer, the ceramic yield of the preceramic monomer is 10 / 11 × 100 = 91%.

[0062] The photopolymerizable organosilicon monomer can be present in the preceramic resin in an amount of at least about 15% by weight, 20% by weight, 25% by weight, 30% by weight, or at least about 35% by weight of the preceramic resin, and up to a maximum of about 98% by weight, 95% by weight, 90% by weight, or about 80% by weight of the preceramic resin. The photopolymerizable organosilicon monomer can also be present in the preceramic resin in an amount of at least about 10% by volume, 15% by volume, 20% by volume, 25% by volume, or at least about 30% by volume of the preceramic resin. The amount of the photopolymerizable organosilicon monomer can be about 95% by volume or less, 90% by volume or less, 80% by volume or less, 75% by volume or less, or about 70% by volume or less of the preceramic resin. Any minimum and maximum values ​​can be combined without limitation. For example, the amount can be 15% to 98% by weight of the preceramic resin, 15% to 80% by weight of the composition, etc. In some embodiments, the photopolymerizable organosilicon monomer may be present in an amount of at least about 60% to about 95% by weight, preferably about 65% to about 90% by weight, more preferably about 70% to about 85% by weight, for example, 75% to 80% by weight.

[0063] The ceramic yield of a preceramic monomer is a chemical property that is typically influenced by the chemical structure of the monomer. Methods for determining the ceramic yield of a preceramic monomer are known in the art and generally involve exposing the preceramic monomer to thermal decomposition conditions in a thermogravimetric analyzer (TGA). Generally, in a TGA, the weight of the preceramic monomer during thermal decomposition as it is converted into a PDC material is measured. The maximum thermal decomposition temperature is typically at least about 600°C and is often about 850°C to ensure complete conversion to a PDC material. Complete conversion is generally indicated by the experimental determination that the weight change between multiple time points at the maximum thermal decomposition temperature is zero. A TGA can determine the starting and final weights after thermal decomposition, and the ceramic yield can be calculated based on these. Detailed methods are shown in the examples. In a preferred embodiment, the ceramic yield is determined using this method, which is referred to herein as "TGA 850 "Ceramic yield" or "TGA" 850 It is sometimes referred to as the "method." "850" represents the highest temperature reached during the analysis.

[0064] Typical photopolymerizable organosilicon monomers include methacryloxypropyl-terminated polydimethylsiloxane (ceramic yield approximately 18%), (mercaptopropyl)methylsiloxane homopolymer (ceramic yield approximately 55%), allyl hydride polycarbosilane, and vinyl methoxysiloxane homopolymer (ceramic yield approximately 50%). When only one type of photopolymerizable organosilicon monomer is present in the resin, (mercaptopropyl)methylsiloxane homopolymer is preferred.

[0065] Other monomers The resins of this disclosure may contain additional photopolymerizable monomers, such as second and subsequent photopolymerizable organosilicon monomers and / or one or more photopolymerizable organic monomers. If the resin contains two or more photopolymerizable organosilicon monomers, the “first photopolymerizable organosilicon monomer” is entirely synonymous with the “photopolymerizable organosilicon monomer” described above, and photopolymerizable organosilicon monomers such as the “second,” “third,” etc., may also be referred to in the same way. The terms “first,” “second,” etc., are not intended to imply any order or hierarchy, but are simply used to distinguish between different photopolymerizable organosilicon monomers.

[0066] Second and subsequent photopolymerizable organosilicon monomers The second photopolymerizable organosilicon monomer can be as described above with respect to the first photopolymerizable organosilicon monomer, but has a different chemical structure in its skeleton, substituents, or photopolymerizable functional groups.

[0067] In other words, in a preferred embodiment, the second photopolymerizable organosilicon monomer is a polysilsesquioxane, polysilsesquicarbodiimide, or polysilsesquiazane having the structure of formula 1, formula 2, formula 3, formula 4, formula 5, formula 6, formula 7, or formula 8, or substituted with one or more of the above-mentioned photopolymerizable functional groups.

[0068] The second photopolymerizable organosilicon monomer can be selected based on the degree of polymerization and / or stability of the polymer material formed from the resin containing this monomer, as described above with respect to the first photopolymerizable organosilicon monomer.

[0069] The photopolymerizable functional group of the second photopolymerizable organosilicon monomer does not need to be complementary to the photopolymerizable functional group of the first photopolymerizable organosilicon monomer. Rather, for the second photopolymerizable organosilicon monomer, one photopolymerizable functional group can be selected that reacts with itself under photopolymerization conditions but does not react with the photopolymerizable functional group of the first photopolymerizable organosilicon monomer. Alternatively, two or more photopolymerizable functional groups that react with each other (i.e., complementary) under photopolymerization conditions but do not react with the photopolymerizable functional group of the first photopolymerizable organosilicon monomer may be used. Or, in addition, the photopolymerizable functional group may be selected to react with a crosslinking agent added to the resin.

[0070] In a preferred embodiment, the photopolymerizable functional group(s) of the second organosilicon monomer are selected to be complementary to the photopolymerizable functional group(s) of the first photopolymerizable organosilicon monomer. In this case, preferred photopolymerizable functional groups of the second photopolymerizable organosilicon monomer are selected from the group consisting of hydroxyl, epoxide, vinyl, allyl, ethynyl, thiol, glycidyl, acrylate, and thiocyanate (preferred photopolymerizable functional groups of the first photopolymerizable organosilicon monomer are shown in parentheses).

[0071] In a preferred embodiment, the photopolymerizable functional group(s) of the second photopolymerizable organosilicon monomer are selected based on their ability to participate in the photopolymerization chemistry of thiol-ene, thiol-acrylate, and acrylate. Therefore, in a preferred embodiment, the second photopolymerizable organosilicon monomer comprises one or two photopolymerizable functional groups, preferably selected from allyl, vinyl, thiol, and acrylate, more preferably from thiol and acrylate, to participate in the photopolymerization chemistry of thiol-acrylate. In a preferred embodiment, if the first photopolymerizable organosilicon monomer is included in the resin, the first photopolymerizable organosilicon monomer comprises one photopolymerizable functional group, preferably thiol, acrylate, allyl, or vinyl, and the second photopolymerizable organosilicon monomer comprises one complementary photopolymerizable functional group, preferably thiol, acrylate, allyl, or vinyl.

[0072] The ceramic yield of photopolymerizable organosilicon monomers typically varies depending on the chemical structure of the monomer. Therefore, since the second photopolymerizable organosilicon monomer is chemically different from the first photopolymerizable organosilicon monomer, the ceramic yield of the second photopolymerizable organosilicon monomer will differ from the ceramic yield of the first photopolymerizable organosilicon monomer. However, this does not preclude the possibility that different photopolymerizable organosilicon monomers may coincidentally have the same ceramic yield, nor does it preclude the applicability of these embodiments to the present disclosure.

[0073] The ceramic yield of the second photopolymerizable organosilicon monomer may be similar to or different from the ceramic yield of the first photopolymerizable organosilicon monomer. In some embodiments, the ceramic yields of the two monomers may differ by about 15% or less, i.e., differences of about 15% or less, 14% or less, 13% or less, 12% or less, 11% or less, 10% or less, 9% or less, 8% or less, 7% or less, 6% or less, 5% or less, 4% or less, 3% or less, 2% or less, and 1% or less, including differences that are undetectable. In some embodiments, the ceramic yields of the two monomers may differ by about 10% or less, or about 5% or less. In some embodiments, the ceramic yields of the two monomers may differ by 5% or more, or by any integer between 10% or more, 15% or more, 20% or more, 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 55% or more, or up to a practical limit. Preferably, the ceramic yield of the two monomers is about 15% or less, as described above. The ceramic yield of the first photopolymerizable organosilicon monomer may be referred to as the "first ceramic yield," and the ceramic yield of the second photopolymerizable organosilicon monomer may be referred to as the "second ceramic yield," and so on.

