CN116949313B - A wide temperature range near-zero expansion multi-phase perovskite manganese nitrogen compound/aluminum composite material and preparation method thereof - Google Patents
A wide temperature range near-zero expansion multi-phase perovskite manganese nitrogen compound/aluminum composite material and preparation method thereof Download PDFInfo
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- RBVYPNHAAJQXIW-UHFFFAOYSA-N azanylidynemanganese Chemical compound [N].[Mn] RBVYPNHAAJQXIW-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 229910017464 nitrogen compound Inorganic materials 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 82
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 70
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000002787 reinforcement Effects 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims description 144
- 239000011701 zinc Substances 0.000 claims description 72
- 239000010949 copper Substances 0.000 claims description 50
- 229910001018 Cast iron Inorganic materials 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 230000008595 infiltration Effects 0.000 claims description 13
- 238000001764 infiltration Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- -1 manganese dinitrogen Chemical compound 0.000 claims description 7
- 239000010953 base metal Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910021364 Al-Si alloy Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 229910017818 Cu—Mg Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000011863 silicon-based powder Substances 0.000 claims description 3
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 2
- 229910000952 Be alloy Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 2
- 229910019086 Mg-Cu Inorganic materials 0.000 claims description 2
- 229910018594 Si-Cu Inorganic materials 0.000 claims description 2
- 229910007981 Si-Mg Inorganic materials 0.000 claims description 2
- 229910008465 Si—Cu Inorganic materials 0.000 claims description 2
- 229910008316 Si—Mg Inorganic materials 0.000 claims description 2
- 229910007565 Zn—Cu Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 4
- 238000009715 pressure infiltration Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000035882 stress Effects 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1073—Infiltration or casting under mechanical pressure, e.g. squeeze casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D23/00—Casting processes not provided for in groups B22D1/00 - B22D21/00
- B22D23/04—Casting by dipping
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1068—Making hard metals based on borides, carbides, nitrides, oxides or silicides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0068—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
一种宽温区近零膨胀多相反钙钛矿锰氮化合物/铝复合材料及其制备方法，涉及一种铝基复合材料及其制备方法。为了解决现有的反钙钛矿锰氮化合物/铝复合材料的近零膨胀温度区间较窄的问题，宽温区近零膨胀多相反钙钛矿锰氮化合物/铝复合材料由多相反钙钛矿锰氮化合物增强体和基体金属复合而成；制备：按照反钙钛矿锰氮化合物增强体的分子式分别称取原料，并烧结得到多种反钙钛矿锰氮化合物，预压、预热后进行加压浸渗得到多相反钙钛矿锰氮化合物/铝复合材料。制备得到的多相反钙钛矿锰氮化合物/铝复合材料在温度区间为‑5～60℃内平均热膨胀系数仅为0.40×10‑6℃‑1，弯曲强度达211MPa，热导率可达46W/(m·K)。
A wide temperature range near-zero expansion multi-phase inverse perovskite manganese nitrogen compound/aluminum composite material and a preparation method thereof, relating to an aluminum-based composite material and a preparation method thereof. In order to solve the problem that the near-zero expansion temperature range of the existing inverse perovskite manganese nitrogen compound/aluminum composite material is relatively narrow, the wide temperature range near-zero expansion multi-phase inverse perovskite manganese nitrogen compound/aluminum composite material is composited by a multi-phase inverse perovskite manganese nitrogen compound reinforcement and a matrix metal; preparation: weighing raw materials respectively according to the molecular formula of the inverse perovskite manganese nitrogen compound reinforcement, sintering to obtain a variety of inverse perovskite manganese nitrogen compounds, pre-pressing and preheating, and then pressurizing and infiltrating to obtain a multi-phase inverse perovskite manganese nitrogen compound/aluminum composite material. The prepared multi-phase inverse perovskite manganese nitrogen compound/aluminum composite material has an average thermal expansion coefficient of only 0.40×10 ‑6 ℃ ‑1 in the temperature range of ‑5 to 60 ℃, a bending strength of 211MPa, and a thermal conductivity of up to 46W/(m·K).
Description
Technical Field
The invention relates to an aluminum-based composite material and a preparation method thereof.
