CN111647386B - Preparation method of silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive - Google Patents
Preparation method of silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims abstract description 44
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 35
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000012700 ceramic precursor Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003292 glue Substances 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 10
- -1 polymethylsiloxane Polymers 0.000 claims abstract description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 9
- 239000005011 phenolic resin Substances 0.000 claims abstract description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 9
- 239000005385 borate glass Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000011863 silicon-based powder Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 229910021418 black silicon Inorganic materials 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 abstract description 23
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012496 blank sample Substances 0.000 abstract description 3
- 206010053206 Fracture displacement Diseases 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
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- 239000002131 composite material Substances 0.000 description 5
- 206010017076 Fracture Diseases 0.000 description 3
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- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
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- 229910045601 alloy Inorganic materials 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/16—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
- C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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Abstract
一种碳化硅纳米线原位生长增韧陶瓷前驱体型高温胶制备方法。其包括利用乙烯基聚碳硅烷、聚甲基硅氧烷、酚醛树脂、二茂铁和异丙醇制备胶基液，以铝粉、镍粉、硅粉、碳化硼粉和硼酸盐玻璃粉末作为填料混合物，再通过混合胶基液和填料混合物制备高温胶等步骤。本发明效果：该高温胶在1100℃可原位生长出碳化硅纳米线而得到强韧化，使其粘结性能在1100～1500℃范围内得到极大改善，尤其在1300℃后，该高温胶常温粘结强度比无纳米线生长的空白样提高59.2％。碳化硅纳米线原位生长后，该高温胶在常温和高温下都表现出较好的韧性，所粘结粘结件的断裂位移曲线上有明显的近似屈服阶段出现，充分表明该高温胶具有很高的使用安全性。
A preparation method of silicon carbide nanowire in-situ growth and toughening ceramic precursor type high temperature adhesive. It includes the preparation of gum base using vinyl polycarbosilane, polymethylsiloxane, phenolic resin, ferrocene and isopropanol, powdered aluminum, nickel, silicon, boron carbide and borate glass powder. As the filler mixture, the high temperature glue is prepared by mixing the gum base liquid and the filler mixture. Effects of the invention: the high-temperature glue can grow silicon carbide nanowires in situ at 1100°C to be strengthened and toughened, so that its bonding performance is greatly improved in the range of 1100-1500°C, especially after 1300°C, the high temperature Compared with the blank sample without nanowire growth, the adhesive strength at room temperature was improved by 59.2%. After the in-situ growth of silicon carbide nanowires, the high-temperature adhesive showed good toughness at room temperature and high temperature, and the fracture displacement curve of the bonded part had an obvious approximate yield stage, which fully indicated that the high-temperature adhesive had High safety of use.
Description
Technical Field
The invention belongs to the technical field of adhesive material preparation, and particularly relates to a preparation method of a silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive.
Background
The adhesive has the characteristics of high connection efficiency, simple operation, low cost and the like, so that the adhesive is widely applied to the production and life of people, wherein the high-temperature adhesive can be directly applied to a high-temperature environment (up to 1500 ℃) after being cured and connected at low temperature, has small stress concentration of a connection interface, has small damage to a base body and the like, and is used for connecting, installing, fixing and repairing certain high-temperature components. These high temperature components typically include components made of high temperature resistant ceramics, ceramic matrix composites, and high temperature alloys. However, the joint strength and toughness of the conventional high-temperature adhesive are still low, and the conventional high-temperature adhesive needs to be toughened and reinforced.
The traditional third-party phase strengthening means limits the application of the method in the preparation of high-temperature glue due to higher cost and difficult solution of agglomeration, and the in-situ grown whisker self-toughening technology is applied to the strengthening of the high-temperature glue due to the characteristics of lower cost, high dispersion of grown whiskers and the like, wherein the in-situ toughening technology for growing mullite whiskers by aluminum fluoride catalysis is most commonly applied. However, the aluminum fluoride catalyst has a severe erosion property to the silicon-containing and aluminum-containing oxides in the glue matrix at high temperature, which easily causes the high-temperature-resistant glue to be porous, and the reduction of compactness causes the attenuation of the bonding effect. Therefore, the method has important significance for preparing the in-situ growth self-toughening type high-temperature adhesive with more prominent strengthening effect by searching for the novel in-situ growth micro-nano phase suitable for the field of adhesive bonding.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a preparation method of a silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive.