[0074] Adding two photopolymerizable organosilicon monomers with different ceramic yields (especially when the difference is 5% or more) is suitable for embodiments for forming porous PDC materials and / or embodiments for causing shrinkage. This is because porosity is formed during thermal decomposition, allowing a larger amount of liquid and gas to escape. In this case, the porosity collapses during thermal decomposition, resulting in a high shrinkage rate.

[0075] The amount of the second photopolymerizable organosilicon monomer in the resin can be such that the first and second photopolymerizable organosilicon monomers are present in a 1:1 ratio with respect to the photopolymerizable functional groups. Alternatively, one photopolymerizable organosilicon monomer may be present in excess of the other with respect to the photopolymerizable functional groups. This may be, for example, a ratio of 1:1 to 1:10, or 1:1 to 1:5, or 1:1 to 1:3, or 1:1 to 1.2, such as 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2. The excess amount can be used to promote the polymerization of the photopolymerizable organosilicon monomer present, for example, as a limiting reagent, compared to when there is no excess, but the excess may remain unpolymerized in the formed polymer material. Residual unpolymerized photopolymerizable organosilicon monomers can be removed during thermal decomposition, for example, when the polymer material is a preceramic polymer. In embodiments for forming porous polymer materials or PDC materials, an excess amount can be used as a preferred means of introducing porosity by removing it during thermal decomposition.

[0076] When present in the resin, the amount of the second photopolymerizable organosilicon monomer can be at least about 15% by weight, 20% by weight, 25% by weight, 30% by weight, or at least about 35% by weight of the resin, and up to a maximum of about 80% by weight, 75% by weight, 70% by weight, or about 65% by weight of the resin. Alternatively, the second photopolymerizable organosilicon monomer may be present in the resin at least about 5% by volume, 10% by volume, 15% by volume, 20% by volume, or at least about 25% by volume of the resin. The amount of the second photopolymerizable organosilicon monomer may be about 75% by volume or less, 70% by volume or less, 65% by volume or less, 60% by volume or less, or about 55% by volume or less of the resin. Any minimum and maximum values ​​can be combined without limitation. For example, this amount may be 15% to 80% by weight of the resin, 15% to 65% by weight of the resin, etc.

[0077] When a first and second photopolymerizable organosilicon monomer are present in the resin, preferred combinations are (mercaptopropyl)methylsiloxane homopolymer and methacryloxypropyl-terminated polydimethylsiloxane, and (mercaptopropyl)methylsiloxane homopolymer and vinyl methoxysiloxane homopolymer.

[0078] Third and subsequent photopolymerizable organosilicon monomers can be selected in the same manner as the second photopolymerizable organosilicon monomer described above. If present, the third and subsequent photopolymerizable organosilicon monomers may be present in an amount of about 1% to about 50% by weight, preferably about 5% to about 30% by weight, and more preferably about 10% to about 20% by weight of the resin.

[0079] If second and subsequent photopolymerizable organosilicon monomers are present, the photopolymerizable organosilicon monomers, together with the first photopolymerizable organosilicon monomer, may be present in the resin in a total amount of at least about 30% by weight, 40% by weight, 50% by weight, 60% by weight, or at least about 70% by weight, and up to a maximum of about 98% by weight, 95% by weight, 90% by weight, or about 80% by weight. Alternatively, the photopolymerizable organosilicon monomers may be present in the resin in a total amount of at least 10% by volume, about 15% by volume, 20% by volume, 25% by volume, or at least about 30% by volume. The total amount of photopolymerizable organosilicon monomers may be about 95% by volume or less, 90% by volume or less, 80% by volume or less, 75% by volume or less, or about 70% by volume or less of the resin. Any minimum and maximum values ​​can be combined without limitation. For example, this amount may be 30% to 98% by weight of the resin, 30% to 80% by weight of the composition, etc. In a preferred embodiment, the photopolymerizable organosilicon monomer may be present in a total amount of at least about 60% to about 90% by weight, preferably about 65% to about 85% by weight, and more preferably about 70% to about 80% by weight of the resin.

[0080] Photopolymerizable organic monomers A "photopolymerizable organic monomer" is an oligomeric or polymeric carbon-containing chemical compound that contains one or more photopolymerizable functional groups and is other than the organosilicon monomers described herein. In other words, it is an oligomeric or polymeric organic compound that is substituted to contain one or more photopolymerizable functional groups and is other than the organosilicon monomers described herein.

[0081] Oligomers or polymers of organic compounds are identifiable to those skilled in the art. They tend to be based on a main chain structure of repeating motifs containing covalent carbon-carbon and carbon-hydrogen bonds, and often contain covalently bonded heteroatoms such as oxygen, nitrogen, and / or sulfur.

[0082] The photopolymerizable functional group may be substituted at two or more positions on the organic compound, including terminal substitution (i.e., one or more terminal groups) of the organic compound. One or more types of photopolymerizable functional groups can be selected with respect to the first photopolymerizable organosilicon monomer as described above, and are preferably selected to be complementary to one or more photopolymerizable functional groups of one or more photopolymerizable organosilicon monomers. The photopolymerizable organic monomer is typically an organic monomer that does not contain silicon.

[0083] The chemical structure of the skeletal structure of a photopolymerizable organic monomer to which one or more photopolymerizable functional groups can be bonded is sometimes called a "spacer group." Therefore, a photopolymerizable organic monomer is represented by the following formula: Spacer (L) n It can be expressed as , where Spacer is a spacer group, L is a photopolymerizable functional group, and n is an integer of 1 or more. In a preferred embodiment, n is an integer from 2 to 4, preferably 2. The spacer group can be based on an optionally branched skeletal structure containing repeating units such as ethylene, ethylene glycol, propylene, polypropylene glycol, ethylamine, propylamine, etc., and therefore can be based on an optionally branched skeletal structure containing polyethylene, polyethylene glycol, polypropylene, polypropylene glycol, polyethyleneimine, and polypropyleneimine, respectively. The photopolymerizable functional group is preferably terminally substituted. Preferably, one type of photopolymerizable functional group is used. The photopolymerizable functional group is preferably selected based on its reactivity with the first photopolymerizable organosilicon monomer, as described above for the second photopolymerizable organosilicon monomer, and therefore preferably selected from a group or motif selected from one or more of hydroxyl, epoxide, vinyl, allyl, ethynyl, thiol, glycidyl, acrylate, and thiocyanate. In a preferred embodiment, the reactive group is an allyl, vinyl, thiol, or acrylate, for example, to participate in thiol-acrylate photopolymerization chemistry with a photopolymerizable organosilicon monomer having a complementary photopolymerizable functional group.

[0084] Typical photopolymerizable organic monomers include polyethylene glycol diacrylate, polyethylene glycol dithiol, polyethylene glycol divinyl ether, and polyethylene glycol diallyl ether.

[0085] Photopolymerizable organic monomers tend to react more readily with other photopolymerizable organosilicon monomers under photopolymerization conditions than with each other. Therefore, photopolymerizable organic monomers can be selected to increase the degree of polymerization of the polymer material formed from the resin compared to a resin without the photopolymerizable organic monomer under the same conditions. This is one reason why photopolymerizable organic monomers are preferred components of the resins described herein.

[0086] Photopolymerizable organic monomers may be present in stoichiometric amounts corresponding to the complete, or as close to complete as possible, reactivity between the photopolymerizable functional groups of the photopolymerizable organosilicon monomer(s) and the photopolymerizable organic monomer(s). The photopolymerizable organosilicon monomer(s) may exist in a 1:1 ratio with respect to the photopolymerizable functional groups.

[0087] Alternatively, an excess amount of photopolymerizable organic monomer or photopolymerizable organosilicon monomer may be used. For example, with respect to the photopolymerizable functional group, the ratio of photopolymerizable organic monomer to photopolymerizable organosilicon monomer, or photopolymerizable organosilicon monomer to photopolymerizable organic monomer, may be 1.01:1 to 2:1. The excess amount can be used to accelerate the reaction toward the complete reaction of the photopolymerizable organosilicon monomer or photopolymerizable organic monomer. This may result in unpolymerized monomers remaining in the formed polymer material, which can be removed during thermal decomposition, for example, if the polymer material is a preceramic polymer. In embodiments forming a porous polymer material or PDC material, the excess amount can be used to introduce porosity that may be formed when unreacted monomers are removed during thermal decomposition.

