CN111018533A - Porous silicon carbide-based composite ceramic material and preparation method and application thereof - Google Patents
Porous silicon carbide-based composite ceramic material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 146
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 106
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 86
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 32
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 30
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000007598 dipping method Methods 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 239000012700 ceramic precursor Substances 0.000 claims abstract description 21
- 238000009413 insulation Methods 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 36
- 229910026551 ZrC Inorganic materials 0.000 claims description 35
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 claims description 35
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000005470 impregnation Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002028 Biomass Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 13
- 239000002023 wood Substances 0.000 claims description 11
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 7
- 241000018646 Pinus brutia Species 0.000 claims description 7
- 235000011613 Pinus brutia Nutrition 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002149 hierarchical pore Substances 0.000 claims description 6
- -1 polysiloxane Polymers 0.000 claims description 6
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 241001330002 Bambuseae Species 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 241000219492 Quercus Species 0.000 claims description 4
- 235000016976 Quercus macrolepis Nutrition 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
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- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
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- 239000000956 alloy Substances 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a porous silicon carbide-based composite ceramic material and a preparation method and application thereof. The method comprises the following steps: 1) dipping the porous carbon template in a liquid polycarbosilane precursor dissolved with a zirconium-containing polymer to obtain a silicon carbide-based composite ceramic precursor dipped carbon template; 2) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor, and then carrying out high-temperature ceramic treatment in a protective atmosphere to obtain the porous silicon carbide-based composite ceramic material. The composite ceramic material belongs to a light composite ceramic material, has low thermal conductivity and a thermal conductivity coefficient of 0.12-0.66 W.m‑1·K‑1The composite material can be used as a heat insulation material and meets the requirements of heat insulation at high temperature, energy conversion and the like. The preparation method enables the porous structure and the microscopic appearance of the carbon template to be well coveredThe method has the advantages of low cost, high yield, good reproducibility, easy realization, strong expansibility and high application value.
Description
Technical Field
The invention relates to the technical field of silicon carbide-based composite ceramic materials, in particular to a porous silicon carbide-based composite ceramic material and a preparation method and application thereof.
Background
Porous silicon carbide-based composite ceramic materials typically exhibit a number of unique properties, such as low density, high specific surface area, high permeability, and good resistance to high temperatures, which are not achievable with solid materials. Therefore, porous silicon carbide-based composites are attractive for industrial applications, and they can be used as catalyst supports, thermal insulation materials, filters, ultra-high temperature lightweight structural members, and the like. The uniform open cell structure and the complex layered microstructure can possess a plurality of unique characteristics, such as lower thermal conductivity at low density, and can be applied to high-temperature resistant thermal insulation and thermal protection materials in the fields of aerospace, energy and transportation.
CN105439563A discloses an integral porous carbon-silicon carbide composite material and a preparation method thereof, the composite material is prepared by firstly fully stirring and dispersing silicon carbide powder, silicon powder, carbon-containing powder and sintering aid in water, then preparing a blank by an ice crystal pore-forming method or an organic polymer foam template pore-forming method, and preparing an integral silicon carbide core body by high-temperature sintering; and then a carbon-containing shell layer with higher mechanical strength and stability is generated on the pore canal of the porous SiC core body by an in-situ generation method or a carbon-containing precursor polymerization carbonization method. The composite material has the characteristics of high specific surface area, easy surface activation, acid and alkali corrosion resistance, high temperature resistance, good thermal conductivity and electrical conductivity, higher and stable mechanical strength, lower gas passing pressure drop, low preparation cost and the like, and can be used as a carrier for loading a metal catalyst or directly used as a non-metal catalyst, so that the defects of easy pulverization, easy blockage, difficult molding, high price and the like of the conventional industrial activated carbon catalytic carrier are overcome, but the method is limited by the size of an organic polymer foam template or ice crystal, so that the carbon-silicon carbide composite material has uneven pore size distribution, unadjustable porosity and poorer reproducibility.
CN108300885A discloses a preparation method of a silicon carbide ceramic composite material, which comprises the following steps: obtaining a network interpenetrating silicon carbide framework, and carrying out pre-oxidation treatment on the network interpenetrating silicon carbide framework; filling alloy powder in the pores of the network interpenetrating silicon carbide skeleton after the pre-oxidation treatment; and sintering the mixture in a nitrogen atmosphere to obtain the silicon carbide ceramic/aluminum matrix composite with interpenetrating networks. The method fills the aluminum-magnesium-silicon alloy powder in the pores of the silicon carbide framework, improves the heat conduction performance of the silicon carbide ceramic composite material, and the heat conduction coefficient of the silicon carbide ceramic composite material is as high as 170--1·K-1And the application of the composite material in the field of thermal insulation is limited.
