CN115466918B - Whisker/fiber surface texturing nano bump structure modification method and toughening application thereof - Google Patents
Whisker/fiber surface texturing nano bump structure modification method and toughening application thereof Download PDFInfo
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62645—Thermal treatment of powders or mixtures thereof other than sintering
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62847—Coating fibres with oxide ceramics
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
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- C04B35/62852—Alumina or aluminates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
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- C04B35/62857—Coating fibres with non-oxide ceramics
- C04B35/6286—Carbides
- C04B35/62863—Silicon carbide
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62844—Coating fibres
- C04B35/62857—Coating fibres with non-oxide ceramics
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- C04B35/62868—Boron nitride
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62889—Coating the powders or the macroscopic reinforcing agents with a discontinuous coating layer
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- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62892—Coating the powders or the macroscopic reinforcing agents with a coating layer consisting of particles
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- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
- C23C4/134—Plasma spraying
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- Chemical & Material Sciences (AREA)
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- Crystals, And After-Treatments Of Crystals (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a whisker/fiber surface texturing nanobump structure modification method and toughening application thereof, and aims to solve the problems that reagents in the existing chemical surface modification whisker/fiber modification method have pollution, and the process is complex and the cost is high. The modification method comprises the following steps: 1. adding whiskers or fibers and nanoparticles to a dispersant to form a whisker/fiber-nanoparticle mixed precursor solution; 2. coating whisker/fiber-nanoparticle mixed precursor solution on a preheated ceramic substrate; 3. and fourthly, repeatedly cleaning the modified whisker/fiber by deionized water. The modified whisker/fiber is used as toughening reinforcing phase to be added into heat protecting coating or composite material. The invention utilizes the high-energy laser technology to grow the textured nanobump structure on the whisker/fiber surface in situ, does not use chemical modification reagents, has simple process and realizes the toughening promotion of the whisker on the matrix material.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a protruding point modification method of a whisker/fiber surface gecko foot-like structure and toughening promotion application thereof.
Background
The whisker/fiber is easy to form a super-strong composite material with high hardness, high toughness, high wear resistance, high temperature resistance, high temperature creep resistance and low thermal expansion coefficient with a matrix material, and has very attractive application prospect in the aspects of preparing nano optoelectronic devices, high-strength composite material components, thin composite material components and surface nano reinforced composite materials. The introduction of whisker/fiber to strengthen and toughen the composite material is considered as an effective method for solving the problem of normal temperature or high temperature toughness of the material, not only the performance of the matrix material is maintained, but also the mechanical performance of the whole material is improved through the whisker/fiber, so that the method for effectively embedding the introduced whisker/fiber into the matrix and achieving the aim of toughening and strengthening the material is one of important research subjects in the aspect of microstructure processing of the composite material.
The process technology of introducing whiskers/fibers to reinforce composite materials has a great influence on the performance of the materials and the cost thereof also depends on the manufacturing process of the materials, so that research and development of high-efficiency preparation processes are important research contents for developing composite materials. Because the whisker/fiber and matrix material have interface wettability problem, the mechanical property of the whole material is greatly affected, so that the regulation and control of the combination effect of two-phase interfaces is the key for controlling the mechanical property of the whisker/fiber toughened composite material.
At present, whisker/fiber is subjected to surface modification to improve good wettability and mechanical combination of heterogeneous interfaces in a matrix material, but most of modification technologies are concentrated on a surface modification method in a chemical mode, and the chemical modification technology is generally low in preparation efficiency and low in yield, and is generally suitable for laboratory researches; on the other hand, the production cost is high, the main expression is that the use amount of chemical reagents is large, and most reagents are pollution-type and extremely toxic, which undoubtedly increases the environmental cost. Other methods such as sol-gel methods also have the problem of expensive raw materials.
Disclosure of Invention
The invention aims to solve the problems of pollution of reagents and complex process and high cost in the existing modification method of the chemical surface modification whisker/fiber, and provides a processing method for carrying out in-situ texturing modification on the surface of the whisker/fiber by utilizing high-energy beams.
The modification method of the whisker/fiber surface textured nanobump structure is realized according to the following steps:
adding whiskers or fibers and nano-particles into a dispersing agent, and dispersing under the condition of mechanical stirring to enable the whiskers/fibers and the nano-particles to be uniformly dispersed in a solvent under the mutual repulsive force action of surface functional groups, so as to form a whisker/fiber-nano-particle mixed precursor solution;
step two, coating whisker/fiber-nanoparticle mixed precursor solution on a preheated ceramic substrate, and forming a precursor coating on the ceramic substrate;
Step three, irradiating the precursor coating with high energy density through laser beams, controlling the laser spot diameter to be 1-6 mm in the laser irradiation process, the laser scanning speed to be 1-30 mm/s and the laser power to be 100-500W, and obtaining modified whisker/fiber;
and step four, repeatedly cleaning the modified whisker/fiber with deionized water to obtain the whisker/fiber with the surface textured nanobump structure modified.