[0088] From a physical quantity standpoint, the amount of photopolymerizable organic monomer present can be at least about 1% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, or at least about 35% by weight of the resin, and up to a maximum of about 80% by weight, 75% by weight, 70% by weight, or about 65% by weight of the resin. Any minimum and maximum values ​​can be combined without limitation. For example, this amount may be 1% to 80% by weight of the resin, 15% to 65% by weight of the composition, etc. Many photopolymerizable organic monomers have lower molecular weights than photopolymerizable organosilicon monomers, and therefore their physical amount tends to be less than that of photopolymerizable organosilicon monomers, typically ranging from about 1% to 25% by weight of the resin, including, for example, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 24% and 25% by weight.

[0089] conductive additives The resins of this disclosure use conductive additives, which are substances that impart conductivity to polymer materials or PDC materials formed from the resin, whether they are conductive substances or conductive substance precursors.

[0090] Conductive additives can be identified by those skilled in the art related to this disclosure. Examples of conductive additives include metals such as copper, gold, nickel, silver, aluminum, iron, platinum, mercury, tin, zinc, lead, and tungsten, and alloys thereof. Conductive additives also include inorganic metal compounds such as metal oxides, nitrides, carbides, carbonitrides, and sulfides, such as MXene. Conductive additives also include allotropes of carbon such as graphite, graphene, carbon nanotubes, and nanoplatelets, as well as carbon-containing inorganic materials including oxides, nitrides, and sulfides of allotropes of carbon, and carbon-containing ceramic materials such as silicon carbide. Metals, their alloys, inorganic metal compounds, allotropes of carbon, and carbon-containing ceramics are generally conductive materials, while carbon-containing inorganic materials may be either conductive materials or conductive material precursors. For example, in the exemplary preceramic resin embodiments described herein, graphene oxide is a conductive material precursor. During thermal decomposition, graphene oxide tends to be reduced to graphene or graphite.

[0091] In preferred embodiments, the conductive additive is selected from one or more of the group consisting of metals, metal alloys, inorganic metal compounds, allotropes of carbon, and carbon-containing inorganic substances. Preferably, the conductive additive is an allotrope of carbon and / or a carbon-containing inorganic substance. Preferably, the conductive additive is selected from the group consisting of graphene, graphene oxide, silicon carbide, and carbon nanotubes. For the highest conductivity, carbon nanotubes are most preferred.

[0092] In a preferred embodiment, the conductive additive is a solid substance under conditions used to form the resin and polymer material or PDC material.

[0093] Preferably, the conductive additive is a particulate material. While many 3D printing methods allow for particle sizes up to 1 mm, many injection molding methods allow for particle sizes up to several mm. However, smaller particles are preferable for improving the rheological properties of the resin (especially for 3D printing) and for improving dispersibility within the resin. Particles are also preferable for introducing porosity into the polymer material or PDC material during the polymerization and thermal decomposition of the resin as described above.

[0094] In some embodiments, the particles are microparticles. "Microparticles" means a group of particles having particle sizes between 1 μm and 1 mm. Particulate matter is commonly supplied within a specific particle size range, which usually reflects that at least the majority of those particles are within that size range. This can be described as a particle size distribution. The particles may be mostly within their particle size range (e.g., greater than 95%, greater than 99%), or they may be entirely within their particle size range. Preferably, at least 90%, 95%, 98%, 99%, 99.5%, and even 99.9% of the microparticles contained in the resin are within that particle size range. Preferably, the microparticles have a size of about 1 μm to about 100 μm, preferably about 1 μm to 50 μm, preferably about 1 μm to 25 μm, and more preferably about 1 μm to 15 μm.

[0095] In some embodiments, the particles are nanoparticles. "Nanoparticles" means a plurality of particles having a particle size of less than 1 μm. Preferably, at least 90%, 95%, 98%, 99%, 99.5%, and even more than 99.9%, of the nanoparticles contained in the resin have a size of less than 1 μm, preferably less than 500 nm, less than 200 nm, and even more than less than 100 nm. Preferably, the nanoparticles have a size of about 1 nm to about 100 nm, preferably about 1 nm to 25 nm, and more preferably about 1 nm to 10 nm.

[0096] In some embodiments, the particles include both microparticles and nanoparticles, in which case the resin may contain multiple particles having a particle size of less than 1 mm. In preferred embodiments, at least 90%, 95%, 98%, 99%, 99.5%, and even 99.9% of the particles contained in the resin have a size of about 1 nm to 1 mm, about 1 nm to 100 μm, about 1 nm to 50 μm, about 1 nm to 25 μm, or about 1 nm to 15 μm. Methods for determining particle size and particle size distribution are known in the art and include small-angle X-ray scattering, dynamic light scattering, and transmission electron microscopy. Preferably, the particle size distribution is determined using transmission electron microscopy (TEM).

[0097] The conductive additive can be present in the resin in an amount of at least about 0.1% by weight, 0.25% by weight, 0.5% by weight, 0.75% by weight, or 1% by weight of the resin. The conductive additive can be present in the resin in an amount of up to about 50% by weight, 40% by weight, 30% by weight, 20% by weight, or 10% by weight of the resin. Any minimum and maximum values ​​can be combined without limitation. In a preferred embodiment, the conductive additive is present in the resin in an amount of 0.1% to 50% by weight, preferably 0.25% to 40% by weight, preferably 0.5% to 30% by weight, preferably 0.75% to 20% by weight, preferably 1% to 10% by weight, preferably 1% to 5% by weight, for example, 1% by weight, or 2% by weight, or 3% by weight, or 4% by weight, or 5% by weight.

[0098] In the resin formation process, conductive additives can be added to other resin components alone or together with a dispersant. Dispersants are applicable to conductive additives that are difficult to disperse in other resin components, such as conductive additives that are difficult to disperse in the photopolymerizable monomer(s) contained therein. For example, carbon-containing inorganic substances such as graphene oxide may be supplied together with the dispersant. Preferably, the dispersant is volatile. Applicable dispersants include methanol, ethanol, isopropanol, diethyl ether, acetone, tetrahydrofuran, hexane, and other petroleum solvents, organic liquids such as ethyl acetate, benzene, toluene, acetonitrile, chloroform, dimethyl sulfoxide, dimethylformamide, dichloromethane, and butanone (liquid under the conditions used for resin formation). Preferred dispersants are alcohols such as methanol, ethanol, and isopropanol, preferably ethanol. The dispersant can be at least partially removed during the resin formation process, for example, by using a drying step before the resin is subjected to photopolymerization conditions. If the dispersant is also a pologen, as described later, a certain amount of the dispersant may remain in the resin as a pologen. Preferably, at least the majority of the dispersant is removed so that only a trace amount remains at most. That is, preferably 95% to 100% of the dispersant is removed, preferably 98% to 100%, preferably 98% to 100%, and preferably 99% to 100%. The drying process will be described later.

[0099] Other ingredients The resins of this disclosure may include additional components such as photopolymerizable crosslinking agents, structural particles, pologens, free radical initiators, free radical inhibitors, light shielding agents, 3D printing resolution enhancers, and colorants.

[0100] structure particles Structural particles can be added to resins. The use of structural particles is advantageous because it tends to make the polymer or PDC material formed from the resin relatively stronger and less susceptible to damage to the integrity of the resulting material. This is particularly advantageous in the formation of PDC materials. In the formation of PDC materials from polymer materials, the material is subjected to stress, for example, due to the release of gases and liquids. Structural particles are thought to help reduce the risk of material fracture under stress. Porous structural particles can also be used to impart porosity to polymer or PDC materials. This provides additional advantages when forming PDC materials. Structural particles are thought to act as a scaffold around the polymer material as it may shrink during the conversion from organic to inorganic under thermal decomposition conditions, thereby creating additional porosity.

