Low-expansion phosphate powder for ultra-stable metal matrix composite and preparation method thereof
阅读说明：本技术 一种超稳定金属基复合材料用低膨胀磷酸盐粉体及其制备方法 (Low-expansion phosphate powder for ultra-stable metal matrix composite and preparation method thereof ) 是由 韩爽 王超 李博弘 陈泽明 曹先启 龙学云 王旭 关悦瑜 杨艳晶 谭蕾 于 2020-07-21 设计创作，主要内容包括：一种超稳定金属基复合材料用低膨胀磷酸盐粉体及其制备方法,它涉及低膨胀磷酸盐粉体及其制备。它要解决现有金属基复合材料热膨胀系数大的问题。产品：由醇溶性磷酸盐树脂、负膨胀AlPO<Sub>4</Sub>-17粉体、固化剂和无机填料制成。方法：制备醇溶性磷酸盐树脂；制备负膨胀AlPO<Sub>4</Sub>-17粉体；固化剂和无机填料进行表面处理；混合制备。本发明中低膨胀磷酸盐粉体,-120～1200℃热膨胀系数为0～1.0×10<Sup>-6</Sup>K<Sup>-1</Sup>,1000℃空气热失重为3.5％。低膨胀磷酸盐粉体加入到金属基复合材料中,使拉伸强度增大、弹性模量增大、热膨胀系数降低、耐热性提高。本发明工艺简单,便于工业化生产。本发明适用于作为金属基复合材料增强体。(A low-expansion phosphate powder for an ultra-stable metal matrix composite and a preparation method thereof relate to low-expansion phosphate powder and preparation thereof. The method aims to solve the problem that the existing metal matrix composite material has a large thermal expansion coefficient. The product is as follows: is prepared from alcohol-soluble phosphate resin and negative-expansion AlPO 4 -17 powder, curing agent and inorganic filler. The method comprises the following steps: preparing alcohol-soluble phosphate resin; preparation of negative expansion AlPO 4 -17 powder; carrying out surface treatment on a curing agent and an inorganic filler; and (4) mixing and preparing. The low-expansion phosphate powder has a thermal expansion coefficient of 0 to 1.0 x 10 at-120 to 1200 DEG C ‑6 K ‑1 The air thermal weight loss at 1000 ℃ is 3.5%. The low expansion phosphate powder is added into the metal matrix composite material, so that the tensile strength is increased, the elastic modulus is increased, the thermal expansion coefficient is reduced, and the heat resistance is improved. The invention has simple process and is convenient for industrial production. The invention is suitable for use asA metal matrix composite reinforcement.)
1. The low-expansion phosphate powder for the ultra-stable metal matrix composite is characterized by comprising 100 parts by mass of alcohol-soluble phosphate resin and 100-200 parts by mass of negative-expansion AlPO417-powder, 50-150 parts of curing agent and 50-200 parts of inorganic filler; wherein the curing agent is alumina; the inorganic filler is composed of, by mass, 20-100 parts of aluminum nitride, 20-100 parts of silicon nitride and 10-50 parts of silicon carbide.
2. The low-expansion phosphate powder for the ultra-stable metal matrix composite according to claim 1, wherein the particle size of the alumina is 50 to 150 nm.
3. The low-expansion phosphate powder for the ultra-stable metal matrix composite according to claim 1, wherein the particle size of the aluminum nitride is 30 to 100 nm; the particle size of the silicon nitride is 50-120 nm; the particle size of the silicon carbide is 80-150 nm.
4. The low-expansion phosphate powder for the ultra-stable metal matrix composite according to claim 1, which is prepared from 100 parts by weight of alcohol-soluble phosphate resin and 130 parts by weight of negatively-expanded AlPO417 parts of powder, 120 parts of curing agent and 150 parts of inorganic filler; the inorganic filler is composed of 40 parts of aluminum nitride, 80 parts of silicon nitride and 30 parts of silicon carbide in parts by mass.
