CN111041323B - Method for regulating and controlling expansion coefficient of light compact near-zero expansion metal matrix composite material - Google Patents

Method for regulating and controlling expansion coefficient of light compact near-zero expansion metal matrix composite material Download PDF

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CN111041323B
CN111041323B CN201911378839.8A CN201911378839A CN111041323B CN 111041323 B CN111041323 B CN 111041323B CN 201911378839 A CN201911378839 A CN 201911378839A CN 111041323 B CN111041323 B CN 111041323B
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metal matrix
expansion
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CN111041323A (en
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欧阳求保
曹贺
崔铎
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Shanghai Jiaotong University
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • 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
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • 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

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Abstract

The invention provides a method for regulating and controlling the expansion coefficient of a light compact near-zero expansion metal matrix composite, which comprises the following steps: with a negative expansion material Mn3(MnxZnySnz) The N powder and the metal matrix powder are used as raw materials, and the metal matrix is selected from any one of pure aluminum, pure copper, aluminum alloy, magnesium alloy, titanium alloy and copper alloy; adding Mn as negative expansion material3(MnxZnySnz) Mixing N powder with the metal matrix powder to obtain mixed powder; adjusting the ratio of the negative expansion material powder to the metal matrix powder, and/or adjusting the Mn of the negative expansion material3(MnxZnySnz) The particle size of the N powder is large, and the light compact near-zero expansion metal matrix composite material is obtained; wherein: the negative expansion material powder accounts for 1-50% of the total volume of the metal matrix composite, and the metal matrix powder accounts for 99-50% of the total volume of the metal matrix composite; negative expansion material Mn3(MnxZnySnz) The particle size of the N powder is adjusted within less than 150 mu m. The invention adjusts the Mn of the negative expansion material3(MnxZnySnz) The particle size and the content of the N powder can realize the regulation and control of the thermal expansion coefficients (including zero expansion) of various metal matrix composite materials.

Description

Method for regulating and controlling expansion coefficient of light compact near-zero expansion metal matrix composite material
Technical Field
The invention relates to a light near-zero expansion composite material, in particular to a method for regulating and controlling the expansion coefficient of a light compact near-zero expansion metal matrix composite material.
Background
Most materials in nature exhibit the phenomenon of "expansion with heat and contraction with cold". The characteristic of the material provides a great deal of convenience for people and brings much trouble to modern life, and mainly causes thermal stress in the material due to expansion with heat and contraction with cold, and even causes the material to crack and fail. The property of the material volume that changes with temperature also has a large effect on the precision of precision parts. For example, for precise focusing and collimating of the optical path of precision optical equipment such as telescopes, laser devices, and fiber-optic communication, the "milli-centimeter" of the size of the components caused by thermal expansion may cause "spurious" of the test results.
The negative thermal expansion material has the special property of thermal shrinkage and cold expansion, and has attracted international attention since the discovery in the 50 s of the last century. This anomalous thermal expansion behavior makes negative thermal expansion materials potentially valuable for many applications. The negative thermal expansion material is used for reducing or eliminating the influence of temperature on parts or structural members, reducing or eliminating internal stress damage caused by thermal expansion, improving the comprehensive performance and the use precision of equipment and prolonging the service life. The method has important significance in the fields of aerospace, electronic elements, optical devices, precise instruments and the like.
Metals are widely used materials in structural design, mechanical systems and electronic packaging due to their excellent thermal and mechanical properties. The metal is a positive thermal expansion material, and the metal and the negative expansion material (reinforcement) are effectively compounded to obtain the metal matrix composite material which has excellent metal performance and nearly zero expansion.
The method for adjusting the thermal expansion coefficient of the composite material mainly changes the type and content of the negative thermal expansion material and preparation process parameters to realize the expansion coefficient of the near-zero expansion metal matrix composite material.