[0101] Structural particles are typically solid particulate matter contained in resins, other than conductive additives, and do not react with other components (under the conditions used to form resins, polymer materials, and PDC materials, where applicable), remaining present as solid matter in the polymer material or PDC material formed from the resin. Structural particles are identifiable to those skilled in the art in relation to this disclosure.

[0102] The preferred polymer materials and PDC materials described herein are based on photopolymerizable organosilicon monomers that form silicon-based ceramic materials after thermal decomposition, at least in the case of PDC materials; therefore, the preferred structural particles are silicon-based ceramic particles. Examples include SiO2, Si3N4, SiC, SiCN, SiCO, SiCNO, SiBCN, SiBCO, SiAlCN, and SiAlCO. In a preferred embodiment, the ceramic particles are silica (SiO2) particles.

[0103] Structural particles may be porous or non-porous. Non-porous structural particles contribute to the formation of higher-density polymer or PDC materials. Porous structural particles can contribute to imparting porosity to polymer or PDC materials formed from resins. Porous structural particles are typically microporous and / or mesoporous in order to impart micropores and mesopores to polymer or PDC materials.

[0104] Structural particles can be of any size suitable for the purpose, as can be the size described above when the particulate conductive additive is particulate. In some embodiments, structural particles are microparticles defined and described above with respect to the particulate conductive additive. In other embodiments, ceramic particles are nanoparticles defined and described above with respect to the particulate conductive additive. In some embodiments, ceramic particles include both microparticles and nanoparticles. In preferred embodiments, at least 90%, 95%, 98%, 99%, 99.5%, and even 99.9% of the structural particles contained in the resin are nanoparticles having a size of about 1 nm to about 100 nm, preferably about 1 nm to 50 nm, and more preferably about 5 nm to 20 nm.

[0105] Structural particles may be present in the resin in amounts of at least about 0.5% by weight, 1% by weight, 2% by weight, 5% by weight, 8% by weight, or 10% by weight of the resin. If present, the amount of structural particles is preferably about 95% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, 50% by weight or less, or 30% by weight or less of the resin. Any minimum and maximum values ​​can be combined without limitation. In a preferred embodiment, if present, structural particles are present in amounts of about 0.5% by weight to about 20% by weight of the resin, preferably about 1% by weight to about 15% by weight, more preferably about 1% by weight to about 10% by weight, and particularly 2% by weight to about 8% by weight.

[0106] Other ingredients "Pologens" are substances that, when added to a resin, can be released during the thermal decomposition of the preceramic polymer during the formation of PDC materials. Pologens are thought to impart porosity by creating spaces that remain as pores during the release process. Pologens typically do not react with other components in the resin (under the conditions used for forming the resin, polymer material, and PDC material, where applicable). Pologens may be organic or inorganic compounds. Preferably, the pologen is an organic compound, sometimes also called an "organic pologen." Many organic pologens are volatile liquids, such as the list of liquids shown above with respect to dispersants. Other examples include cyclohexanol, dodecanol, 1,2-propanediol, water, 1-propanol, 1,4-butanediol, decane, decanol, and polyethylene glycol (PEG), e.g., PEG200, PEG400, and PEG20000. Adding pologens to a resin may result in a polymer material or PDC material that is less conductive than the same resin formed by the same process but without pologens. This is because, at least in part, the porosity of the material increases as a result of the presence of pologens. Therefore, if pologens are present, they can be present in an amount of up to about 10% by weight. Expressed as a range, pologens can be present in an amount of about 1% to about 10% by weight of the resin, preferably about 1% to about 7% by weight, and more preferably about 1% to about 5% by weight. In a preferred embodiment, pologens are not added to the resin. Preferably, the resin does not contain pologens to a detectable degree. Also in a preferred embodiment, the PDC material described herein is formed from a preceramic polymer that is substantially or virtually free of pologens.

[0107] As explained above, monomers (or sometimes multiple monomers) can react via crosslinking agents. A crosslinking agent is a chemical species comprising a crosslinking group and two or more photopolymerizable functional groups that react with (i.e., are complementary to) one or more photopolymerizable functional groups of any one or more photopolymerizable monomers contained in the resin. After crosslinking occurs, the photopolymerizable functional groups of the photopolymerizable monomer(s) are crosslinked and become crosslinking groups in the structure of the polymer material. If present, the crosslinking agent is usually selected based on the photopolymerizable functional groups of the photopolymerizable organosilicon monomer(s) so as to have complementary photopolymerizable functional groups (or sometimes multiple) as described above. Crosslinking agents differ from photopolymerizable organic monomers in that they are not oligomeric or polymeric themselves. Typical crosslinking agents include ethylene glycol diacrylate, ethylene glycol dithiol, ethylene glycol divinyl ether, ethylene glycol diallyl ether, and hexanedithiol. In some preferred embodiments, no crosslinking agent is added to the resin. In other words, the resin does not contain a crosslinking agent.

[0108] Since the functional groups of the photopolymerizable organosilicon monomers (there may be more than one) are photopolymerizable, the resin may further contain free radical generators, such as photoinitiators, that can catalyze the reaction of the photopolymerizable functional groups. If present, the amount of the free radical generator can be about 0.01% to about 20% by weight, preferably about 0.1% to about 5% by weight, and more preferably about 0.2% to about 1% by weight of the preceramic resin. Examples of photoinitiators include 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, camphorquinone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO), benzophenone, and benzoyl peroxide. In a preferred embodiment, the photoinitiator is BAPO.

[0109] Examples of light-blocking agents include 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BBOT), 4,4'-bis(benzoxazolyl)-cis-stilbene, and 4,4-diamino-2,2-stilbendisulfonic acid. In preferred embodiments, the light-blocking agent is BBOT. If a light-blocking agent is present, the preferred light-blocking agent is 2,5-bis(5-tert-butyl-benzoxazol-2-yl)thiophene (BBOT). If present, the light-blocking agent may be present in an amount of about 0.01% to about 20% by weight of the resin, preferably about 0.1% to about 5% by weight, and more preferably about 0.2% to about 1% by weight.

[0110] The resin may further contain a free radical inhibitor (also known as a free radical scavenger). Examples include hydroquinone, methylhydroquinone, ethylhydroquinone, methoxyhydroquinone, ethoxyhydroquinone, monomethyletherhydroquinone, propylhydroquinone, propoxyhydroquinone, tert-butylhydroquinone (TBHQ), and n-butylhydroquinone. In a preferred embodiment, the free radical inhibitor is tert-butylhydroquinone. If present, the free radical inhibitor may be present in an amount of about 0.01% to about 20% by weight, preferably about 0.05% to about 5% by weight, and more preferably about 0.1% to about 2% by weight of the resin.

[0111] Typical Embodiments Typical embodiments of the resins described herein include a photopolymerizable organosilicon monomer and a conductive additive, optionally and independently comprising the following other components: a) A second photopolymerizable organosilicon monomer; b) Photopolymerizable organic monomers; c) structural particles; d) A second photopolymerizable organosilicon monomer and a photopolymerizable organic monomer; e) Second photopolymerizable organosilicon monomer and structural particles; f) Photopolymerizable organic monomers and structural particles; or, g) Also includes a second photopolymerizable organosilicon monomer, a photopolymerizable organic monomer, and structural particles, The above components may be as described herein, and optionally, any embodiment further comprises one or more of the following: crosslinking agents, pologens, free radical initiators, free radical inhibitors, light shielding agents, 3D printing resolution enhancers, and colorants.

[0112] Method of disclosure The methods of this disclosure include subjecting a resin described herein to photopolymerization conditions to form a conductive polymer material. Where a PDC material is intended to be formed, the photopolymerization conditions may form a conductive polymer material precursor or a conductive polymer material. In these embodiments, the polymer material is a preceramic polymer, and the methods of this disclosure may further include subjecting the preceramic polymer to thermal decomposition conditions to form a conductive PDC material.

[0113] "Photopolymerization conditions" are the conditions under which a photopolymerization reaction occurs. Photopolymerization is typically a free radical reaction catalyzed by light.