Therefore, how to develop a porous silicon carbide-based composite material with uniform pore size distribution, controllable porosity, good reproducibility and heat insulation effect becomes a problem to be solved at present.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a porous silicon carbide-based composite ceramic material and a preparation method and application thereof. The porous silicon carbide-based composite ceramic material has a hierarchical pore structure, uniform pore size distribution, high and controllable porosity, low thermal conductivity and good heat insulation effect; the method has the advantages of low cost, high yield, good reproducibility, easy realization, strong expansibility and wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a porous silicon carbide-based composite ceramic material, comprising the following steps:
(1) dipping the porous carbon template in a liquid polycarbosilane precursor dissolved with a zirconium-containing polymer to obtain a silicon carbide-based composite ceramic precursor dipped carbon template;
(2) and (2) curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor obtained in the step (1), and then carrying out high-temperature ceramic treatment in a protective atmosphere to obtain the porous silicon carbide-based composite ceramic material.
The preparation method of the porous silicon carbide-based composite ceramic material provided by the invention adopts a liquid polycarbosilane precursor dissolved with a zirconium-containing polymer as a impregnant, a carbon template as a raw material and no need of adding an organic solvent, and the porous silicon carbide-based composite ceramic material is obtained by a dipping and high-temperature ceramic method, wherein the dipping temperature is room temperature and no high-pressure equipment is needed. By adjusting the proportion of the precursor, the dipping process, controlling the curing and high-temperature ceramic parameters and the like, the silicon carbide-based composite ceramic material can be uniformly coated on the pore channel of the carbon template to form the porous silicon carbide-based composite ceramic material, so that the porous structure and the microscopic morphology of the carbon template can be well reserved; the method has the advantages of low cost, simple process, high yield, good reproducibility, easy realization, strong expansibility and wide application prospect.
Preferably, the zirconium-containing polymer of step (1) comprises any one of or a combination of at least two of a zirconium polysiloxane, a zirconium tetraallylamino, or a zirconium acetylacetonate, wherein the typical but non-limiting combination is: zirconium oxide and acetylacetonate, zirconium oxide and tetraallylamino zirconium, zirconium acetylacetonate and tetraallylamino zirconium, preferably zirconium acetylacetonate.
Preferably, the mass ratio of the liquid polycarbosilane to the zirconium-containing polymer is (3-6: 1), and may be, for example, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, and preferably (4.5-5.5: 1; if the mass ratio is less than 3:1, the prepared precursor has overlarge viscosity and is not beneficial to impregnation; the mass ratio is more than 6:1, and the ceramic conversion rate is low due to the fact that the viscosity of the prepared precursor is too low.
Preferably, the viscosity of the liquid polycarbosilane precursor dissolved with the zirconium-containing polymer in the step (1) is 0.8 to 5 pas, for example, 0.8 pas, 1.2 pas, 2.6 pas, 3 pas, 4.1 pas or 4.9 pas, preferably 1.2 to 3 pas; if the viscosity is less than 0.8Pa · s, the ceramic yield of the precursor is low; the viscosity is higher than 5 pas, resulting in lower impregnation efficiency of the precursor.
Preferably, the impregnation in step (1) comprises any one or a combination of at least two of vacuum impregnation, equal volume impregnation or excess impregnation, wherein the combination is typically but not limited to: vacuum impregnation and equal volume impregnation, vacuum impregnation and excess impregnation, preferably vacuum impregnation.
Preferably, the temperature of the impregnation in the step (1) is 20-28 ℃, for example, 20 ℃, 22 ℃, 25 ℃ or 28 ℃ and the like, and the temperature is normal temperature.
In the present invention, the impregnation process saturates the uptake of the porous carbon template.
Preferably, the impregnation time in step (1) is 12-100h, for example, 12h, 15h, 18h, 24h, 30h, 36h, 42h, 48h, 60h, 72h, 84h, 96h or 100h, etc., preferably 48-96 h.
Preferably, the porous carbon template of step (1) comprises any one of, or a combination of at least two of, a biomass carbon template, a foamed porous carbon or a MOF carbon material, wherein a typical but non-limiting combination: the biomass carbon template and the foamed porous carbon, the biomass carbon template and the MOF carbon material, the foamed porous carbon and the MOF carbon material, preferably the biomass carbon template.
In the invention, the biomass carbon template is low in cost, environment-friendly, renewable and easy to obtain, and as the uniform open cell structure and the complex layered microstructure can have a plurality of unique characteristics, such as high strength, high hardness and high toughness at low density, the carbonized material has high porosity and the pore surface is easy to modify, in recent years, the biomass structure in natural resources is widely used as a replica template for preparing advanced porous ceramic materials. Furthermore, the oriented tracheids in the wood also provide a unique porous structure of unidirectional array channels, suitable for applications in thermal insulation and lightweight high temperature components.