In order to achieve the aim, the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive provided by the invention comprises the following steps in sequence:
(1) uniformly mixing vinyl polycarbosilane, polymethylsiloxane, phenolic resin, ferrocene and isopropanol according to the mass ratio of 3.5-4.5: 1-2: 0.75-1.25: 0.6-0.9: 1.5-2.5, and then stirring for 5-6 h at 65 ℃ to prepare a gel base solution;
(2) fully and uniformly mixing aluminum powder, nickel powder, silicon powder, boron carbide powder and borate glass powder according to the mass ratio of 1.5-2.5: 1-1.5: 0.35-0.6: 0.15-0.3: 0.1-0.2 to prepare a filler mixture;
(3) and (3) mixing the glue base liquid prepared in the step (1) and the filler mixture prepared in the step (2) in a ball milling tank according to a liquid-solid mass ratio of 5-7: 4-5, and carrying out ball milling for 2-3 h at a rotating speed of 150-200 r/min to obtain the gray black silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature glue with the viscosity of 2500-3000 cps.
In step (1), the vinyl polycarbosilane is in liquid state, and is purchased from chemical research institute of Chinese academy of sciences, with a model number of VHCPS and a viscosity of 650-1000 cps.
In step (1), the polymethylsiloxane is a white powder available from Wacker-Belsil, GermanyTMCompany, chemical formula (CH)3–SiO3/2)x。
In the step (1), the phenolic resin is in a liquid state, is purchased from Jining HuaKai resin Co., Ltd, and has a viscosity of 1000 to 1500 cps.
In the step (1), the ferrocene and the isopropanol are purchased from Aladdin chemical reagent, Inc., and the components are analytically pure.
In the step (2), the aluminum powder is purchased from Beijing Xin Rui technology limited and has a particle size of 3-5 μm.
In the step (2), the silicon powder and the nickel powder are both purchased from Guangzhou Tuoyi trade company Limited and have the particle size of 0.5 μm.
In step (2), the boron carbide powder is obtained from Heilongjiang morning boron carbide Co., Ltd and has a particle size of 6 to 10 μm.
The silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive provided by the invention has the following beneficial effects:
1. compared with a blank control sample without nanowire growth, the bonding strength of the high-temperature adhesive is obviously improved at 1100-1500 ℃, and particularly the bonding strength of the high-temperature adhesive is improved by about 59.2% after treatment at 1300 ℃.
2. After treatment at 1300-1500 ℃, the high-temperature adhesive shows obvious anti-fracture yield effect at both normal temperature and high temperature, which shows that the brittleness is obviously improved;
3. the silicon carbide nanowires grow in the space (cracks, holes and the like) of the high-temperature glue, play a role in repairing the glue internal structure, and are the main reason why the high-temperature glue has an excellent bonding effect.
Drawings
FIG. 1 is a scanning electron microscope image of the surface morphology of the silicon carbide nanowire in-situ growth toughened ceramic precursor type high temperature adhesive prepared in example 1 after being processed at different temperatures; wherein FIG. 1(a) is 1000 ℃, FIG. 1(b) is 1100 ℃, FIG. 1(c) is 1300 ℃, and FIG. 1(d) is 1500 ℃;
FIG. 2 is a TEM photograph of a single SiC nanowire in the SiC nanowire in-situ grown toughened ceramic precursor type high temperature glue prepared in example 1;
FIG. 3 is a comparison of the shear strength of the carbon/carbon composite material bonded part of the silicon carbide nanowire in-situ growth toughened ceramic precursor type high temperature glue prepared in example 1 and a blank sample without nanowire growth after treatment at different temperatures;
FIG. 4 is a comparison of the loading force-displacement curves of the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive prepared in example 1 and the carbon/carbon composite material adhesive bonded by the blank sample without nanowire growth under different conditions;
FIG. 5 is a fracture surface morphology analysis of a carbon-carbon composite material bonded piece bonded with the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive prepared in example 1 after a shear test; in FIG. 5, the wavelength was 500nm in FIG. 5(a), 400nm in FIG. 5(b), and 1 μm in FIG. 5 (c).
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive provided by the embodiment comprises the following steps in sequence:
(1) uniformly mixing vinyl polycarbosilane, polymethylsiloxane, phenolic resin, ferrocene and isopropanol according to the mass ratio of 3.5:1.5:1:0.6:2.5, and stirring for 5 hours at the temperature of 65 ℃ to prepare a gel base solution;
(2) fully and uniformly mixing aluminum powder, nickel powder, silicon powder, boron carbide powder and borate glass powder according to the mass ratio of 1.5:1:0.35:0.2:0.1 to prepare a filler mixture;
(1) and (3) mixing the glue base liquid prepared in the step (1) and the filler mixture prepared in the step (2) in a ball milling tank according to the liquid-solid mass ratio of 5:4, and carrying out ball milling for 2h at the rotating speed of 200r/min to obtain the gray-black silicon carbide nanowire in-situ growth toughened ceramic precursor high-temperature glue with the viscosity of about 2500 cps.
Example 2
(1) Uniformly mixing vinyl polycarbosilane, polymethylsiloxane, phenolic resin, ferrocene and isopropanol according to the mass ratio of 4:2:1.25:0.9:2, and stirring for 6 hours at the temperature of 65 ℃ to prepare the colloidal base solution.