[0114] Resins are typically formed by mixing resin components together. All components of the resin may be added together and subjected to a single mixing step, or multiple components may be added to each other in any particular order and mixed in between additions. In embodiments in which a dispersant is used, a suspension of the conductive additive in the dispersant may be formed separately. That is, the conductive additive may first be suspended in the dispersant, and then this suspension may be combined with other components, preferably at least a photopolymerizable organosilicon monomer, before undergoing a mixing step. Preferably, at least a portion of the dispersant is removed before the resin is subjected to photopolymerization conditions. At least a portion of the dispersant can be removed using drying steps such as leaching, cannulation, decantation, and / or evaporation. It is preferable to remove all but a trace amount of the dispersant. Preferably, the removal of the dispersant is carried out using evaporation, preferably using evaporation under negative pressure, i.e., reduced pressure.

[0115] The photopolymerization conditions are preferably applied during the 3D printing process. That is, preferably, the photopolymerization step is applied during the 3D printing process. The 3D printing process typically includes a shaping step, in which a resin is deposited using a 3D printing apparatus to form a shaped article, and a curing step, in which the deposited resin is subjected to photopolymerization conditions to form a green body. The shaping step and the curing step may be performed together or separately. That is, the deposited resin may be cured simultaneously with or during deposition, or the deposited resin may be cured after deposition to fully form the shaped article. Accordingly, the present disclosure provides 3D printed polymer materials for conductive polymer materials or PDC materials, i.e., polymer materials for conductive polymer materials or PDC materials formed by a 3D printing process using a photopolymerization step.

[0116] "Thermal decomposition conditions" are conditions that include high temperatures to which thermal decomposition occurs. "Thermal decomposition" is the thermally induced conversion of preceramic polymers from organic materials to inorganic (i.e., PDC) materials. Methods of thermal decomposition are well known to those skilled in the art. Generally speaking, preceramic polymers are placed in a low-temperature furnace, the temperature is raised to a maximum temperature, and then the temperature is lowered again. During thermal decomposition, the formed inorganic material may exist in one or more material phases. Typically, inorganic materials can transition from an amorphous phase to a crystalline phase as the temperature rises. The temperature at which this transition begins is sometimes called the "phase transition temperature." The phases present depend on the temperature to which the material is exposed. In other words, amorphous or crystalline PDC materials can be formed by controlling the temperature. The phase transition temperature depends on the components of the resin. Similarly, for preceramic polymers that are porous or capable of forming porosity during thermal decomposition, the porosity of the formed PDC material depends similarly on the temperature to which the material is exposed. In other words, porosity tends to exist at low thermal decomposition temperatures, but decreases or disappears when temperatures higher than those that cause pore collapse are reached. The temperature at which pores collapse to a detectable degree is sometimes called the "porosity transition temperature." Similar to the phases of a material, porous or nonporous materials can be formed by controlling the temperature. Typically, the phase transition temperature is higher than the porosity transition temperature, in which case amorphous porous materials and crystalline nonporous materials can be selectively formed by controlling the thermal decomposition temperature. In relation to this disclosure, the following thermal decomposition temperature principle is generally applicable to PDC materials: a) The conversion of photopolymerized monomers (or multiple monomers) of preceramic polymers into PDC materials begins at approximately 300°C and is substantially complete when the temperature reaches approximately 600°C. b) In PDC materials capable of forming porosity during thermal decomposition, porosity begins to form at approximately 300°C, when the material is converted to PDC material. Maximum porosity exists near the point of complete conversion to PDC material, or at a temperature thereafter, just before the temperature at which pores begin to collapse (porosity transition temperature). This is thought to be within the temperature range of approximately 600°C to 1000°C. c) When the temperature rises beyond the range of maximum porosity, the pores begin to collapse, reducing porosity, increasing the density of the PDC material, and improving conductivity. With the addition of conductive additives, the porosity transition temperature is typically around 1000°C or higher. This is in contrast to other PDC materials, which are generally said to have a porosity transition temperature of less than 1000°C, and even less than 900°C. d) The temperature can continue to rise up to the phase transition temperature. By adding conductive additives, the phase transition temperature typically exceeds 1400°C, and can even exceed 1450°C or 1500°C. This is in contrast to other PDC materials, which generally have a phase transition temperature of 1300°C to 1400°C.

[0117] These principles are illustrated in Figures 1 and 2, which compare the conductivity and porosity of PDC materials of embodiments illustrated herein. Figure 1 shows that for PDC materials containing graphene, graphene oxide nanoplatelets, and carbon nanotubes as conductive additives, the electrical conductivity tends to increase with increasing thermal decomposition temperature from 300°C to 1000°C and / or from 1000°C to 1200°C. Figure 1 also shows that for carbon nanotubes, the conductivity tends to increase with increasing amounts of conductive additives in PDC materials. Figure 2 shows that for PDC materials containing graphene, graphene oxide nanoplatelets, and carbon nanotubes as conductive additives, the porosity increases with increasing thermal decomposition temperature up to the porosity transition temperature (approximately 1000°C here), and then tends to decrease with increasing thermal decomposition temperature (up to 1200°C here).

[0118] Since conductive PDC materials that also possess porosity are beneficial in many applications, in some embodiments, the maximum temperature of thermal decomposition is preferably lower than the porosity transition temperature. However, since conductivity is maximized in materials with low porosity, in some embodiments, the maximum temperature of thermal decomposition is preferably higher than the temperature at which maximum porosity is achieved. In this context, "maximum temperature" means the highest temperature reached during thermal decomposition. Therefore, in some preferred embodiments, the maximum temperature of thermal decomposition is about 900°C to 1200°C. This may be a maximum temperature of about 900°C, 950°C, 1000°C, 1050°C, 1100°C, 1150°C, or 1200°C. In these embodiments, the maximum temperature of thermal decomposition is preferably about 900°C to 1100°C, preferably about 900°C to 1150°C, and preferably about 1000°C to 1100°C. This temperature has been found to provide a balance between available porosity and electrical conductivity.

[0119] When porosity is not required, the maximum thermal decomposition temperature may exceed the porosity transition temperature, but in preferred embodiments, the maximum temperature is less than 1600°C, which is the temperature at which many PDC materials are considered to begin approaching their melting point. Therefore, in these embodiments, the maximum thermal decomposition temperature is 1000°C to 1600°C, preferably 1100°C to 1600°C, and may also be 1300°C to 1600°C.

[0120] The maximum temperature of thermal decomposition can be combined with the minimum temperature of thermal decomposition, and the minimum temperature is preferably at least 300°C for efficient conversion from organic materials to inorganic materials.

[0121] The thermal decomposition conditions may be characterized by a heating rate of 10°C / min or less during the time between the lowest and highest thermal decomposition temperatures, or for the entire time between the lowest and highest thermal decomposition temperatures (preferably the latter). For the time between the lowest thermal decomposition temperature and the porosity transition temperature, or for the entire time between the lowest thermal decomposition temperature and the porosity transition temperature, a slower heating rate of 7°C / min or less, preferably 5°C / min or less, preferably 3°C / min or less, more preferably 2°C / min or less, and most preferably 1°C / min or less is preferred. This can promote the formation of greater porosity and slow down the rate at which liquids and gases are generated and released from the material, thereby reducing the risk of pressure rise and the risk of deterioration of the integrity of the PDC material. In certain preferred embodiments, the rate may be even slower, such as 0.5°C / min or less, and even 0.3°C / min or less, for a certain period of time. Expressed as a range, the heating rate may be 0.1°C / min to 10°C / min, 0.1°C / min to 7°C / min, 0.1°C / min to 5°C / min, 0.2°C / min to 3°C / min, 0.2°C / min to 2°C / min, preferably 0.3°C / min to 1°C / min, over the time between the lowest thermal decomposition temperature and the porous transition temperature, or over the entire time between the lowest thermal decomposition temperature and the porous transition temperature. The cooling rate can be controlled in the same way as the heating rate, and is usually 10°C / min or less, and may be even slower for a certain period of time, for example, to about 0.5°C / min to 1°C / min or 2°C / min.