Background
In recent years, with the development of technology, the fields of aerospace, electronic packaging and the like have higher requirements on instrument performance. The traditional material generates dimensional change when the ambient temperature changes due to the property of thermal expansion and contraction, and the dimensional change affects the structure of the instrument on one hand, thereby affecting the precision; on the other hand, thermal stress can be generated due to inconsistent thermal deformation amounts of different materials, and fatigue is easy to generate for a long time to influence the service life of the instrument, so that the development of near-zero expansion materials is a difficult problem to be solved. The use of reinforcements with negative thermal expansion to inhibit thermal expansion of metal substrates and organics is an effective means by composite design.
The inverse perovskite manganese-nitrogen compound is known for its great magnetic volume effect, which produces great volume shrinkage at the magnetic transition temperature point, thus producing a negative thermal expansion phenomenon. At present, the anti-perovskite manganese-nitrogen compound with the thermal expansion performance of-60 to-150 multiplied by 10 -6℃-1 can be obtained within the temperature range of 10-20 ℃ through element doping relaxation of the magnetic transformation behavior. Because of its large negative thermal expansion coefficient, the anti-perovskite manganese nitrogen compound is considered as an ideal reinforcement for suppressing high thermal expansion materials such as metals, organics, and the like. Meanwhile, the elastic modulus of the anti-perovskite manganese-nitrogen compound can reach 150-200 GPa, the thermal conductivity can reach 1.8-4.0W/(m.K), and the prepared composite material can also have excellent mechanical property and thermal conductivity. However, the negative thermal expansion temperature range of the single anti-perovskite manganese nitrogen compound is narrow although the negative thermal expansion coefficient is extremely large. The prepared anti-perovskite manganese-nitrogen compound/aluminum composite material only realizes near zero expansion in the temperature range of 10-15 ℃. Therefore, how to widen the near zero expansion temperature interval of the inverse perovskite manganese nitrogen compound/aluminum composite material is a current problem.
Disclosure of Invention
The invention provides a perovskite manganese-nitrogen compound/aluminum composite material with wide temperature range and near zero expansion and multiple opposite expansion, and a preparation method thereof, aiming at solving the problem that the existing anti-perovskite manganese-nitrogen compound/aluminum composite material is narrower in near zero expansion temperature range.
The wide-temperature-zone near-zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material is formed by compounding a multi-phase anti-perovskite manganese-nitrogen compound reinforcement and a matrix metal; the volume fraction of the multi-phase inverse perovskite manganese-nitrogen compound reinforcement in the composite material is 20-70%;
The heterogeneous inverse perovskite manganese nitrogen compound reinforcement includes at least two of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x- ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN, wherein 0< x <1,0< y <1,0< x+y <1;
The preparation method of the wide-temperature-zone near-zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material comprises the following steps:
1. Respectively weighing raw materials according to at least two of molecular formulas Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x-ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x- ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN of the anti-perovskite manganese-nitrogen compound reinforcement, and respectively performing briquetting and vacuum sintering to obtain various anti-perovskite manganese-nitrogen compounds, wherein 0< x <1,0< y <1,0< x+y <1;
2. Mixing the multiple anti-perovskite manganese-nitrogen compounds obtained in the first step to obtain mixed powder, and then placing the mixed powder in a cast iron mold for prepressing to obtain the multi-opposite perovskite manganese-nitrogen compound;
the mass fraction of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x-ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN in the multiphase inverse perovskite manganese-nitrogen compound is 0-50%;
3. placing the cast iron mould filled with the multi-contrary perovskite manganese-nitrogen compound in the second step into a furnace for preheating;
4. pouring the molten matrix metal into a preheated iron mold, then carrying out pressurized infiltration, and finally cooling and demolding to obtain the multi-opposite perovskite manganese-nitrogen compound/aluminum composite material; the volume fraction of the multi-phase inverse perovskite manganese nitrogen compound reinforcement in the composite material is 20-70%.
The principle and beneficial effects of the invention are as follows:
1. the preparation method adopts a preposition process to prepare a plurality of anti-perovskite manganese-nitrogen compounds with different temperature areas and combines the plurality of anti-perovskite manganese-nitrogen compounds according to a specific proportion, so that the negative thermal expansion temperature interval of the anti-perovskite manganese-nitrogen compounds is expanded from a single-phase temperature interval to a multi-phase temperature interval; the negative thermal expansion coefficient of the obtained multiphase inverse perovskite manganese-nitrogen compound with the wide temperature range and near zero expansion reaches minus 10 to minus 40 multiplied by 10 -6/DEG C within the temperature range of 50-100 ℃.