(2) Fully and uniformly mixing aluminum powder, nickel powder, silicon powder, boron carbide powder and trace borate glass powder according to the mass ratio of 2:1.5:0.5:0.15:0.2 to prepare a filler mixture;
(3) and (3) mixing the glue base liquid prepared in the step (1) and the filler mixture prepared in the step (2) in a ball milling tank according to the liquid-solid mass ratio of 6:5, and carrying out ball milling for 3 hours at the rotating speed of 200r/min to obtain the gray-black silicon carbide nanowire in-situ growth toughened ceramic precursor high-temperature glue with the viscosity of about 2500 cps.
Example 3
(1) Uniformly mixing vinyl polycarbosilane, polymethylsiloxane, phenolic resin, ferrocene and isopropanol according to the mass ratio of 4.5:1.5:0.75:0.7:1.5, and stirring for 6 hours at the temperature of 65 ℃ to prepare the colloidal base solution.
(2) Fully and uniformly mixing aluminum powder, nickel powder, silicon powder, boron carbide and trace borate glass powder according to the mass ratio of 2.5:1:0.6:0.3:0.1 to prepare a filler mixture;
(3) and (3) mixing the glue base liquid prepared in the step (1) and the filler mixture prepared in the step (2) in a ball milling tank according to the liquid-solid mass ratio of 7:5, and carrying out ball milling for 3 hours at the rotating speed of 150r/min to obtain the gray-black silicon carbide nanowire in-situ growth toughened ceramic precursor high-temperature glue with the viscosity of about 2500 cps.
In the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive prepared by the method, the main binding phase is a copolymer of polycarbosilane, polysiloxane and resin; ferrocene is a growth catalyst of the silicon carbide nanowire; the silicon powder, the aluminum powder and the nickel powder are used as the most main additives, and are used for generating a high-temperature ceramic phase on one hand and a temperature-resistant intermetallic compound on the other hand; boron carbide and glass powder are mainly melted at high temperature to improve the structure of the high-temperature glue; meanwhile, the oxidation of boron carbide can effectively compensate the volume shrinkage of the high-temperature agent in the heat treatment process.
In order to verify the toughening and reinforcing effects of the high temperature adhesive provided in the above embodiment, the inventor uses the high temperature adhesive without nanowire growth (without ferrocene) as a blank control sample, and the preparation method of the blank control sample is as follows:
(1) uniformly mixing vinyl polycarbosilane, polymethylsiloxane, phenolic resin and isopropanol according to the mass ratio of 3.5:1.5:1:2.5, and stirring for 5 hours at 65 ℃ to prepare the rubber base liquid.
(2) Fully and uniformly mixing aluminum powder, nickel powder, silicon powder, boron carbide and trace borate glass powder according to the mass ratio of 1.5:1:0.35:0.2:0.1 to prepare a filler mixture;
(3) and (3) mixing the glue base liquid prepared in the step (1) and the mixed filler prepared in the step (2) in a ball milling tank according to the liquid-solid mass ratio of 5:4, and carrying out ball milling for 2 hours at the rotating speed of 200r/min to obtain the gray-black high-temperature glue with the viscosity of about 2500 cps.
The experimental procedure was as follows:
1) the carbon/carbon composite material plate (30 multiplied by 10 multiplied by 3mm) which is polished, cleaned and dried is laid on a smooth and flawless glass plate, and the bonding surface is placed upwards;
2) the high-temperature glue and the blank control sample prepared in the above example were respectively spread on the entire one surface of each adherend using a spatula, and then the thickness of the high-temperature glue was controlled to 200 μm using an applicator;
3) bonding two carbon/carbon composite material plates together in a mode that bonding surfaces are opposite, pressing the plates into a bonding piece, curing the bonding piece at 200 ℃ for 2 hours, and then cutting the bonding piece into a double-notch test piece, wherein the area of the bonding surface is 12 multiplied by 10mm2；
4) Calcining the test piece in a high temperature furnace at different temperatures (300 deg.C, 400 deg.C, 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C, 1000 deg.C, 1100 deg.C, 1200 deg.C, 1300 deg.C, 1400 deg.C, 1500 deg.C) for 1 h;
5) and (3) observing the microstructure of the high-temperature adhesive: the bonded parts treated at different temperatures were prepared into SEM test samples, and the morphology of the high temperature glue in the bonded area was observed with a scanning electron microscope analyzer (Nanosem430, FEI), as shown in fig. 1.
As can be seen from FIG. 1, after the treatment at 1000 ℃, no nanowire is generated in the high-temperature glue; after the treatment at 1100 ℃, a small amount of short and thick linear bodies begin to be generated; after 1300 ℃, the slender nanowires are fully distributed with the glue matrix, the length-diameter ratio of the nanowires is about 30-40, and the high-temperature glue structure is still compact; after 1500 ℃, the length-diameter ratio of the nanowire is continuously increased to be more than 50.