Preferably, the biomass carbon template is prepared by the following method: and carbonizing the wood in a protective atmosphere to obtain the biomass carbon template.
Preferably, the gas of the protective atmosphere comprises any one or a combination of at least two of hydrogen, nitrogen, argon or helium, among which typical but non-limiting combinations: hydrogen and argon, nitrogen and helium, and the like.
Preferably, the wood comprises any one of pine, oak or bamboo or a combination of at least two of them, with typical but non-limiting combinations: pine and oak, oak and bamboo, and the like.
Preferably, the temperature rise rate of the carbonization is 1 to 5 ℃/min, for example, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 4 ℃/min, 4.5 ℃/min, or 5 ℃/min, etc., preferably 1.5 to 2.5 ℃/min; if the temperature rise rate is lower than 1 ℃/min, the carbonization time is too long; the temperature rise rate is higher than 5 ℃/min, so that the local carbonization of the porous carbon template is not uniform, and cracks and deformation are generated.
Preferably, the carbonization temperature is 500-; if the temperature is lower than 500 ℃, insufficient carbonization results in high amorphous carbon content; temperatures above 1200 ℃ result in a decrease in the pore volume and specific surface area of the carbon template.
Preferably, the carbonization time is 2-8h, for example, 2h, 3h, 4h, 5h, 6h, 7h, 8h, etc.
Preferably, the curing temperature in step (2) is 160-240 ℃, such as 160 ℃, 170 ℃, 180 ℃, 200 ℃, 220 ℃, 230 ℃ or 240 ℃, and the like, and the curing temperature can increase the degree of the crosslinking reaction, thereby reducing the volatilization of the cracking gas and increasing the yield of the ceramic.
Preferably, the curing time in step (2) is 1-6h, such as 1h, 2h, 3h, 4h, 5h or 6 h.
Preferably, the gas of the protective atmosphere of step (2) comprises any one or a combination of at least two of hydrogen, nitrogen, argon or helium, wherein a typical but non-limiting combination is: hydrogen and argon, nitrogen and helium, and the like.
Preferably, the temperature rise rate of the high-temperature ceramic-making in the step (2) is 1-15 ℃/min, for example, 1 ℃/min, 2 ℃/min, 3 ℃/min, 5 ℃/min, 8 ℃/min, 10 ℃/min, 12 ℃/min or 15 ℃/min is preferably 5-10 ℃/min; if the temperature rise rate is lower than 1 ℃/min, the density of the composite ceramic material is increased, which is contrary to the requirement of pursuing light weight and high porosity; the temperature rise rate is higher than 15 ℃/min, so that the composite ceramic material has larger volume shrinkage and is accompanied with crack occurrence, and the mechanical strength of the composite ceramic material is reduced.
Preferably, the temperature of the high-temperature ceramic formation in the step (2) is 1000-1600 ℃, for example, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, 1550 ℃ or 1600 ℃, etc., preferably 1100-1500 ℃; if the temperature is lower than 1000 ℃, the obtained cracking product is in an amorphous state, and the product contains a large amount of free carbon, so that the self mechanical strength of the composite ceramic material is low; when the temperature is higher than 1600 ℃, the crystal quantity of the cracking product is increased, the grains grow further to cause the generation of brittle phases, and the mechanical property of the composite ceramic material is reduced.
Preferably, the high-temperature ceramming in the step (2) is carried out for 2-10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10 h.
As a further preferred embodiment of the present invention, the method comprises the steps of:
(1) in a protective atmosphere, heating the wood to 500-1200 ℃ at the speed of 1-5 ℃/min, and carrying out carbonization treatment for 2-8h to obtain a biomass carbon template;
(2) soaking a biomass carbon template in a liquid polycarbosilane precursor dissolved with a zirconium-containing polymer at the temperature of 20-28 ℃ by using a vacuum impregnation method, keeping for 12-100h, controlling the mass ratio of the liquid polycarbosilane to the zirconium-containing polymer to be (3-6):1, and controlling the viscosity of the precursor to be 0.8-5 Pa.s to obtain a silicon carbide-based composite ceramic precursor-impregnated carbon template;
(3) curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at the temperature of 160-240 ℃ for 1-6h, heating to 1000-1600 ℃ at the speed of 1-15 ℃/min in a protective atmosphere, and carrying out high-temperature ceramic treatment for 2-10h to obtain the porous silicon carbide-based composite ceramic material.
In a second aspect, the present invention provides a porous silicon carbide-based composite ceramic material prepared by the method according to the first aspect, wherein the composite ceramic material comprises a carbon template and a silicon carbide/zirconium carbide composite ceramic coated on the carbon template.