2. The composite material prepared by the pressure infiltration method is a multiphase inverse perovskite manganese-nitrogen compound/aluminum composite material. The negative thermal expansion effect of various anti-perovskite manganese-nitrogen compounds in the composite material is exerted in different temperature ranges, so that the thermal expansion of an aluminum matrix is restrained in a wider temperature range, and the design of a near-zero expansion material in a wide temperature range is realized. The average thermal expansion coefficient of the finally prepared multiphase inverse perovskite manganese-nitrogen compound/aluminum composite material is only 0.40 multiplied by 10 -6℃-1 in the temperature range of-5 to 60 ℃, meanwhile, the bending strength can reach 211MPa, the thermal conductivity can reach 46W/(m.K), and the composite material has excellent comprehensive performance.
Drawings
FIG. 1 is a graph of thermal expansion curve in example 1;
FIG. 2 is a graph of bending stress strain for the multi-phase perovskite manganese nitrogen compound/aluminum composite material of example 1;
FIG. 3 is a graph of thermal expansion curve in example 2;
FIG. 4 is a graph of thermal expansion curve in example 3.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also comprises any reasonable combination of the specific embodiments.
The first embodiment is as follows: the wide-temperature-zone near-zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material is formed by compounding a multi-phase anti-perovskite manganese-nitrogen compound reinforcement body and a matrix metal; the volume fraction of the multi-phase inverse perovskite manganese-nitrogen compound reinforcement in the composite material is 20-70%;
The heterogeneous inverse perovskite manganese nitrogen compound reinforcement includes at least two of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x- ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN, where 0< x <1,0< y <1,0< x+y <1.
The negative thermal expansion coefficient of the multiphase inverse perovskite manganese-nitrogen compound with the wide temperature range and near zero expansion reaches-10 to-40 multiplied by 10 -6/DEG C within the temperature range of 50-100 ℃. In the multi-contrary perovskite manganese nitrogen compound/aluminum composite material of the embodiment, various anti-perovskite manganese nitrogen compounds exert negative thermal expansion effects in different temperature ranges, so that thermal expansion of an aluminum matrix is inhibited in a wider temperature range, and the design of a near-zero expansion material in a wide temperature range is realized. The average thermal expansion coefficient of the multi-contrary perovskite manganese-nitrogen compound/aluminum composite material is only 0.40 multiplied by 10 -6℃-1 in the temperature range of-5 to 60 ℃, meanwhile, the bending strength can reach 211MPa, the thermal conductivity can reach 46W/(m.K), and the multi-contrary perovskite manganese-nitrogen compound/aluminum composite material has excellent comprehensive performance.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the base metal is pure aluminum or aluminum alloy.
And a third specific embodiment: the second difference between this embodiment and the second embodiment is that: the aluminum alloy is one or a mixture of more of Al-Si alloy, al-Cu alloy, al-Mg alloy, al-Si-Cu alloy, al-Si-Mg alloy, al-Cu-Mg alloy, al-Zn-Cu alloy, al-Zn-Mg-Cu alloy, al-Be alloy, al-Li alloy and Al-Si-Cu-Mg alloy.
The specific embodiment IV is as follows: the preparation method of the perovskite manganese-nitrogen compound/aluminum composite material with the wide temperature range and near zero expansion and multiple opposite directions comprises the following steps:
1. Respectively weighing raw materials according to at least two of molecular formulas Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x-ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x- ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN of the anti-perovskite manganese-nitrogen compound reinforcement, and respectively performing briquetting and vacuum sintering to obtain various anti-perovskite manganese-nitrogen compounds, wherein 0< x <1,0< y <1,0< x+y <1;
2. Mixing the multiple anti-perovskite manganese-nitrogen compounds obtained in the first step to obtain mixed powder, and then placing the mixed powder in a cast iron mold for prepressing to obtain the multi-opposite perovskite manganese-nitrogen compound;
the mass fraction of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x-ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN in the multiphase inverse perovskite manganese-nitrogen compound is 0-50%;
3. placing the cast iron mould filled with the multi-contrary perovskite manganese-nitrogen compound in the second step into a furnace for preheating;
4. pouring the molten matrix metal into a preheated iron mold, then carrying out pressurized infiltration, and finally cooling and demolding to obtain the multi-opposite perovskite manganese-nitrogen compound/aluminum composite material; the volume fraction of the multi-phase inverse perovskite manganese nitrogen compound reinforcement in the composite material is 20-70%.