The application of the whisker/fiber modified by the surface texture nanobump structure is that the modified whisker/fiber is used as a toughening reinforcing phase to be added into a thermal protection coating or a composite material.
The invention utilizes the high-energy laser technology to grow a textured nano bump structure on the whisker/fiber surface, improves the specific surface area of the whisker/fiber and the physical adsorption and mechanical blocking capability of the contact site with the matrix material through the bump structure, and uses the bump structure as a second phase toughening body to carry out reinforcing toughening modification on the material. Wherein, the heat insulation and mass transfer capacity of the coating or the composite material is regulated and controlled by controlling the arrangement mode of the surface texture whisker/fiber in the heat protection coating or the composite material; by designing the form of the nano-bumps on the surface of the whisker, the mechanical stability of the material between internal phase interfaces under the coupling of mechanical external force or thermal force and the failure behavior caused by stress mismatch generated by material phase change are controlled, so that the toughening of the whisker to the matrix material is improved.
The whisker/fiber surface texturing nanobump structure modification method and the stiffening application thereof have the following beneficial effects:
(1) The invention utilizes the high-energy laser technology to grow the textured nanobump structure on the whisker/fiber surface in situ, does not use chemical modification reagents, can improve the specific surface area of the whisker/fiber and the physical adsorption and mechanical blocking capacity of the contact site with the matrix material, and can be added into a thermal protection coating or a composite material as a second-phase toughening body to enhance the reinforcing and toughening performance of the matrix material.
(2) The invention adopts high-energy laser technology to greatly improve the preparation efficiency of whisker/fiber surface modified samples, does not influence the physical and mechanical properties of the original materials, achieves the purpose of regulating and controlling the morphology and shape characteristics of textured bumps on the whisker/fiber surface by controlling laser parameters and precursor proportions, and has good scientific significance and engineering application value.
Drawings
FIG. 1 is a scanning electron microscope image of a bump structure of in-situ grown silicon carbide nano particles on the surface of a laser irradiation silicon carbide whisker prepared in example 1;
FIG. 2 is a scanning electron microscope image of a bending port of a modified whisker doped thermal barrier coating prepared in example 1.
Detailed Description
The first embodiment is as follows: the modification method of the whisker/fiber surface texturing nanobump structure in the embodiment is implemented according to the following steps:
Adding whisker/fiber and nano-particles into a dispersing agent, and dispersing under the condition of mechanical stirring to enable the whisker/fiber and the nano-particles to be uniformly dispersed in a solvent under the mutual repulsive force action of surface functional groups, so as to form a whisker/fiber-nano-particle mixed precursor solution;
step two, coating whisker/fiber-nanoparticle mixed precursor solution on a preheated ceramic substrate, and forming a precursor coating on the ceramic substrate;
Step three, irradiating the precursor coating with high energy density through laser beams, controlling the laser spot diameter to be 1-6 mm in the laser irradiation process, the laser scanning speed to be 1-30 mm/s and the laser power to be 100-500W, and obtaining modified whisker/fiber;
and step four, repeatedly cleaning the modified whisker/fiber with deionized water to obtain the whisker/fiber with the surface textured nanobump structure modified.
In the first step of the embodiment, a certain amount of whisker/fiber and nano-particles are placed in a dispersing agent, and after a certain time of mechanical stirring and dispersing, the whisker/fiber and the particles are uniformly dispersed in a solvent under the mutual repulsive force action of hydroxyl functional groups to form a precursor solution; then vacuum drying the precursor solution and coating the precursor solution on a ceramic substrate; wherein, the ceramic substrate is preheated to reduce the heat dissipation rate of the energy field in the laser irradiation process and promote the sufficient growth of the whisker/fiber surface nanobump structure. The whiskers/fibers and nanoparticles of this embodiment may be homogenous materials or heterogeneous materials that may undergo a solid solution reaction.