5. The method for preparing the low-expansion phosphate powder for the ultra-stable metal matrix composite material according to claim 1 is characterized by comprising the following steps:
firstly, preparing alcohol-soluble phosphate resin:
according to the mass parts, heating 100 parts of industrial grade chromium dihydrogen phosphate aluminum solution in a water bath at 80-100 ℃, decompressing, carrying out rotary evaporation on the obtained product to remove a water solvent until the chromium dihydrogen phosphate aluminum is completely crystallized, adding 40-100 parts of an alcohol solvent, and fully dissolving to obtain alcohol-soluble phosphate resin;
two, negative expansion AlPO4-17 preparation of the powder:
adding aluminum hydroxide into deionized water, stirring until a uniform turbid liquid is formed, then dropwise adding phosphoric acid and cyclohexylamine at the stirring speed of 60-100 r/min, sealing into a high-pressure reaction kettle, heating for 96 hours at 200 ℃ under the hydrothermal self-generating condition, filtering, washing and drying the obtained solid product, and then calcining for 2-3 hours at 500 ℃ to obtain the negative expansion AlPO4-17 powder;
thirdly, carrying out surface treatment on the curing agent and the inorganic filler:
adding a surface treatment agent into absolute ethyl alcohol to prepare a 1.5 wt% solution, spraying the solution on a curing agent and an inorganic filler, putting the solution into a solid stirrer, stirring the solution at a rotating speed of 200-300 r/min for 10-30 min, and treating the solution at 120 ℃ for 1-2 h to finish the surface treatment of the curing agent and the inorganic filler; the surface treating agent is aluminum titanate, titanate or stearic acid;
fourthly, mixing preparation:
taking 100 parts of the alcohol-soluble phosphate resin obtained in the step one and the negative expansion AlPO obtained in the step two4100-200 parts of-17 powder, 50-150 parts of curing agent obtained in the third step and 50-200 parts of inorganic filler, uniformly mixing, curing at 150-180 ℃ for 1-2 h, treating at 600-800 ℃ for 2-3 h, taking out, and grinding into powder to finish the preparation of the low-expansion phosphate powder for the ultra-stable metal matrix composite;
wherein the curing agent in the third step is alumina; the inorganic filler consists of 20-100 parts of aluminum nitride, 20-100 parts of silicon nitride and 10-50 parts of silicon carbide in parts by weight; the particle size of the alumina is 50-150 nm; the particle size of the aluminum nitride is 30-100 nm; the particle size of the silicon nitride is 50-120 nm; the particle size of the silicon carbide is 80-150 nm.
6. The method according to claim 5, wherein the alcohol solvent is methanol, absolute ethanol, ethylene glycol, isopropanol or n-butanol.
7. The method according to claim 5, wherein the step two is carried out by heating at 200 ℃ for 96h under hydrothermal autogenous conditions to form an oxide of the initial gel within 1-5 min, wherein the molar composition of the oxide of the initial gel is 1P2O5:1Al2O3:1CHA:50H2O。
8. The method for preparing the low-expansion phosphate powder for the ultra-stable metal matrix composite according to claim 5, wherein the dropping speed in the second step is 400-500 mL/h.
9. The method for preparing a low-expansion phosphate powder for a super-stable metal matrix composite according to claim 5, wherein the filtering, washing and drying in step two: filtering with a 20-mesh screen, washing with deionized water for 3 times, and drying at 120-150 ℃ for 2-3 h.
10. The method of claim 5, wherein the grinding in step four is performed to obtain a powder with a particle size D50<20 um.
Technical Field
The invention relates to low-expansion phosphate powder and a preparation method thereof.
Background
With the continuous development of science and technology, the structural materials are required to be used more highly whether aviation, aerospace, national defense weaponry, and civil products such as automobiles and electronics. The metal matrix composite material is widely applied due to high specific strength, high specific modulus, and good heat conduction and electric conduction performance. However, in order to meet the use requirements of some ultra-stable components (such as control devices of missiles, satellites and the like), adding a certain volume fraction of reinforcement bodies into a metal or alloy matrix becomes one of the most effective solutions for reducing the thermal expansion coefficient. The phosphate has the advantages of small curing shrinkage, high temperature resistance, thermal stability, good heat conductivity, easy molding and processing and the like, and is widely used for aerospace high-temperature resistant parts; curing agents such as alumina, aluminum nitride, silicon carbide and the like, inorganic fillers, phosphate resin and negative expansion AlPO with excellent comprehensive performances such as high temperature resistance, low expansion, heat conduction and the like4And (4) mixing, curing and grinding the-17 powder to form the metal matrix composite material reinforcement.
Disclosure of Invention
The invention provides a low-expansion phosphate powder for an ultra-stable metal-based composite material and a preparation method thereof, aiming at solving the problem of large thermal expansion coefficient of the existing metal-based composite material and providing a novel metal-based composite material reinforcement.