1. In the embodiment, a prepositive process is adopted to prepare a plurality of anti-perovskite manganese-nitrogen compounds with different temperature areas for negative thermal expansion, and then the plurality of anti-perovskite manganese-nitrogen compounds are combined according to a specific proportion, so that the negative thermal expansion temperature interval of the anti-perovskite manganese-nitrogen compounds is expanded from a single-phase temperature interval to a multi-phase temperature interval; the negative thermal expansion coefficient of the obtained multiphase inverse perovskite manganese-nitrogen compound with the wide temperature range and near zero expansion reaches minus 10 to minus 40 multiplied by 10 -6/DEG C within the temperature range of 50-100 ℃.
2. The composite material prepared by the pressure infiltration method is a multiphase inverse perovskite manganese-nitrogen compound/aluminum composite material. The negative thermal expansion effect of various anti-perovskite manganese-nitrogen compounds in the composite material is exerted in different temperature ranges, so that the thermal expansion of an aluminum matrix is restrained in a wider temperature range, and the design of a near-zero expansion material in a wide temperature range is realized. The average thermal expansion coefficient of the finally prepared multiphase inverse perovskite manganese-nitrogen compound/aluminum composite material is only 0.40 multiplied by 10 -6℃-1 in the temperature range of-5 to 60 ℃, meanwhile, the bending strength can reach 211MPa, the thermal conductivity can reach 46W/(m.K), and the composite material has excellent comprehensive performance.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the raw materials in the first step are manganese dinitrogen, manganese tetranitrogen, zinc powder, tin powder, copper powder, germanium powder or silicon powder.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the temperature of the vacuum sintering is 700-1000 ℃; the vacuum degree of the vacuum sintering is 1×10 -5Pa～1×10-4 Pa.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: and step two, the pre-pressing pressure is 2-20 MPa.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: step three, the preheating temperature is 400-800 ℃; the preheating time is 1-4 h.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: and step four, the temperature of the molten matrix metal is 700-900 ℃.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: the pressure during the pressurized infiltration is 20-40 MPa; the time for the pressurized infiltration is 10-30 min.
Example 1:
The preparation method of the perovskite manganese-nitrogen compound/aluminum composite material with the wide temperature range and near zero expansion and multiple opposite directions comprises the following steps:
1. respectively weighing raw materials according to molecular formula Mn3Zn0.6Sn0.4N、Mn3Zn0.65Sn0.35N、Mn3Zn0.7Sn0.3N、Mn3Zn0.75Sn0.25N、Mn3Zn0.8Sn0.2N of the anti-perovskite manganese-nitrogen compound reinforcement, and respectively performing briquetting and vacuum sintering to obtain 5 anti-perovskite manganese-nitrogen compounds;
The raw materials are manganese dinitrogen, zinc powder and tin powder;
The temperature of the vacuum sintering is 850 ℃;
The vacuum degree of the vacuum sintering is 1 multiplied by 10 -5 Pa;
2. Mixing the multiple anti-perovskite manganese-nitrogen compounds obtained in the first step to obtain mixed powder, and then placing the mixed powder in a cast iron mold for prepressing to obtain the multi-opposite perovskite manganese-nitrogen compound; the mass ratio of each anti-perovskite manganese-nitrogen compound in the multi-opposite perovskite manganese-nitrogen compound is ：Mn3Zn0.6Sn0.4N：Mn3Zn0.65Sn0.35N：Mn3Zn0.7Sn0.3N：Mn3Zn0.75Sn0.25N：Mn3Zn0.8Sn0.2N＝0.35：0.15：0.23：0.14：0.13,, and the internal thermal expansion coefficient of the multi-phase anti-perovskite manganese-nitrogen compound is-30 multiplied by 10 -6/DEG C at 0-75 ℃;
the size of the cast iron mold is 90mm in diameter;
The pre-pressing pressure is 5MPa;
3. placing the cast iron mould filled with the multi-contrary perovskite manganese-nitrogen compound in the second step into a furnace for preheating;
The preheating temperature is 600 ℃;
The preheating time is 1h;
4. Pouring the molten matrix metal into a preheated iron mold, then carrying out pressurized infiltration, and finally cooling and demolding to obtain the multi-opposite perovskite manganese-nitrogen compound/aluminum composite material; the volume fraction of the multi-phase inverse perovskite manganese nitrogen compound reinforcement in the composite material is 50%; the matrix alloy is Al-Si alloy;
the temperature of the molten base metal is 800 ℃;
the pressure during the pressurized infiltration is 30MPa;
the time for the pressurized impregnation was 10min.