According to the porous silicon carbide-based composite ceramic material provided by the invention, a multi-stage pore structure generates larger interface thermal resistance, and the mutually communicated three-dimensional ordered porous structures further obstruct the transmission process of heat transfer phonons, so that the thermal conductivity of the material can be effectively reduced; the porous silicon carbide-based composite ceramic material has uniform pore size distribution, high porosity and controllability, and is a light composite ceramic material; the porous silicon carbide-based composite ceramic material has the advantages of low thermal conductivity, good heat insulation effect, high temperature resistance, high mechanical strength and excellent creep resistance, and meets the requirements of heat insulation, energy conversion and the like at high temperature.
Preferably, the composite ceramic material has a hierarchical pore structure comprising a pore channel structure with a micron scale, and compared with the existing technology for preparing the porous silicon carbide ceramic by using the silicon carbide-based ceramic powder, the porous silicon carbide-based composite ceramic material provided by the invention has the porosity of 65-85% and the thermal conductivity of 0.12-0.66 W.m-1·K-1The ceramic material has the characteristics of uniform pores, controllable porosity, high ceramic yield, high mechanical strength, low thermal conductivity, stable pore structure and difficulty in generating defects.
Preferably, the composite ceramic material has an average pore size of 10 to 50 μm, and may be, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 40 μm, or 48 μm, etc.
Preferably, the porosity of the composite ceramic material is 65-85%, for example 65%, 70%, 75%, 80%, 85% or the like.
Preferably, the composite ceramic material has a thermal conductivity of 0.12-0.66 W.m-1·K-1For example, it may be 0.12 W.m-1·K-1、0.15W·m-1·K-1、0.2W·m-1·K-1、0.25W·m-1·K-1、0.3W·m-1·K-1、0.4W·m-1·K-1、0.5W·m-1·K-1、0.55W·m-1·K-1、0.6W·m-1·K-1、0.65W·m-1·K-1Or 0.66 W.m-1·K-1And the like.
In a third aspect, the present invention also provides the use of the porous silicon carbide-based composite ceramic material according to the second aspect in the fields of thermal insulation and energy conversion.
Due to the existence of a large number of pore structures, the porous silicon carbide-based composite ceramic material provided by the invention not only has the high temperature resistance, wear resistance, high mechanical strength and excellent chemical and shape stability of the silicon carbide-based composite ceramic, but also has low density, high specific surface area, low thermal conductivity and good impact resistance, is a light and high thermal resistance composite ceramic material, and has wide application prospects in the fields of heat insulation and energy conversion.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the porous silicon carbide-based composite ceramic material provided by the invention has a hierarchical pore structure, uniform pore size distribution and controllable porosity, and is a light composite ceramic material; the porous silicon carbide-based composite ceramic material has low thermal conductivity and the thermal conductivity coefficient of 0.12-0.66 W.m-1·K-1Can be used as a heat insulating material to meet the requirements of heat insulation at high temperature, energy conversion and the like;
(2) according to the preparation method of the porous silicon carbide-based composite ceramic material, the porous silicon carbide-based composite ceramic material is obtained by a dipping and high-temperature ceramic method, and the tight combination of the carbon template and the silicon carbide-based composite ceramic material can be realized by adjusting process parameters, so that the silicon carbide-based composite ceramic material is uniformly coated on the carbon template, and the porous structure and the microscopic appearance of the carbon template are well reserved; the method has the advantages of low cost, high yield, good reproducibility, easy realization, strong expansibility and high application value.
Drawings
Fig. 1 is XRD patterns of the carbon template and the porous silicon carbide/zirconium carbide composite ceramic material prepared in example 1, in which (a) shows the XRD pattern of the carbon template and (b) shows the XRD pattern of the porous silicon carbide/zirconium carbide composite ceramic material.
Fig. 2 is an axial SEM image of the porous silicon carbide/zirconium carbide composite ceramic material prepared in example 2.
Fig. 3 is a radial SEM image of the porous silicon carbide/zirconium carbide composite ceramic material prepared in example 3.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In the invention, the porosity of the porous silicon carbide-based ceramic composite material is tested by adopting an Archimedes drainage method.
The pore size distribution was tested using an AutoPore V mercury porosimeter, Inc. of Michelia, USA.
X-ray diffraction was measured using an X-ray diffractometer model PANALYTICAL X' Pert Pro, the Netherlands.
The scanning electron microscope was characterized by using a Hitachi S-4800 field emission scanning electron microscope.
The thermal conductivity was measured by using a NETZSCH LFA 457MicroFlash laser thermal conductivity meter, a germany navy company.