[0122] Pyrolysis can be carried out in an inert or reactive atmosphere. A reactive atmosphere is typically characterized by the presence of a reactive gas, i.e., a gas that is reactive to at least one component of the preceramic polymer material under pyrolysis conditions. Examples of reactive gases include oxygen, carbon dioxide, water (e.g., water vapor), methane, iodine, and ammonia. Air is an example of a reactive gas, containing oxygen and carbon dioxide, and possibly water. An inert atmosphere is generally characterized by the absence of reactive gases. Examples of inert environments are a nitrogen gas environment or a vacuum environment. In a preferred embodiment, pyrolysis is carried out in an inert atmosphere, preferably under vacuum.

[0123] The thermal decomposition conditions may include one or more holding times, in which the thermal decomposition temperature is maintained at a specific temperature for a certain period of time. Examples of suitable time points for using holding times include near or just before the porous transition temperature, and near or just before the phase transition temperature. The holding time can be 30 to 300 minutes, or 60 to 240 minutes, with a predetermined holding time preferably being 60 to 180 minutes.

[0124] The specific PDC material produced is usually determined by the type of photopolymerizable organosilicon monomer(s) used. Using the preferred photopolymerizable organosilicon monomers described herein, silicon-based PDC materials can typically be based on SiO, Si3N4, SiC, SiCN, SiCO, SiCNO, SiBCN, SiBCO, SiAlCN, SiAlCO, SiON, and / or SiBN. The specific PDC material produced may also depend on the thermal decomposition conditions used. For example, the presence of a reactive environment typically affects the properties of the gases released from the material during thermal decomposition, and consequently, the properties of the resulting PDC material. For example, when a preceramic polymer formed from polysiloxane organosilicon monomers is thermally decomposed in an inert atmosphere, silicon oxycarbide ceramic material is usually produced. On the other hand, when a preceramic polymer formed from polysiloxane organosilicon monomers is thermally decomposed in a reactive air environment, gases in the air (e.g., O2) react with carbon atoms in the organosilicon skeleton structure of the polysiloxane, releasing them as carbon-containing gases, thus producing silica ceramic material. [Examples]

[0125] TGA for determining the ceramic yield of organosilicon monomers 850The procedure is as follows: A known amount of photopolymerizable organosilicon monomer (preferably between 10 mg and 20 mg) was transferred to an alumina crucible approved for use in a thermogravimetric analyzer. The crucible was placed in the analyzer, and its weight change with respect to time and temperature was observed according to the manufacturer's instructions for use. The sample crucible was subjected to a thermal cycle from room temperature to 850°C under nitrogen, and then returned to room temperature. The sample was equilibrated at 30°C for 30 minutes, and after tare of the resulting weight, the temperature was increased from 30°C to 850°C at a heating rate of 1°C / min. The sample was further equilibrated at 850°C for 60 minutes, and then cooled from 850°C to room temperature at a rate of 5°C / min. The ceramic yield was calculated using the percentage of the weight change of the sample during this thermal cycle. Here, the percentage of ceramic yield is calculated as (1 - sample weight loss / initial sample weight) × 100.

[0126] Table 1 outlines the materials and thermal decomposition conditions used in the production of conductive polymer materials or PDC materials.

[0127] [Table 1] TIFF2026524914000004.tif245170TIFF2026524914000005.tif245170

[0128] Example 1 - Conductive ceramic: Carbon-enriched black glass electrode Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + graphene particles A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2.3% by weight of micron-sized graphene particles (1.5 μm in diameter) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and the prepared resin was then vacuum-embedded for 15 minutes.

[0129] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0130] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0131] Figure 3 shows a 3D-printed and pyrolytically manufactured carbon-enriched black glass electrode with comb-shaped pillars. As shown in the inserted SEM image in Figure 3a) and the SEM image in Figure 3b), the electrode was found to be hierarchically porous. Conductivity testing of the electrode using the four-point probe method reported a sheet resistance of 4.3 kΩ / square, an electrical resistivity of 2.15 Ω / m, and an electrical conductivity of 465 mS / m.

[0132] Example 2 - Conductive ceramic: Carbon-enriched black glass electrode Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + graphene oxide nanoplatelets A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5nm-20nm) was added to this resin. Finally, 4% by weight of graphene oxide nanoplatelets (1nm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and the prepared resin was then vacuum-embedded for 15 minutes.

[0133] Using a digital light projection (DLP) printer (Miicraft Ultra), the resin was 3D printed according to the manufacturer's standard operating procedures to produce a 3D printed green object.

[0134] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0135] Figure 4 shows the 3D-printed fabricated carbon-enriched black glass electrode. As shown in the inserted SEM image in Figure 4, the electrode was found to be hierarchically porous. Figure 14 shows a) an SEM image and b) a BET isotherm of the fabricated PDC material. Conductivity tests using the four-point probe method reported a sheet resistance of 121.2 kΩ / square, an electrical resistivity of 60.6 Ω / m, and an electrical conductivity of 16.5 mS / m.

[0136] Example 3 - Conductive Polymer Ethanol dispersion of first and second photopolymerizable organosilicon monomers + ceramic particles + graphene A 2 wt% ethanol dispersion of graphene was added to 100 wt% (mercaptopropyl)methylsiloxane homopolymer at a ratio of 40 wt%. The components were thoroughly mixed in a vortex mixer and an ultrasonic chamber. To this mixture, 10 wt% porous silicon dioxide nanoparticles (spherical, 10 nm to 20 nm) were added. The resulting mixture was placed in a vacuum oven at 30°C for 12 hours to evaporate the ethanol. The decrease in ethanol was monitored using thermogravimetric analysis. After vacuum treatment, 100 wt% methacryloxypropyl-terminated polydimethylsiloxane, 0.9 wt% phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.8 wt% tert-butylhydroquinone (TBHQ) were added and thoroughly mixed in a vortex mixer and an ultrasonic chamber. The prepared resin was vacuumed for 15 minutes.

[0137] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0138] Figure 5 shows a 3D-printed, fabricated polydimethylsiloxane polymer electrode with comb-shaped pillars. As shown in the inserted SEM image of Figure 5, the electrode was found to be hierarchically porous.

[0139] Example 4 - Conductive Ceramic: SiC & SiC Composite Electrode Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + SiC particles A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). Finally, 5% by weight of silicon carbide nanoparticles (20 nm, laser synthesized) were added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and then the prepared resin was vacuum-embedded for 15 minutes.

[0140] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0141] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0142] Figure 6 shows a 3D-printed composite electrode made of silicon carbide and silicon oxycarbide. As shown in the inserted SEM image in Figure 6, the electrode was found to be hierarchically porous. Conductivity tests using the four-point probe method reported a sheet resistance of 12.4 MΩ / square, an electrical resistivity of 3.1 kΩ / m, and an electrical conductivity of 321 μS / m.

[0143] Example 5 - Conductive ceramic: Carbon-enriched black glass electrode First photopolymerizable organosilicon monomer + first photopolymerizable organosilicon monomer + ceramic particles + graphene particles A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer (ceramic yield approximately 55%) and 100 parts methacryloxypropyl-terminated polydimethylsiloxane (ceramic yield approximately 18%) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5nm-20nm) was added to this resin. Finally, 2.5% by weight of micron-sized graphene particles was added to the resin. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and the prepared resin was then vacuum-embedded for 15 minutes.

[0144] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0145] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0146] Figure 7 shows the 3D-printed fabricated carbon-enriched black glass electrode. As shown in the inserted SEM image in Figure 7, the electrode was found to be hierarchically porous. Conductivity tests using the four-point probe method reported a sheet resistance of 24.7 kΩ / square, an electrical resistivity of 12.4 Ω / m, and an electrical conductivity of 80.7 mS / m.

[0147] Example 6 - Conductive ceramic: Carbon-enriched black glass electrode First photopolymerizable organosilicon monomer + first photopolymerizable organosilicon monomer + ceramic particles + graphene particles A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer (ceramic yield approximately 55%) and 70 parts vinyl methoxysiloxane homopolymer (ceramic yield approximately 50%) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2.3% by weight of micron-sized graphene particles (diameter 1.5 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and the prepared resin was then vacuum-embedded for 15 minutes.