Comparative example: the preparation method of the single-contrary perovskite manganese nitrogen compound/aluminum composite material of the present comparative example is different from that of example 1 in that: the reinforcement was a single-phase inverse perovskite manganese nitrogen compound Mn 3Zn0.7Sn0.3 N, and the other steps and parameters were the same as in example 1.
FIG. 1 is a graph of thermal expansion curve in example 1; in the figure, curve 1 is the thermal expansion curve of the single-phase inverse perovskite manganese nitrogen compound (Mn 3Zn0.7Sn0.3 N)/aluminum composite material in the comparative example; curve 2 is the thermal expansion curve of the multi-phase inverse perovskite manganese nitrogen compound/aluminum composite material prepared in step four of example 1; curve 3 is the thermal expansion curve of the multi-inverse perovskite manganese nitrogen compound prepared in step two of example 1; as can be seen in fig. 1, the temperature range of near zero expansion of the multi-phase design of the anti-perovskite manganese nitrogen compound/aluminum composite material in example 1 is widened by a factor of 3 to 4 compared to the single-phase anti-perovskite manganese nitrogen compound/aluminum composite material. FIG. 2 is a graph of bending stress strain curves for the multi-phase perovskite manganese nitrogen compound/aluminum composite material of example 1. Example 1a plurality of anti-perovskite manganese nitrogen compounds with different temperature areas negative thermal expansion are prepared first, and then the plurality of anti-perovskite manganese nitrogen compounds are combined according to a specific proportion, so that the negative thermal expansion coefficient of the multi-opposite perovskite manganese nitrogen compounds can reach-30 multiplied by 10 -6/°c within the temperature range of 0-75 ℃. The multi-phase perovskite manganese-nitrogen compound/aluminum composite material prepared by pressure infiltration inhibits the thermal expansion of an aluminum matrix in a wide temperature range, and the thermal expansion coefficient of the composite material in a temperature range of-5 to 60 ℃ is only 0.40X10 -6/DEG C. Meanwhile, the bending strength can reach 211MPa, the thermal conductivity can reach 46W/(m.K), and the composite material has excellent comprehensive performance.
Example 2:
The preparation method of the perovskite manganese-nitrogen compound/aluminum composite material with the wide temperature range and near zero expansion and multiple opposite directions comprises the following steps:
1. Respectively weighing raw materials according to molecular formulas Mn 3Zn0.7Sn0.2Mn0.1 N and Mn 3Zn0.53Sn0.27Si0.2 N of the anti-perovskite manganese-nitrogen compound reinforcement, and respectively performing briquetting and vacuum sintering to obtain 2 anti-perovskite manganese-nitrogen compounds;
the raw materials are manganese dinitrogen, zinc powder, tin powder and silicon powder;
The temperature of the vacuum sintering is 800 ℃;
The vacuum degree of the vacuum sintering is 1 multiplied by 10 -5 Pa;
2. Mixing the multiple anti-perovskite manganese-nitrogen compounds obtained in the first step to obtain mixed powder, and then placing the mixed powder in a cast iron mold for prepressing to obtain the multi-opposite perovskite manganese-nitrogen compound;
The mass fractions of Mn 3Zn0.7Sn0.2Mn0.1 N and Mn 3Zn0.53Sn0.27Si0.2 N in the multiphase inverse perovskite manganese-nitrogen compound are 50%;
The size of the cast iron mould is 60mm in diameter;
the pre-pressing pressure is 10MPa;
3. placing the cast iron mould filled with the multi-contrary perovskite manganese-nitrogen compound in the second step into a furnace for preheating;
The preheating temperature is 500 ℃;
The preheating time is 2 hours;
4. Pouring the molten matrix metal into a preheated iron mold, then carrying out pressurized infiltration, and finally cooling and demolding to obtain three multi-phase anti-perovskite manganese-nitrogen compound/aluminum composite materials (double-phase anti-perovskite manganese-nitrogen compound/aluminum composite materials); wherein the volume fractions of the multi-opposite perovskite manganese nitrogen compound reinforcements in the composite material are 35%, 50% and 60% respectively; the matrix alloy is Al-Si alloy;
the temperature of the molten base metal is 800 ℃;
the pressure during the pressurized infiltration is 30MPa;
the time for the pressurized impregnation was 10min.