Through search, the Chinese patent with the application number of 201611041751.3 discloses a preparation method of a composite material with adjustable thermal expansion, the method comprises the composite material with adjustable thermal expansion, and the thermal expansion coefficient and the thermal conductivity coefficient can pass through a negative thermal expansion material Al2(WO4)3The volume content in the composite material is regulated and controlled. However, the above patents have the following disadvantages: patent 201611041751.3 fails to achieve a wide range of adjustment of the coefficient of thermal expansion, it is difficult to prepare zero expansion composites, and patent 201611041751.3 fails to change the temperature window where low coefficients of thermal expansion occur. For practical engineering application, adjustment of thermal expansion coefficient in service temperature range is more expectedAnd it is desirable that its coefficient of thermal expansion be as close to about zero as possible. The above patent cannot realize the adjustment of the thermal expansion coefficients in different temperature ranges by selecting multiple negative expansion systems, and the purpose of zero expansion can be realized by adjusting the thermal expansion coefficient of the composite material by changing the particle size distribution and content of the negative expansion material and the preparation process.
At present, the research on near-zero expansion composite materials in China is still in the beginning stage, and the research on the near-zero expansion materials uses resin as a matrix. The resin-based composite material has the defects of brittleness, easy aging, no temperature resistance, easy damage and the like due to the characteristics of the material, so that the application range of the resin-based composite material is greatly limited. The research on the metal matrix composite material with light weight, near-zero expansion characteristic and metallic performance has no related report at home and abroad.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for regulating and controlling the expansion coefficient of a light and compact near-zero expansion metal matrix composite material, so that the regulation and control of the near-zero expansion temperature interval of the near-zero expansion metal matrix composite material are realized.
The invention provides a method for regulating and controlling the expansion coefficient of a light compact near-zero expansion metal matrix composite material,
the method comprises the following steps: adopting a negative expansion material Mn3(MnxZnySnz) The N powder and the metal matrix powder are used as raw materials, and the metal matrix is any one of metal powders of pure aluminum, pure copper, pure titanium, aluminum alloy, magnesium alloy, titanium alloy and copper alloy; the negative expansion material Mn3(MnxZnySnz) N powder, x + y + z being 1;
adding Mn as negative expansion material3(MnxZnySnz) Mixing N powder with the metal matrix powder to obtain mixed powder;
adjusting the proportion of the negative expansion material powder to the metal matrix powder, and/or adjusting the Mn of the negative expansion material3(MnxZnySnz) The particle size of the N powder is small, and the light, compact and near-zero expansion is obtainedExpanding the metal matrix composite; wherein:
the negative expansion material powder accounts for 1-50% of the total volume of the metal matrix composite material, and the metal matrix powder accounts for 99-50% of the total volume of the metal matrix composite material;
the negative expansion material Mn3(MnxZnySnz) The particle size of the N powder is adjusted within less than 150 mu m.
Preferably, the method further comprises the following steps: preparing the negative expansion material Mn with different grade grain diameters3(MnxZnySnz) N powder is used as a raw material, wherein:
subjecting the block to negative expansion material Mn3(MnxZnySnz) Ball-milling N on a vacuum ball mill to prepare Mn3(MnxZnySnz) And screening the N powder into three grades of less than 40 microns, 40-75 microns and 75-150 microns.
Preferably, the method further comprises the following steps: and putting the mixed powder with the adjusted proportion and particle size into a hot pressing furnace for hot pressing and sintering to obtain the light compact near-zero expansion metal matrix composite material.
Preferably, the vacuum hot press sintering, wherein: the sintering temperature is 300-.
Preferably, the negative expansion material Mn3(MnxZnySnz) Mixing N powder with the metal matrix powder to obtain mixed powder, wherein: the powder mixing time is 5-30 hours, and the rotating speed is 100-200 r/min.
Preferably, the particle size of the metal matrix powder is 5-30 μm.
Compared with the prior art, the invention has at least one of the following beneficial effects:
the invention adjusts the Mn of the negative expansion material3(MnxZnySnz) The particle size and the content of the N powder can realize the large-range regulation of the thermal expansion coefficient of the metal-based composite material to the zero-expansion metal-based composite material, so that the near-zero-expansion metal-based composite material has good mechanical property and electric and heat conduction characteristics.