The low-expansion phosphate powder for the ultra-stable metal matrix composite comprises, by mass, 100 parts of alcohol-soluble phosphate resin and 100-200 parts of negative-expansion AlPO417-powder, 50-150 parts of curing agent and 50-200 parts of inorganic filler; wherein the curing agent is alumina; the inorganic filler is composed of, by mass, 20-100 parts of aluminum nitride, 20-100 parts of silicon nitride and 10-50 parts of silicon carbide.
The preparation method of the low-expansion phosphate powder for the ultra-stable metal matrix composite material is realized by the following steps:
firstly, preparing alcohol-soluble phosphate resin:
according to the mass parts, heating 100 parts of industrial grade chromium dihydrogen phosphate aluminum solution in a water bath at 80-100 ℃, decompressing, carrying out rotary evaporation on the obtained product to remove a water solvent until the chromium dihydrogen phosphate aluminum is completely crystallized, adding 40-100 parts of an alcohol solvent, and fully dissolving to obtain alcohol-soluble phosphate resin;
two, negative expansion AlPO4-17 preparation of the powder:
adding aluminum hydroxide into deionized water, stirring until a uniform turbid liquid is formed, then dropwise adding phosphoric acid and cyclohexylamine at the stirring speed of 60-100 r/min, sealing into a high-pressure reaction kettle, heating for 96 hours at 200 ℃ under the hydrothermal self-generating condition, filtering, washing and drying the obtained solid product, and then calcining for 2-3 hours at 500 ℃ to obtain the negative expansion AlPO4-17 powder;
thirdly, carrying out surface treatment on the curing agent and the inorganic filler:
adding a surface treatment agent into absolute ethyl alcohol to prepare a 1.5 wt% solution, spraying the solution on a curing agent and an inorganic filler, putting the solution into a solid stirrer, stirring the solution at a rotating speed of 200-300 r/min for 10-30 min, and treating the solution at 120 ℃ for 1-2 h to finish the surface treatment of the curing agent and the inorganic filler; the surface treating agent is aluminum titanate, titanate or stearic acid;
fourthly, mixing preparation:
taking 100 parts of the alcohol-soluble phosphate resin obtained in the step one and the alcohol-soluble phosphate resin obtained in the step twoNegative expansion AlPO4100-200 parts of-17 powder, 50-150 parts of curing agent obtained in the third step and 50-200 parts of inorganic filler, uniformly mixing, curing at 150-180 ℃ for 1-2 h, treating at 600-800 ℃ for 2-3 h, taking out, and grinding into powder, thus completing the preparation of the low-expansion phosphate powder for the ultra-stable metal matrix composite.
The invention has the beneficial effects that:
the low-expansion phosphate powder for the ultra-stable metal matrix composite material has a thermal expansion coefficient of 0 to 1.0 multiplied by 10 at-120 to 1200 DEG C-6K-1Has a density of 2.08g/cm3The heat resistance is higher than 1700 ℃, and the air thermal weight loss at 1000 ℃ is 3.5%. The low-expansion phosphate powder for the ultra-stable metal matrix composite is added into the metal matrix composite, so that the tensile strength, the elastic modulus, the thermal expansion coefficient and the heat resistance of the metal matrix composite are increased; taking the example of adding ZK60A magnesium alloy into low expansion phosphate powder, the tensile strength is improved by 61%, the elastic modulus is improved by more than one time, and the thermal expansion coefficient is reduced by one time.
The preparation process of the low-expansion phosphate powder for the ultra-stable metal matrix composite material is simple and is convenient for industrial production.
The invention is suitable for being used as a metal matrix composite reinforcement.
Drawings
FIG. 1 shows the negative expansion AlPO with different volume fractions in the examples4-17 thermal expansion coefficient curve of low expansion phosphate powder for ultra stable metal matrix composite prepared from powder, wherein ■ represents negative expansion AlPO4-17 powder volume fraction of 0%, ● representing negatively expanded AlPO417-powder volume fraction of 10%, a-up representing negative expansion AlPO4-17 powder volume fraction of 20%, (t.t.) denotes negative expansion AlPO430% in volume fraction of-17 powder, diamond-solid representing negatively expanded AlPO4-17% by volume of the powder is 33%,
FIG. 2 is a thermogravimetric analysis graph of the low-expansion phosphate powder for the ultra-stable metal matrix composite in the example.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.