Example 2a plurality of anti-perovskite manganese nitrogen compounds with different temperature areas negative thermal expansion are prepared, and then the two anti-perovskite manganese nitrogen compounds are combined according to a specific proportion, so that the negative thermal expansion coefficient of the double-phase anti-perovskite manganese nitrogen compound can reach-25 multiplied by 10 -6/DEG C within the temperature range of-25 to 50 ℃. The double-opposite perovskite manganese-nitrogen compound/aluminum composite material with different volume fractions is prepared through pressure infiltration, and the thermal expansion of an aluminum matrix is restrained in a wide temperature range. In fig. 3, curve 1 is the thermal expansion curve of 35vol.% of the double-opposing perovskite manganese-nitrogen compound/aluminum composite material, curve 2 is the thermal expansion curve of 50vol.% of the double-opposing perovskite manganese-nitrogen compound/aluminum composite material, and curve 3 is the thermal expansion curve of 60vol.% of the double-opposing perovskite manganese-nitrogen compound/aluminum composite material; in the temperature range of-25 to 50 ℃, the thermal expansion coefficient of the 35vol.% double-opposite perovskite manganese-nitrogen compound/aluminum composite material is only 6 multiplied by 10 -6/DEG C; 50vol.% of the dual-reversed perovskite manganese nitrogen compound/aluminum composite material has a coefficient of thermal expansion of only 1x 10 -6/°c; 60vol.% of the dual-reversed perovskite manganese nitrogen compound/aluminum composite material has a coefficient of thermal expansion of only-2 x 10 -6/°c;
example 3:
The preparation method of the perovskite manganese-nitrogen compound/aluminum composite material with the wide temperature range and near zero expansion and multiple opposite directions comprises the following steps:
1. Respectively weighing raw materials according to molecular formulas Mn 3Zn0.8Sn0.2N、Mn3Zn0.77Sn0.23 N and Mn 3Zn0.7Sn0.3 N of the anti-perovskite manganese-nitrogen compound reinforcement, and respectively performing briquetting and vacuum sintering to obtain 3 anti-perovskite manganese-nitrogen compounds;
The raw materials are manganese dinitrogen, zinc powder and tin powder;
the temperature of the vacuum sintering is 750 ℃;
The vacuum degree of the vacuum sintering is 1 multiplied by 10 -5 Pa;
2. Mixing the multiple anti-perovskite manganese-nitrogen compounds obtained in the first step to obtain mixed powder, and then placing the mixed powder in a cast iron mold for prepressing to obtain the multi-opposite perovskite manganese-nitrogen compound;
the mass ratio of each anti-perovskite manganese-nitrogen compound in the multi-opposite perovskite manganese-nitrogen compound is as follows ：Mn3Zn0.8Sn0.2N：Mn3Zn0.77Sn0.23N：Mn3Zn0.7Sn0.3N＝0.33：0.33：0.33;
The size of the cast iron mould is 60mm in diameter;
The pre-pressing pressure is 5MPa;
3. placing the cast iron mould filled with the multi-contrary perovskite manganese-nitrogen compound in the second step into a furnace for preheating;
The preheating temperature is 540 ℃;
The preheating time is 2 hours;
4. Pouring the molten matrix metal into a preheated iron mold, then carrying out pressurized infiltration, and finally cooling and demolding to obtain the multi-opposite perovskite manganese-nitrogen compound/aluminum composite material; the volume fraction of the multi-phase inverse perovskite manganese nitrogen compound reinforcement in the composite material is 50%; the matrix alloy is Al-Si alloy;
the temperature of the molten base metal is 800 ℃;
the pressure during the pressurized infiltration is 30MPa;
the time for the pressurized impregnation was 10min.
FIG. 4 is a graph of thermal expansion curve in example 3; in fig. 4, curve 1 is the thermal expansion curve of the multi-phase inverse perovskite manganese-nitrogen compound obtained in the second step; curve 2 is the thermal expansion curve of the multi-phase inverse perovskite manganese-nitrogen compound/aluminum composite material obtained in the step four; the negative thermal expansion coefficient of the multiphase inverse perovskite manganese-nitrogen compound obtained in the second step can reach-14 multiplied by 10 -6/DEG C within the temperature range of-40-50 ℃. The thermal expansion coefficient of the multiphase inverse perovskite manganese-nitrogen compound/aluminum composite material obtained in the step four is only 1 multiplied by 10 -6/DEG C within the temperature range of-40 to 50 ℃.