[0148] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0149] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0150] In the four-point probe method electrical conductivity test, the sheet resistance was reported to be 13.7 kΩ / square, the electrical resistivity 19.8 Ω / m, and the electrical conductivity 52 mS / m.

[0151] Example 7 - Conductive ceramic: Ceramic electrode Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + graphene particles A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). Nonporous silicon dioxide nanoparticles (spherical, 10 nm to 20 nm) (4.5% by weight) were added to the resin. Finally, 2.3% by weight of micron-sized graphene particles (diameter 1.5 μm) were added to the resin. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0152] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0153] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0154] Example 8 - Conductive ceramic: Ceramic electrode Photopolymerizable organosilicon monomer + crosslinking agent + SiC particles A resin was prepared by mixing 100 parts allyl hydride polycarbosilane and 50 parts 1,6-hexanedithiol with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight tert-butylhydroquinone (TBHQ). Finally, 5% by weight of silicon carbide nanoparticles (20 nm, laser synthesized) were added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and then the prepared resin was vacuum-embedded for 15 minutes.

[0155] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0156] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 12 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes. Next, the furnace was cooled from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 450°C and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0157] Example 9 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 5% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0158] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0159] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.3 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0160] Figure 8 shows a 3D-printed, fabricated carbon-enriched black glass disk. As shown in the inserted SEM image, the disk was found to be hierarchically porous. Conductivity testing using the four-point probe method reported a sheet resistance of 24.6 Ω / square, an electrical resistivity of 8 mΩ / m, and an electrical conductivity of 124.7 S / m.

[0161] Example 10 - Conductive Polymer Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 5% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0162] This resin was 3D printed using a digital light projection (DLP) printer (Miicraft Ultra) according to the manufacturer's standard operating procedures to produce 3D printed conductive polydimethylsiloxane polymer material.

[0163] Figure 9 shows a 3D-printed, fabricated carbon-enriched polydimethylsiloxane polymer disk. As shown in the inserted SEM image, the disk was found to be hierarchically porous. Conductivity testing using the four-point probe method reported a sheet resistance of 1.3 kΩ / square, an electrical resistivity of 2.7 Ω / m, and an electrical conductivity of 356 mS / m.

[0164] Example 11 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 4% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0165] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0166] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.3 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes. The furnace was then cooled from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0167] Figure 10 shows a 3D-printed, fabricated carbon-enriched black glass electrode. As shown in the inserted SEM image in Figure 10, the electrode was found to be hierarchically porous. Conductivity tests using the four-point probe method reported a sheet resistance of 1.154 kΩ / square, an electrical resistivity of 966.7 mΩ / m, and an electrical conductivity of 6.1 S / m.

[0168] Example 12 - Conductive Polymer Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 4% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0169] This resin was 3D printed using a digital light projection (DLP) printer (Miicraft Ultra) according to the manufacturer's standard operating procedures to produce 3D printed conductive polydimethylsiloxane polymer material.

[0170] In a four-point probe test, the electrical resistivity was reported to be 27.5 Ω / m and the electrical conductivity 36.2 mS / m.

[0171] Example 13 - Conductive Polymer Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 3% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0172] This resin was 3D printed using a digital light projection (DLP) printer (Miicraft Ultra) according to the manufacturer's standard operating procedures to produce 3D printed conductive polydimethylsiloxane polymer material.

[0173] In a four-point probe test, the electrical resistivity was reported to be 175 Ω / m and the electrical conductivity 5.7 mS / m.

[0174] Example 14 - Conductive Polymer Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0175] This resin was 3D printed using a digital light projection (DLP) printer (Miicraft Ultra) according to the manufacturer's standard operating procedures to produce 3D printed conductive polydimethylsiloxane polymer material.

[0176] In a four-point probe test, the electrical resistivity was reported to be 29.9 kΩ / m and the electrical conductivity 33.4 μS / m.

[0177] Example 15 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 1% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0178] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0179] The green material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes. Next, the furnace was cooled from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 450°C and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0180] In a four-point probe test, the electrical resistivity was reported to be 4 Ω / m and the electrical conductivity 256 mS / m.

[0181] Example 16 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0182] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0183] The green material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes. Next, the furnace was cooled from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 450°C and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0184] Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 0.96 Ω / m and an electrical conductivity of 1.04 S / m. Brunauer-Emmett-Teller (BET) surface area analysis revealed a surface area of ​​119.35 m². 2 It was reported to be / g.

[0185] Example 17 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 3% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0186] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0187] The green material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes. Next, the furnace was cooled from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 450°C and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0188] Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 117.5 mΩ / m and an electrical conductivity of 8.5 S / m. Brunauer-Emmett-Teller (BET) surface area analysis showed a surface area of ​​410.5 m². 2 It was reported to be / g.

[0189] Example 18 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 4% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0190] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0191] The green material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes. Next, the furnace was cooled from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 450°C and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0192] Figure 15 shows the BET isotherms of the manufactured PDC material. Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 60.5 mΩ / m and an electrical conductivity of 16.5 S / m. Brunauer-Emmett-Teller (BET) surface area analysis showed a surface area of ​​423.9 m². 2 It was reported to be / g.

[0193] Example 19 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 1% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0194] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0195] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0196] Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 2.8 Ω / m and an electrical conductivity of 360.5 mS / m. Brunauer-Emmett-Teller (BET) surface area analysis revealed a surface area of ​​432.74 m². 2 It was reported to be / g.

[0197] Example 20 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0198] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0199] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0200] Figure 11 shows the BET isotherms of the manufactured PDC material. Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 0.79 Ω / m and an electrical conductivity of 12.5 S / m. Brunauer-Emmett-Teller (BET) surface area analysis showed a surface area of ​​442.49 m². 2 It was reported to be / g.

[0201] Example 21 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 3% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0202] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0203] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0204] Figure 12 shows the BET isotherms of the manufactured PDC material. Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 27.6 mΩ / m and an electrical conductivity of 36.2 S / m. Brunauer-Emmett-Teller (BET) surface area analysis showed a surface area of ​​419.01 m². 2 It was reported to be / g.

[0205] Example 22 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 4% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0206] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0207] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1000°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1000°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0208] Figure 13 shows an SEM image of the manufactured PDC material. Conductivity tests using the four-point probe method reported an electrical resistivity of 9.9 mΩ / m and an electrical conductivity of 100.9 S / m.

[0209] Example 23 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + graphene oxide nanoplatelets A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5nm-20nm) was added to this resin. Finally, 4% by weight of graphene oxide nanoplatelets (1nm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and the prepared resin was then vacuum-embedded for 15 minutes.

[0210] Using a digital light projection (DLP) printer (Miicraft Ultra), the resin was 3D printed according to the manufacturer's standard operating procedures to produce a 3D printed green object.

[0211] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1200°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1200°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0212] Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 30.7 mΩ / m and an electrical conductivity of 32.55 S / m. Brunauer-Emmett-Teller (BET) surface area analysis showed a surface area of ​​5.3 m². 2 It was reported to be / g.

[0213] Example 24 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + graphene particles A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2.3% by weight of micron-sized graphene particles (1.5 μm in diameter) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath, and the prepared resin was then vacuum-embedded for 15 minutes.

[0214] Using a digital light projection (DLP) printer (Miicraft Ultra), the resin was 3D printed according to the manufacturer's standard operating procedures to produce a 3D printed green object.

[0215] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1200°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1200°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 2°C / min.

[0216] In a four-point probe test, the electrical resistivity was reported to be 47.9 mΩ / m and the electrical conductivity 20.9 S / m.

[0217] Example 25 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + ceramic particles + carbon nanotubes A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 2% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0218] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0219] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1200°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1200°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0220] In a four-point probe test, the electrical resistivity was reported to be 26.4 mΩ / m and the electrical conductivity 38 S / m.