Example 1
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 30 μm, a porosity of 75%, and a thermal conductivity of 0.49 w.m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) heating pine wood with the size of 20mm multiplied by 10mm to 1000 ℃ at the speed of 1.5 ℃/min, and carbonizing for 3h under the protection of argon to obtain a porous carbon template;
(2) dipping a porous carbon template in a liquid polycarbosilane precursor dissolved with poly-zirconium siloxane at 20 ℃, dipping for 48 hours in vacuum, increasing the weight by 65% after dipping, controlling the mass ratio of the liquid polycarbosilane to a zirconium-containing polymer to be 4.5:1, and controlling the viscosity of the precursor to be 3 Pa.s to obtain the silicon carbide-based composite ceramic precursor dipped carbon template;
(3) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at 180 ℃ for 2h, heating to 1550 ℃ at the speed of 5 ℃/min under the protection of argon, and cracking for 4h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
The porous silicon carbide/zirconium carbide composite ceramic material prepared in this example is subjected to characterization by XRD, and the characterization result is shown in fig. 1. As can be seen from the XRD pattern (a) of the carbon template in the figure, two obvious wider characteristic diffraction peaks of carbon appear, which indicates that the carbon template has more amorphous carbon content; as can be seen from the XRD spectrum (b) of the porous silicon carbide/zirconium carbide composite ceramic material in the figure, the diffraction peak of the porous silicon carbide/zirconium carbide composite ceramic material is sharper and the half-peak width is smaller, indicating that the crystallinity is higher and the grains are larger; the diffraction peak of the SiC/ZrC phase in the porous silicon carbide/zirconium carbide composite ceramic material is higher in relative intensity, which indicates that the content of the SiC/ZrC phase is higher. In addition, the diffraction peak for carbon is significantly reduced, indicating that the free carbon content in the porous composite is less.
Example 2
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 25 μm, a porosity of 85%, and a thermal conductivity of 0.12 w.m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) heating pine wood with the size of 30mm multiplied by 20mm multiplied by 10mm to 1100 ℃ at the speed of 2 ℃/min, and carbonizing for 5 hours under the protection of argon to obtain a porous carbon template;
(2) dipping a porous carbon template in a liquid polycarbosilane precursor dissolved with zirconium acetylacetonate at 22 ℃, dipping for 60h under vacuum, increasing the weight by 70% after dipping, controlling the mass ratio of the liquid polycarbosilane to a zirconium-containing polymer to be 5.5:1, and controlling the viscosity of the precursor to be 1.2 Pa.s to obtain the silicon carbide-based composite ceramic precursor dipped carbon template;
(3) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at 200 ℃ for 3h, heating to 1500 ℃ at the speed of 10 ℃/min under the protection of argon, and cracking for 6h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
SEM characterization is performed on the porous silicon carbide/zirconium carbide composite ceramic material prepared in this example in the axial direction, and the characterization result is shown in fig. 2. As can be seen from the figure, the porous silicon carbide/zirconium carbide composite ceramic material has a hierarchical pore structure, uniform pore size distribution, high porosity and an average pore size of 25 μm.
Example 3
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 15 μm, a porosity of 80%, and a thermal conductivity of 0.29W · m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) heating pine wood with the size of 40mm multiplied by 20mm to 1000 ℃ at the speed of 2.5 ℃/min, and carbonizing for 3h under the protection of argon to obtain a porous carbon template;
(2) dipping a porous carbon template in a liquid polycarbosilane precursor dissolved with poly-zirconium siloxane at 25 ℃, dipping for 72h in vacuum, increasing the weight by 75% after dipping, controlling the mass ratio of the liquid polycarbosilane to a zirconium-containing polymer to be 5:1, and controlling the viscosity of the precursor to be 2.6 Pa.s to obtain the silicon carbide-based composite ceramic precursor dipped carbon template;
(3) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at 180 ℃ for 4h, heating to 1300 ℃ at the speed of 8 ℃/min under the protection of argon, and cracking for 4h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
The porous silicon carbide/zirconium carbide composite ceramic material prepared in this example is subjected to SEM characterization in the radial direction, and the characterization result is shown in fig. 3. As can be seen from the figure, the porous silicon carbide/zirconium carbide composite ceramic material has uniform pore size distribution, SiC/ZrC crystal phase is formed on the pore wall of the carbon template, and the porous structures are communicated with each other.