The near-zero expansion metal matrix composite material has the characteristics of adjustable and programmable performance, and the adjusting and controlling method is simple and easy to implement. The material can be widely applied to the fields of aerospace, electronic components, optical fiber communication and the like by adjusting the thermal expansion behavior.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of a method for controlling the expansion coefficient of a metal matrix composite according to a preferred embodiment of the present invention;
FIG. 2 is a thermal expansion curve diagram of two metal matrix composites in which the negative expansion material and the metal matrix powder are mixed according to different volume ratios in a preferred embodiment of the present invention;
FIG. 3 is a thermal expansion diagram of the composite material in example 2 of the present invention;
FIG. 4 is a thermal expansion diagram of the composite material of example 3 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
Referring to fig. 1, a flow chart of a method for regulating and controlling an expansion coefficient of a light dense near-zero expansion metal matrix composite according to an embodiment of the present invention is shown, where the flow chart includes the following steps:
negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Preparing N powder: adding block-shaped negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Grinding N with vacuum ball mill, and sieving to obtain powder of 75-150 μm.
Then will prepareNegative expansion material Mn of3(Mn0.1Zn0.5Sn0.4) And mixing the N powder and pure aluminum powder with the purity of 99.95 percent and the particle size of 25 mu m according to the volume ratio of 2:8, 3:7 and 4:6 respectively, wherein the powder mixing time is 30 hours, and the powder mixing rotating speed is 150r/min, so as to respectively obtain first composite material mixed powder, second composite material mixed powder and third composite material mixed powder for later use.
Besides pure aluminum, the metal matrix can be any one of common metal powder such as pure copper, pure titanium, aluminum alloy, magnesium alloy, titanium alloy, copper alloy and the like.
And respectively putting the prepared first composite material mixed powder, second composite material mixed powder and third composite material mixed powder into a vacuum hot-pressing sintering furnace for hot-pressing sintering, wherein the sintering temperature is 450 ℃, the sintering pressure is 400MPa, the heat preservation time is 20min, cooling along with the furnace, taking out the sintered body, and finally obtaining the first metal-based composite material, the second metal-based composite material and the third metal-based composite material.
Referring to FIG. 2, a negative expansion material Mn is included3(Mn0.1Zn0.5Sn0.4) The thermal expansion curves of the first metal matrix composite, the second metal matrix composite and the third metal matrix composite with the N volume fractions of 20%, 30% and 40% respectively show that the thermal expansion coefficients of the three composites are obviously changed in the range of 50-100 ℃, wherein the minimum thermal expansion coefficient of the composite with the volume fraction of 20% in the range is 6.48 multiplied by 10-6The minimum coefficient of thermal expansion of the composite material with a volume fraction of 30% is 2.30X 10 DEG C-6The minimum coefficient of thermal expansion of the composite material is 0.43X 10/deg.C and 40% by volume-6The temperature is higher than the temperature, so that the thermal expansion coefficient of the composite material is changed by adjusting the content of the negative expansion material.
Example 2
Referring to fig. 1, a flow chart of a method for regulating and controlling an expansion coefficient of a light dense near-zero expansion metal matrix composite according to an embodiment of the present invention is shown, where the flow chart includes the following steps:
negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Preparing N powder: adding block-shaped negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Grinding N with vacuum ball mill, and sieving to obtain 2-40 μm powder.
Then the prepared negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Mixing the N powder with 99.95% aluminum powder with the particle size of 25 mu m according to the volume ratio of 3:7, wherein the powder mixing time is 30h, and the powder mixing speed is 150r/min, so as to obtain the composite material mixed powder for later use.
And respectively putting the prepared composite material mixed powder into a vacuum hot-pressing sintering furnace for hot-pressing sintering, wherein the sintering temperature is 450 ℃, the sintering pressure is 400MPa, the heat preservation time is 10min, and after furnace cooling, taking out the sintered body to obtain the metal matrix composite material.