According to the method, the whisker/nanoparticle mixed precursor is irradiated by a laser beam with high energy density, a classical VS (gas-solid) growth model is combined to control the growth mechanism of the nanoparticle at the top end of the whisker/fiber surface, and the supersaturation degree in the VS reaction process is controlled to be biased towards a medium or large supersaturation trend, so that the bump forms of flaky, dendritic, small spherical crystals, axises or particles are regulated, and the purpose of high designability of whisker surface modification is achieved. The energy input efficiency is realized by controlling the laser energy density, the crystallization saturation and the growth form of the nano particles in the VS (gas-solid) growth process are controlled, and finally the metallurgical bonding and the form of the nano bump structure on the whisker surface are controlled.
The embodiment provides a material micro-processing technology of a whisker/fiber surface texture physical modification mode with low cost and high preparation efficiency, so that the difficult problem of material surface modification is solved, the interface wettability of the whisker/fiber in a matrix material is improved, and the mechanical embedding effect of heterogeneous interfaces inside a composite material is improved, thereby realizing the rapid preparation of a toughening phase material and the improvement and application of the performance of the modified composite material.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that the whisker or fiber in the first step is silicon carbide, boron nitride, aluminum oxide, aluminum borate or YSZ (yttrium doped zirconia).
And a third specific embodiment: the difference between the present embodiment and the first or second embodiment is that the material of the nanoparticle in the first step is silicon carbide, boron nitride, aluminum oxide, aluminum borate or YSZ.
The specific embodiment IV is as follows: the difference between the present embodiment and one to three embodiments is that the dispersant in the first step is polyvinyl alcohol, polypropylene, stearamide, polyethylene glycol or absolute ethanol.
Fifth embodiment: the present embodiment differs from the first to fourth embodiments in that the volume ratio of the whiskers or fibers to the nanoparticles is controlled to be (8 to 12) in the first step: 1.
Specific embodiment six: the present embodiment differs from one to fifth embodiments in that the mechanical stirring time in the first step is 30 to 120 minutes.
Seventh embodiment: the present embodiment differs from the first to sixth embodiments in that the preheating temperature of the ceramic substrate in the second step is 40 to 60 ℃.
Eighth embodiment: the difference between the embodiment and the specific embodiment is that the diameter of the laser spot is controlled to be 1-3 mm, the laser scanning speed is 5-15 mm/s, and the laser power is 100-300W in the third step.
Detailed description nine: the application of the whisker/fiber modified by the surface texture nanobump structure in the embodiment is to add the modified whisker/fiber into a thermal protection coating or a composite material as a toughening reinforcing phase.
Detailed description ten: the difference between the embodiment and the specific embodiment is that the thermal protection coating is prepared by adopting a thermal spraying process, and the composite material is prepared by adopting a thermal sintering or thermal deposition process.
In the embodiment, the modified whisker/fiber is used as a second phase additive for toughening and reinforcing and added into a thermal protection coating or a composite material, and the whisker/fiber subjected to surface texturing treatment can improve the high-low temperature mechanical stability of a matrix material and adjust the thermal mass transfer and the thermal physical properties.
Example 1: the modification method of the whisker surface texturing nanobump structure is implemented according to the following steps:
Firstly, selecting silicon carbide whiskers with the length-diameter ratio of more than 20 and silicon carbide particles with the granularity of less than 40nm, adding 10 parts of silicon carbide whiskers and 1 part of nano silicon carbide particles into deionized water containing 5 parts of PVA dispersing agent according to parts by weight, and dispersing for 60 minutes under the condition of mechanical stirring, so that the whiskers and the nano particles are uniformly dispersed in a solvent under the mutual repulsive force of surface functional groups to form whisker-nano particle mixed precursor solution;
step two, uniformly spraying whisker-nanoparticle mixed precursor solution on a preheated ceramic substrate through a high-frequency spray valve, wherein the preheating temperature of the ceramic substrate is 50 ℃, and forming a precursor coating on the ceramic substrate;
Step three, irradiating the precursor coating with high energy density by laser beams, controlling the diameter of a laser spot to be 1mm, the laser scanning speed to be 10mm/s and the laser power to be 200W in the laser irradiation process, so as to control the crystallization saturation and the growth morphology of nano particles in the VS (gas-solid) growth process, promote the sufficient growth of nano bump structures on the whisker surface, and finally control the metallurgical bonding effect and the final morphology of the nano bump structures on the whisker surface to obtain modified whiskers;
And step four, repeatedly cleaning the modified whisker with deionized water to obtain the whisker with the surface textured nanobump structure modified.