Example 4
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 48 μm, a porosity of 82%, and a thermal conductivity of 0.22W · m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) heating pine wood with the size of 30mm multiplied by 20mm multiplied by 10mm to 1100 ℃ at the speed of 2 ℃/min, and carbonizing for 5 hours under the protection of argon to obtain a porous carbon template;
(2) dipping a porous carbon template in a liquid polycarbosilane precursor dissolved with zirconium acetylacetonate at 28 ℃, dipping for 96h under vacuum, increasing the weight by 80% after dipping, controlling the mass ratio of the liquid polycarbosilane to a zirconium-containing polymer to be 6:1, and controlling the viscosity of the precursor to be 0.8 Pa.s to obtain the silicon carbide-based composite ceramic precursor dipped carbon template;
(3) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at 200 ℃ for 5h, heating to 1400 ℃ at the speed of 10 ℃/min under the protection of argon, and cracking for 6h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
Example 5
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 40 μm, a porosity of 78%, and a thermal conductivity of 0.43W · m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) dipping the porous carbon foam in a liquid polycarbosilane precursor dissolved with tetraallylamino zirconium at 20 ℃, vacuum-dipping for 100h, increasing the weight by 85% after dipping, controlling the mass ratio of the liquid polycarbosilane to the zirconium-containing polymer to be 4.5:1, and controlling the viscosity of the precursor to be 3 Pa.s to obtain the silicon carbide-based composite ceramic precursor-dipped porous carbon foam;
(2) curing the foam porous carbon impregnated with the silicon carbide-based composite ceramic precursor at 160 ℃ for 6h, heating to 1600 ℃ at the speed of 15 ℃/min under the protection of argon, and cracking for 2h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
Example 6
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 10 μm, a porosity of 65%, and a thermal conductivity of 0.66W · m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) heating bamboo with size of 15mm × 10mm × 5mm to 500 deg.C at a rate of 1 deg.C/min, and carbonizing for 2h under hydrogen protection to obtain porous carbon template;
(2) dipping a porous carbon template in a liquid polycarbosilane precursor dissolved with poly-zirconium siloxane at 20 ℃, dipping for 12h in vacuum, increasing the weight by 40% after dipping, controlling the mass ratio of the liquid polycarbosilane to a zirconium-containing polymer to be 3.5:1, and controlling the viscosity of the precursor to be 4.1 Pa.s to obtain the silicon carbide-based composite ceramic precursor dipped carbon template;
(3) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at 240 ℃ for 1h, heating to 1150 ℃ at the speed of 1 ℃/min under the protection of hydrogen, and cracking for 2h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
Example 7
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 20 μm, a porosity of 79%, and a thermal conductivity of 0.37W · m-1·K-1；
The preparation method of the composite ceramic material comprises the following steps:
(1) heating oak with the size of 50mm multiplied by 30mm multiplied by 20mm to 1200 ℃ at the speed of 5 ℃/min, and carrying out carbonization treatment for 8h under the protection of nitrogen to obtain a porous carbon template;
(2) dipping a porous carbon template in a liquid polycarbosilane precursor dissolved with zirconium acetylacetonate at 20 ℃, dipping for 24h under vacuum, increasing the weight by 50% after dipping, controlling the mass ratio of the liquid polycarbosilane to a zirconium-containing polymer to be 3:1, and controlling the viscosity of the precursor to be 4.9 Pa.s to obtain the silicon carbide-based composite ceramic precursor dipped carbon template;
(3) and curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at 220 ℃ for 6h, heating to 1500 ℃ at the speed of 3 ℃/min under the protection of nitrogen, and cracking for 8h to obtain the porous silicon carbide/zirconium carbide composite ceramic material.
Example 8
The embodiment provides a porous silicon carbide/zirconium carbide composite ceramic materialThe average pore diameter of the composite ceramic material is 30 mu m, the porosity is 65 percent, and the heat conductivity coefficient is 0.65 W.m-1·K-1；
Compared with the preparation method of the composite ceramic material in the embodiment 1, the preparation method of the composite ceramic material is only different in that the high-temperature ceramic temperature in the step (3) is replaced by 850 ℃.
Example 9
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 25 μm, a porosity of 73%, and a thermal conductivity of 0.56 w.m-1·K-1；
Compared with the embodiment 1, the preparation method of the composite ceramic material is different only in that the high-temperature ceramic temperature in the step (3) is replaced by 1800 ℃.
Example 10
This example provides a porous silicon carbide/zirconium carbide composite ceramic material, which has an average pore diameter of 30 μm, a porosity of 67%, and a thermal conductivity of 0.62W · m-1·K-1；
Compared with the preparation method of the composite ceramic material in the embodiment 1, the preparation method of the composite ceramic material is only different in that the zirconium-containing polymer in the step (2) is replaced by the combination of the poly-zirconium-siloxane and the zirconium acetylacetonate, and the mass ratio is 1: 1.
It can be seen from the comprehensive examples 1-10 that, in examples 1-10, porous silicon carbide/zirconium carbide composite ceramic materials with uniform pore size distribution, higher porosity and lower thermal conductivity are prepared by adopting a method of combining impregnation and high-temperature ceramization, wherein, in examples 8 and 9, the high-temperature ceramization temperatures are respectively 850 ℃ and 1800 ℃, and the prepared porous silicon carbide-based composite ceramic material has higher thermal conductivity than that of example 1 and poorer mechanical properties than that of example 1, thereby indicating that the high-temperature ceramization temperature adopted in example 1 is more favorable for obtaining the porous silicon carbide-based composite ceramic material with lower thermal conductivity, good thermal insulation effect, high temperature resistance, higher mechanical strength and excellent creep resistance.