6) Transmission analysis of nanowires: transmission scanning electron microscopy (Tecnai G2F 20, FEI) was used to demonstrate that the in-situ grown nanowire composition is silicon carbide, and a high-low power transmission photograph thereof is shown in FIG. 2. As can be seen from fig. 2: single crystal electron diffraction showed (111), (210) and
three facets, with a interplanar spacing along the growth direction of 0.25nm, is sufficient to demonstrate that the in situ grown nanowire component is beta-silicon carbide.
6) And (3) shear testing: the ordinary temperature bonding strength of the bonding piece treated at different temperatures is tested by using a CSS-44001 universal testing machine, the high temperature shearing strength of the bonding piece at high temperature is tested by using an RDL-15 high temperature universal testing machine, the bonding performance and the fracture toughness of the high temperature adhesive prepared in the comparative example and the blank control sample without nanowire growth are evaluated, and the ordinary temperature bonding strength of the two high temperature adhesives treated at different temperatures and the loading force-displacement curve under different conditions are respectively shown in fig. 3 and fig. 4;
as can be seen from FIG. 3, the bonding strength of the high temperature adhesive prepared in the example is improved from 1000 ℃, and the bonding strength at normal temperature is much higher than that of the blank control sample in the temperature range of 1100-1500 ℃; the bonding strength of the high temperature glue prepared in the above example after treatment at 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃ and 1500 ℃ was improved by 24.8%, 41.7%, 59.2%, 55.4% and 51.0%, respectively, compared to a blank control sample without nanowire growth.
As can be seen from fig. 4, compared with the blank control sample without nanowire growth, the fracture toughness of the high-temperature adhesive bonding piece prepared in the above embodiment is obviously improved after being treated at 1300 ℃ and tested at normal temperature, and an obvious approximate yield stage appears on the loading displacement curve, which proves that the growth of the nanowire effectively obtains the toughening effect. Meanwhile, the fracture displacement of the bonded part bonded by the high-temperature adhesive is higher than the test result of the normal temperature even at 1300 ℃, which is enough to show that the high-temperature adhesive prepared in the embodiment has higher damage resistance at high temperature.
7) And (3) observing a fracture surface: the morphology of the bonded surface after fracture by shear test was observed using a scanning electron microscope, as shown in fig. 5. The silicon carbide nanowires mainly grow in existing defect cracks of the high-temperature-resistant adhesive, and the cracks are effectively repaired in a bridging or overlapping mode, namely the structure of the high-temperature-resistant adhesive is improved; furthermore, as can be seen from fig. 5c, the growth of the nanowires also effectively hinders the propagation of cracks, which is another important reason for the toughening enhancement.
Those skilled in the art, having the benefit of this disclosure, will appreciate numerous modifications and variations there from, and fall within the scope of the invention.
Claims (8)
1. A preparation method of a silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive is characterized by comprising the following steps: the preparation method comprises the following steps which are carried out in sequence:
(1) uniformly mixing vinyl polycarbosilane, polymethylsiloxane, phenolic resin, ferrocene and isopropanol according to the mass ratio of 3.5-4.5: 1-2: 0.75-1.25: 0.6-0.9: 1.5-2.5, and then stirring for 5-6 h at 65 ℃ to prepare a gel base solution;
(2) fully and uniformly mixing aluminum powder, nickel powder, silicon powder, boron carbide powder and borate glass powder according to the mass ratio of 1.5-2.5: 1-1.5: 0.35-0.6: 0.15-0.3: 0.1-0.2 to prepare a filler mixture;
(3) and (3) mixing the glue base liquid prepared in the step (1) and the filler mixture prepared in the step (2) in a ball milling tank according to a liquid-solid mass ratio of 5-7: 4-5, and carrying out ball milling for 2-3 h at a rotating speed of 150-200 r/min to obtain the gray black silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature glue with the viscosity of 2500-3000 cps.
2. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in the step (1), the vinyl polycarbosilane is in a liquid state, the model is VHCPS, and the viscosity is 650-1000 cps.
3. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in the step (1), the polymethylsiloxane is white powder.
4. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in the step (1), the phenolic resin is in a liquid state, and the viscosity is 1000-1500 cps.
5. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in step (1), the ferrocene and isopropanol components are analytically pure.
6. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in the step (2), the particle size of the aluminum powder is 3-5 μm.
7. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in the step (2), the particle size of the silicon powder and the nickel powder is 0.5 μm.
8. The method for preparing the silicon carbide nanowire in-situ growth toughened ceramic precursor type high-temperature adhesive according to claim 1, which is characterized by comprising the following steps: in the step (2), the particle size of the boron carbide powder is 6-10 μm.
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