Application examples: the modified whisker/fiber is used as a toughening reinforcing phase to be added into a thermal protection coating or a composite material, namely, the whisker with the modified surface texture nano bump structure prepared in the embodiment 1 is doped into YSZ ceramic powder, the ceramic powder is fully stirred and uniformly mixed to form composite ceramic powder, then the composite ceramic powder is sprayed and deposited on a base material through an atmospheric plasma spraying process, and a thermal barrier ceramic layer with the thickness of 300 mu m is stacked on the surface of the base material.
The comparative examples used conventional silicon carbide whiskers, unstructured modified.
In the second step of this embodiment, preheating the ceramic substrate has two effects, namely, fast evaporation of the liquid phase solvent in the precursor, and prevention of cracking of the ceramic due to fast temperature rise caused by too fast heat dissipation rate of the energy field during laser irradiation.
In the embodiment, the metallographic sample is obtained by preparing the surface texture modified whisker obtained in the step four and the sprayed thermal barrier coating bending-resistant port sample, and is characterized in that, as shown in the attached figures 1 and 2, the nano particles can be subjected to metallurgical reaction through laser high-energy irradiation and grow on the whisker surface in situ to form the texture salient points imitating the gecko foot structure, and the preparation efficiency of the method is high, the cost is low, and the method is suitable for industrial popularization. The three-point bending port of the composite thermal protection coating prepared by adding the modified whisker into the thermal barrier coating also presents a ductile pit state similar to that of a ductile material when the ductile material breaks to a certain extent, which indicates that the whisker/fiber surface texturing nanobump structure modification method and the toughening application thereof have good practical engineering application value and are suitable for industrialized popularization. Compared with the thermal barrier coating added with the textured modified whisker, the thermal barrier coating toughened by the unmodified whisker has lower bending strength than the thermal barrier coating toughened by the unmodified whisker, and the width of a yield platform of the thermal barrier coating toughened by the unmodified whisker in the bending yield process is longer than that of the thermal barrier coating toughened by the textured modified whisker, so that the mechanical toughening effect of the textured modified whisker on the thermal barrier coating is better than that of the unmodified whisker.
Claims (9)
1. The modification method of the whisker/fiber surface textured nanobump structure is characterized by comprising the following steps of:
adding whiskers or fibers and nano-particles into a dispersing agent, and dispersing under the condition of mechanical stirring to form whisker/fiber-nano-particle mixed precursor solution;
step two, coating whisker/fiber-nanoparticle mixed precursor solution on a preheated ceramic substrate, and forming a precursor coating on the ceramic substrate;
Step three, irradiating the precursor coating with high energy density through laser beams, controlling the laser spot diameter to be 1-6 mm in the laser irradiation process, the laser scanning speed to be 1-30 mm/s and the laser power to be 100-500W, and obtaining modified whisker/fiber;
repeatedly cleaning the modified whisker/fiber with deionized water to obtain the whisker/fiber with the modified surface textured nanobump structure;
The nano particles in the first step are made of silicon carbide, boron nitride, aluminum oxide, aluminum borate or YSZ.
2. The method of claim 1, wherein the whisker or fiber material in the step one is silicon carbide, boron nitride, aluminum oxide, aluminum borate or YSZ.
3. The method for modifying a whisker/fiber surface textured nanobump structure according to claim 1, wherein the dispersant in the first step is polyvinyl alcohol, polypropylene, stearamide, polyethylene glycol or absolute ethanol.
4. The method for modifying a whisker/fiber surface textured nanobump structure according to claim 1, wherein in the first step, the volume ratio of the whisker or fiber to the nanoparticle is controlled to be (8-12): 1.
5. The method for modifying a textured nanobump structure on a whisker/fiber surface according to claim 1, wherein the mechanical stirring time in the first step is 30 to 120 minutes.
6. The method for modifying a whisker/fiber surface textured nanobump structure according to claim 1, wherein the preheating temperature of the ceramic substrate in the second step is 40-60 ℃.
7. The method for modifying the whisker/fiber surface textured nanobump structure according to claim 1, wherein in the third step, the laser spot diameter is controlled to be 1-3 mm, the laser scanning speed is 5-15 mm/s, and the laser power is 100-300W.
8. The use of the surface-textured nanobump structure-modified whiskers/fibers prepared in accordance with claim 1, characterized in that the surface-textured nanobump structure-modified whiskers/fibers are added as a toughening reinforcement phase to a thermal protective coating or composite material.
9. The application of the whisker/fiber modified by the surface-textured nanobump structure according to claim 8, wherein the thermal protection coating is prepared by a thermal spraying process, and the composite material is prepared by a thermal sintering or thermal deposition process.
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