In conclusion, the porous silicon carbide-based composite ceramic material provided by the invention belongs to light composite ceramicsThe ceramic material has a hierarchical pore structure, uniform pore size distribution and high and controllable porosity; the porous silicon carbide-based composite ceramic material has low thermal conductivity and the thermal conductivity coefficient of 0.12-0.66 W.m-1·K-1Can be used as heat insulating material; in addition, the porous silicon carbide-based composite ceramic material also has the performances of high temperature resistance, higher mechanical strength and excellent creep resistance, and can meet the requirements of heat insulation, energy conversion and the like at high temperature; the preparation method of the porous silicon carbide-based composite ceramic material provided by the invention can well reserve the porous structure and the microscopic appearance of the carbon template; the method has the advantages of low cost, high yield, good reproducibility, easy realization, strong expansibility and wide application prospect.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A preparation method of a porous silicon carbide-based composite ceramic material is characterized by comprising the following steps:
(1) dipping the porous carbon template in a liquid polycarbosilane precursor dissolved with a zirconium-containing polymer to obtain a silicon carbide-based composite ceramic precursor dipped carbon template;
(2) and (2) curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor obtained in the step (1), and then carrying out high-temperature ceramic treatment in a protective atmosphere to obtain the porous silicon carbide-based composite ceramic material.
2. The method of claim 1, wherein the zirconium-containing polymer of step (1) comprises any one or a combination of at least two of a zirconium polysiloxane, a zirconium tetraallylamine, or a zirconium acetylacetonate, preferably zirconium acetylacetonate;
preferably, the mass ratio of the liquid polycarbosilane to the zirconium-containing polymer in the step (1) is (3-6):1, preferably (4.5-5.5): 1.
3. The method according to claim 1 or 2, wherein the viscosity of the liquid polycarbosilane precursor dissolved with the zirconium-containing polymer in step (1) is 0.8 to 5 Pa-s, preferably 1.2 to 3 Pa-s;
preferably, the impregnation in step (1) comprises any one or a combination of at least two of vacuum impregnation, equal volume impregnation or excess impregnation, preferably vacuum impregnation;
preferably, the temperature of the impregnation in the step (1) is 20-28 ℃;
preferably, the impregnation time in step (1) is 12 to 100h, preferably 48 to 96 h.
4. The method of any one of claims 1 to 3, wherein the porous carbon template of step (1) comprises any one or a combination of at least two of a biomass carbon template, a foamed porous carbon or a MOF carbon material, preferably a biomass carbon template; preferably, the biomass carbon template is prepared by the following method: carbonizing wood in a protective atmosphere to obtain a biomass carbon template;
preferably, the gas of the protective atmosphere comprises any one or a combination of at least two of hydrogen, nitrogen, argon or helium;
preferably, the wood comprises any one of pine, oak or bamboo or a combination of at least two thereof;
preferably, the temperature rise rate of the carbonization is 1-5 ℃/min, preferably 1.5-2.5 ℃/min;
preferably, the carbonization temperature is 500-1200 ℃, preferably 650-850 ℃;
preferably, the carbonization time is 2-8 h.
5. The method as claimed in any one of claims 1 to 4, wherein the temperature for curing in step (2) is 160 ℃ to 240 ℃;
preferably, the curing time of the step (2) is 1-6 h.
6. The method according to any one of claims 1 to 5, wherein the gas of the protective atmosphere of step (2) comprises any one or a combination of at least two of hydrogen, nitrogen, argon or helium;
preferably, the heating rate of the high-temperature ceramic in the step (2) is 1-15 ℃/min, preferably 5-10 ℃/min;
preferably, the temperature of the high-temperature ceramic in the step (2) is 1000-1600 ℃, preferably 1100-1500 ℃;
preferably, the high-temperature ceramic-forming time in the step (2) is 2-10 h.
7. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
(1) in a protective atmosphere, heating the wood to 500-1200 ℃ at the speed of 1-5 ℃/min, and carrying out carbonization treatment for 2-8h to obtain a biomass carbon template;
(2) soaking a biomass carbon template in a liquid polycarbosilane precursor dissolved with a zirconium-containing polymer at the temperature of 20-28 ℃ by using a vacuum impregnation method, keeping for 12-100h, controlling the mass ratio of the liquid polycarbosilane to the zirconium-containing polymer to be (3-6):1, and controlling the viscosity of the precursor to be 0.8-5 Pa.s to obtain a silicon carbide-based composite ceramic precursor-impregnated carbon template;
(3) curing the carbon template impregnated with the silicon carbide-based composite ceramic precursor at the temperature of 160-240 ℃ for 1-6h, heating to 1000-1600 ℃ at the speed of 1-15 ℃/min in a protective atmosphere, and carrying out high-temperature ceramic treatment for 2-10h to obtain the porous silicon carbide-based composite ceramic material.