Claims (10)
1. A wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material is characterized in that: the wide-temperature-zone near-zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material is formed by compounding a multi-phase anti-perovskite manganese-nitrogen compound reinforcement and a base metal; the volume fraction of the multi-phase inverse perovskite manganese-nitrogen compound reinforcement in the composite material is 20-70%;
The heterogeneous inverse perovskite manganese nitrogen compound reinforcement includes at least two of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x- ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN, wherein 0< x <1,0< y <1,0< x+y <1;
The mass fraction of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x-ySnxSiyN、Mn3Zn1- xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN in the multiphase inverse perovskite manganese-nitrogen compound is 0-50%.
2. The wide temperature zone near zero expansion multi-phase perovskite manganese nitrogen compound/aluminum composite material according to claim 1, wherein: the base metal is pure aluminum or aluminum alloy.
3. The wide temperature zone near zero expansion multi-phase perovskite manganese nitrogen compound/aluminum composite material according to claim 2, wherein: the aluminum alloy is one or a mixture of more of Al-Si alloy, al-Cu alloy, al-Mg alloy, al-Si-Cu alloy, al-Si-Mg alloy, al-Cu-Mg alloy, al-Zn-Cu alloy, al-Zn-Mg-Cu alloy, al-Be alloy, al-Li alloy and Al-Si-Cu-Mg alloy.
4. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material as claimed in claim 1, wherein the method comprises the following steps: the preparation method of the perovskite manganese-nitrogen compound/aluminum composite material with the wide temperature zone and near zero expansion and multiple opposite directions comprises the following steps:
1. Respectively weighing raw materials according to at least two of molecular formulas Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x- ySnxSiyN、Mn3Zn1-xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN of the anti-perovskite manganese-nitrogen compound reinforcement, and respectively performing briquetting and vacuum sintering to obtain various anti-perovskite manganese-nitrogen compounds, wherein 0< x <1,0< y <1,0< x+y <1;
2. Mixing the multiple anti-perovskite manganese-nitrogen compounds obtained in the first step to obtain mixed powder, and then placing the mixed powder in a cast iron mold for prepressing to obtain the multi-opposite perovskite manganese-nitrogen compound;
The mass fraction of Mn3Zn1-xSnxN、Mn3Zn1-xGexN、Mn3Zn1-x-ySnxSiyN、Mn3Zn1- xSixN、Mn3Zn1-x-ySnxMnyN、Mn3Cu1-xSnxN、Mn3Cu1-xGexN、Mn3Cu1-x-ySnxSiyN、Mn3Cu1-xSixN、Mn3Cu1-x-ySnxMnyN in the multiphase inverse perovskite manganese-nitrogen compound is 0-50%;
3. placing the cast iron mould filled with the multi-contrary perovskite manganese-nitrogen compound in the second step into a furnace for preheating;
4. pouring the molten matrix metal into a preheated iron mold, then carrying out pressurized infiltration, and finally cooling and demolding to obtain the multi-opposite perovskite manganese-nitrogen compound/aluminum composite material; the volume fraction of the multi-phase inverse perovskite manganese nitrogen compound reinforcement in the composite material is 20-70%.
5. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material, which is characterized in that: the raw materials in the first step are manganese dinitrogen, manganese tetranitrogen, zinc powder, tin powder, copper powder, germanium powder or silicon powder.
6. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material, which is characterized in that: the temperature of the vacuum sintering is 700-1000 ℃; the vacuum degree of the vacuum sintering is 1×10 -5Pa～1×10-4 Pa.
7. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material, which is characterized in that: and step two, the pre-pressing pressure is 2-20 MPa.
8. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material, which is characterized in that: step three, the preheating temperature is 400-800 ℃; the preheating time is 1-4 h.
9. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material, which is characterized in that: and step four, the temperature of the molten matrix metal is 700-900 ℃.
10. The method for preparing the wide temperature range near zero expansion multi-opposite perovskite manganese-nitrogen compound/aluminum composite material, which is characterized in that: the pressure during the pressurized infiltration is 20-40 MPa; the time for the pressurized infiltration is 10-30 min.
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