[0221] Example 26 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + carbon nanotube A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 3% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0222] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0223] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1200°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1200°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0224] In a four-point probe test, the electrical resistivity was reported to be 16.7 mΩ / m and the electrical conductivity 60 S / m.

[0225] Example 27 - Conductive Ceramic Photopolymerizable organosilicon monomer + photopolymerizable organic monomer + carbon nanotube A resin was prepared by mixing 100 parts (mercaptopropyl)methylsiloxane homopolymer and 54.35 parts poly(ethylene glycol) diacrylate (average Mn250) with 0.9 parts phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide and 0.8 parts by weight of tert-butylhydroquinone (TBHQ). 5% by weight of porous silicon dioxide nanoparticles (spherical, 5 nm to 20 nm) was added to this resin. Finally, 4% by weight of multi-walled carbon nanotubes (3 μm to 12 μm) was added. The resin components were thoroughly mixed in a vortex mixer and an ultrasonic bath.

[0226] Using a digital light projection (DLP) printer (Miicraft Ultra) and following the manufacturer's standard operating procedures, this resin was 3D printed to produce a 3D printed conductive green body.

[0227] Green's material was thermally decomposed in a tubular furnace under vacuum (pressure 0.05 mbar). The decomposition was carried out by heating from room temperature to 100°C at a rate of 1°C / min, followed by heating from 100°C to 600°C at a rate of 0.2°C / min. The furnace was held at 600°C for 180 minutes, then heated to 1200°C at a rate of 1°C / min and held for 60 minutes. The furnace was then cooled from 1200°C to 600°C at a rate of 1°C / min, then from 600°C to 450°C, and then to 300°C at a rate of 2°C / min. The furnace was held at 600°C, 450°C, and 300°C for 60 minutes each. Finally, it was cooled to room temperature at a rate of 7°C / min.

[0228] Electrical conductivity tests using the four-point probe method reported an electrical resistivity of 8.8 mΩ / m and an electrical conductivity of 113.6 S / m. Brunauer-Emmett-Teller (BET) surface area analysis showed a surface area of ​​18.9 m². 2 It was reported to be / g.

[0229] The embodiments described above are merely preferred examples of the present disclosure. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present disclosure, and such improvements and modifications are within the scope of the present disclosure.

[0230] Where any prior art publications are referenced in this specification, it should be understood that such references do not constitute common knowledge in the art in Australia or any other country.

[0231] In the attached claims and the detailed description of the above disclosure, unless otherwise specifically required by the context through express language or necessary implications, the term “comprise” or variations such as “comprises” or “comprising” are used in a comprehensive sense, that is, to identify the presence of a specified feature, but not to exclude the presence or addition of further features in the various embodiments of the present disclosure.

[0232] Where used herein, unless otherwise specifically required by the context through explicit language or necessary implication, the articles “a” and “an” are used to refer to one or more (i.e., at least one) grammatical objects of the article. For example, “an element” means one or more elements.

Claims

1. A resin for forming a conductive polymer material or polymer-derived ceramic (PDC) material, comprising a photopolymerizable organosilicon monomer and a conductive additive.

2. The resin according to claim 1, wherein the photopolymerizable organosilicon monomer is based on an organosilicon monomer selected from the group consisting of polysiloxane, polycarbosiloxane, polysilsesquioxane, polycarbosilane, polysilylcarbodiimide, polysilsesquicarbodiimide, polysilazane, polysilsesquiazan, polyborosilane, polyborosiloxane, and polyborosilazane.

3. The aforementioned photopolymerizable organosilicon monomer is a) Chemical structures of the following formulas: 【Chemistry 1】 (In the formula, n represents the main chain structure of repeating motifs containing silicon atoms, and is an independent integer between 2 and 15, and R １ 、 R ２ 、 R ３ 、 and R ４ are each independently, for each integer n, selected from the group consisting of H, C １ ~C １８ substituted or unsubstituted alkyl, C １ ~C １８ substituted or unsubstituted alkyl ether, phenyl, and halide, provided that the pair of R １ and R ２ and the pair of R ３ and R ４ are not both H, alkyl ether, or halide for all integers n) with an organosilicon monomer; b) The chemical structure of formula 6, formula 7, or formula 8 below: 【Chemistry 2】 (In the formula, n represents the main chain structure of repeating motifs containing silicon atoms, and is an independent integer between 2 and 15. R １ , R ２ , R ３ , and R ４ This is as defined above, and, R ５ and R ６ For each integer n, H, OH, and C are independent. １ ~C １８ Substituted or unsubstituted alkyl, C １ ~C １８ An organosilicon monomer having an organosilicon monomer (independently selected from the group consisting of substituted or unsubstituted alkyl ethers and phenyl); The resin according to claim 1 or 2, which is based on an organosilicon monomer selected from the group consisting of the following.

4. The resin according to any one of claims 1 to 3, wherein the photopolymerizable organosilicon monomer comprises a photopolymerizable functional group selected from the group consisting of hydroxyl, epoxide, vinyl, allyl, ethynyl, thiol, glycidyl, acrylate, and thiocyanate.

5. The resin according to claim 4, wherein the photopolymerizable functional group is a thiol.

6. The resin according to any one of claims 1 to 5, wherein the conductive additive is selected from the group consisting of metals, metal alloys, inorganic metal compounds, allotropes of carbon, and carbon-containing inorganic substances.

7. The resin according to any one of claims 1 to 6, wherein the conductive additive is carbon nanotubes.

8. The resin according to any one of claims 1 to 7, further comprising a photopolymerizable organic monomer.

9. The photopolymerizable organic monomer is defined by the following formula: Spacer(L)n The resin according to claim 8, having (wherein Spacer is a spacer group, L is a photopolymerizable functional group, and n is an integer of 1 or more).

10. The resin according to claim 9, wherein the photopolymerizable functional group is selected from the group consisting of hydroxyl, epoxide, vinyl, allyl, ethynyl, thiol, glycidyl, acrylate, and thiocyanate.

11. The resin according to claim 10, wherein the photopolymerizable functional group is an acrylate.

12. The resin according to any one of claims 8 to 11, wherein the photopolymerizable organic monomer is present with respect to the photopolymerizable functional group in a 1:1 ratio with respect to the photopolymerizable organosilicon monomer.

13. The resin according to any one of claims 1 to 12, further comprising structural particles.

14. The resin according to claim 13, wherein the structural particles are ceramic particles.

15. A conductive polymer material or PDC material formed by using a photopolymerization step from the resin according to any one of claims 1 to 14.

16. The conductive polymer material or PDC material according to claim 15, wherein the photopolymerization step is applied during a 3D printing process.

17. A conductive polymer material comprising a photopolymerized photopolymerizable organosilicon monomer and a conductive substance.

18. A conductive polymer material according to any one of claims 15 to 17, having an electrical conductivity of 0.1 μS / m to 1 S / m.

19. A conductive PDC material comprising a thermally decomposed preceramic polymer and a conductive substance, wherein the preceramic polymer comprises a photopolymerized photopolymerizable organosilicon monomer and a conductive additive.

20. A conductive polymer material according to any one of claims 15, 16, or 19, having an electrical conductivity of 0.1 μS / m to 600 S / m.

21. A polymer material for forming a conductive PDC material, comprising a photopolymerized photopolymerizable organosilicon monomer and a conductive additive.

22. The conductive polymer material, polymer material, or conductive PDC material according to any one of claims 15 to 21, wherein the polymer material or preceramic polymer is 3D printed.

23. A method for forming a conductive polymer material, comprising subjecting a resin according to any one of claims 1 to 14 to photopolymerization conditions to form a conductive polymer material.

24. A method for forming a conductive PDC material, a) To subject the resin according to any one of claims 1 to 14 to photopolymerization conditions to optionally form a conductive preceramic polymer, b) Forming a conductive PDC material by subjecting the optionally conductive preceramic polymer to thermal decomposition conditions, Methods that include...

25. The method according to claim 23 or 24, wherein the photopolymerization conditions are applied during the 3D printing process.

26. A polymer material, a conductive polymer material, or a conductive PDC material formed by the method described in any one of claims 23 to 25.

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