8. The porous silicon carbide-based composite ceramic material prepared by the method according to any one of claims 1 to 7, wherein the composite ceramic material comprises a carbon template and a silicon carbide/zirconium carbide composite ceramic coated on the carbon template.
9. The composite ceramic material of claim 8, wherein the composite ceramic material has a hierarchical pore structure, including a micron-scale pore structure;
preferably, the composite ceramic material has an average pore size of 10 to 50 μm;
preferably, the porosity of the composite ceramic material is 65-85%;
preferably, the composite ceramic material has a thermal conductivity of 0.12-0.66 W.m-1·K-1。
10. Use of the porous silicon carbide-based composite ceramic material according to claim 8 or 9 in the fields of thermal insulation and energy conversion.
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| CN114085085A (en) * | 2021-12-13 | 2022-02-25 | 广东盛唐新材料技术有限公司 | Bio-based silicon carbide ceramic cotton cloth and preparation method thereof |
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| CN116376519A (en) * | 2023-03-16 | 2023-07-04 | 南京航空航天大学 | Sugarcane-derived porous silicon carbide ceramic-based heat storage material, preparation method and device |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319194A (en) * | 2013-06-24 | 2013-09-25 | 航天材料及工艺研究所 | Preparation method of high-strength anti-contact-damage porous SiC |
| CN104140537A (en) * | 2014-07-21 | 2014-11-12 | 航天材料及工艺研究所 | Hybridization liquid precursor, preparing method and method for preparing ZrC-SiC superhigh temperature ceramics and composite materials of ZrC-SiC superhigh temperature ceramics through hybridization liquid precursor |
| CN106083114A (en) * | 2016-06-03 | 2016-11-09 | 苏州赛力菲陶纤有限公司 | A kind of C/C ZrC SiC ceramic based composites brake disc and preparation method thereof |
-
2019
- 2019-12-25 CN CN201911357430.8A patent/CN111018533A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319194A (en) * | 2013-06-24 | 2013-09-25 | 航天材料及工艺研究所 | Preparation method of high-strength anti-contact-damage porous SiC |
| CN104140537A (en) * | 2014-07-21 | 2014-11-12 | 航天材料及工艺研究所 | Hybridization liquid precursor, preparing method and method for preparing ZrC-SiC superhigh temperature ceramics and composite materials of ZrC-SiC superhigh temperature ceramics through hybridization liquid precursor |
| CN106083114A (en) * | 2016-06-03 | 2016-11-09 | 苏州赛力菲陶纤有限公司 | A kind of C/C ZrC SiC ceramic based composites brake disc and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079639A (en) * | 2020-08-21 | 2020-12-15 | 西安理工大学 | Method for preparing porous zirconium carbide ceramic by adopting polymer precursor |
| CN113604195A (en) * | 2021-07-29 | 2021-11-05 | 西北工业大学 | X-waveband full-frequency wave-absorbing porous bentonite composite material and preparation method thereof |
| CN113604195B (en) * | 2021-07-29 | 2024-01-30 | 西北工业大学 | Porous bentonite composite material with X-band full-frequency wave absorption function and preparation method thereof |
| CN114085085A (en) * | 2021-12-13 | 2022-02-25 | 广东盛唐新材料技术有限公司 | Bio-based silicon carbide ceramic cotton cloth and preparation method thereof |
| CN115010510A (en) * | 2022-04-25 | 2022-09-06 | 上海交通大学 | Low-thermal-conductivity zirconium carbide-coated zirconia ceramic foam material and preparation method thereof |
| CN116376519A (en) * | 2023-03-16 | 2023-07-04 | 南京航空航天大学 | Sugarcane-derived porous silicon carbide ceramic-based heat storage material, preparation method and device |
| CN116376519B (en) * | 2023-03-16 | 2024-03-29 | 南京航空航天大学 | Sugarcane-derived porous silicon carbide ceramic-based heat storage material, preparation method and device |
| CN116514577A (en) * | 2023-05-05 | 2023-08-01 | 天津大学 | Super-elastic precursor ceramic spring for wide temperature range, pressure sensor of super-elastic precursor ceramic spring and preparation method of super-elastic precursor ceramic spring |
| CN116514577B (en) * | 2023-05-05 | 2023-10-20 | 天津大学 | Super-elastic precursor ceramic spring for wide temperature range, pressure sensor of super-elastic precursor ceramic spring and preparation method of super-elastic precursor ceramic spring |
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Application publication date: 20200417 |