Referring to FIG. 3, a negative thermal expansion material Mn is included3(Mn0.1Zn0.5Sn0.4) The volume fraction of N is 30%, the grain size range is 2-40 μm, and the thermal expansion curve of the composite material prepared from pure aluminum is shown in the figure, the thermal expansion coefficient of the composite material is obviously changed within the range of 50-100 ℃, and the thermal expansion coefficient is 5.06 multiplied by 10-6V. C. It can be obtained by changing the Mn of the negative expansion material3(MnxZnySnz) The particle size of the N powder can regulate and control the thermal expansion coefficient of the composite material.
Example 3
Referring to fig. 1, a flow chart of a method for regulating and controlling an expansion coefficient of a light dense near-zero expansion metal matrix composite according to an embodiment of the present invention is shown, where the flow chart includes the following steps:
negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Preparing N powder: adding block-shaped negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) Grinding N with vacuum ball mill, and sieving to obtain powder of 40-75 μm.
Then the prepared negative expansion material Mn3(Mn0.1Zn0.5Sn0.4) The N powder and the aluminum powder with the purity of 99.95 percent and the particle diameter of 25 mu m are prepared according to the following stepsMixing the materials according to the volume ratio of 3:7, wherein the powder mixing time is 30h, and the powder mixing speed is 150r/min, so as to obtain the composite material mixed powder for later use.
And respectively putting the prepared composite material mixed powder into a vacuum hot-pressing sintering furnace for hot-pressing sintering, wherein the sintering temperature is 450 ℃, the sintering pressure is 400MPa, the heat preservation time is 10min, and after furnace cooling, taking out the sintered body to obtain the metal matrix composite material.
Referring to FIG. 4, there is shown a negative thermal expansion material Mn3(Mn0.1Zn0.5Sn0.4) The volume fraction of N is 30%, the grain size range is 40-75 μm, and the thermal expansion curve of the composite material prepared from pure aluminum is shown in the figure, the thermal expansion coefficient of the composite material is obviously changed within the range of 50-100 ℃, and the thermal expansion coefficient is 4.00 multiplied by 10-6V. C. It can be obtained by changing the Mn of the negative expansion material3(MnxZnySnz) The particle size of the N powder can regulate and control the thermal expansion coefficient of the composite material.
The method for regulating and controlling the expansion behavior of the light compact near-zero expansion metal matrix composite material can adopt the following modes: changing the Mn of the negative expansion material3(MnxZnySnz) The particle size of the N powder can be selected from different particle sizes of 0-40 μm, 40-75 μm, 75-150 μm and the like; changing the Mn of the negative expansion material3(MnxZnySnz) The doping proportion of the N powder can be selected from Mn which is a negative expansion material3(MnxZnySnz) The volume ratio of N to aluminum powder (purity 99.95%, particle size 25 μm) is 3:7, 4:6, etc.
The above examples were conducted by applying Mn to the negative expansion material3(MnxZnySnz) The regulation and control of the particle size and the doping proportion of the N powder can realize the regulation and control of the expansion behavior of the light compact near-zero expansion metal matrix composite material. The method is simple and easy to operate, and can realize the adjustment of the thermal expansion temperature coefficient of the composite material within a certain temperature range.
The regulating method of the invention specifically refers to a method for regulating the thermal expansion coefficient of a light compact near-zero expansion metal matrix composite material, which is realized byThe method adjusts the thermal expansion coefficient of the metal matrix composite material by changing the content and the particle size distribution of the negative expansion material, and keeps good mechanical property, electric conduction and heat conduction characteristics. The thermal expansion behavior of the material can be regulated and controlled by a negative expansion material Mn3(MnxZnySnz) The content and the particle size distribution of the N powder in the composite material are controlled; the material has the characteristics of adjustable and programmable performance, and the adjusting and controlling method is simple and easy to implement. The material can be widely applied to the fields of aerospace, electronic components, optical fiber communication and the like by adjusting the thermal expansion behavior.
The above is part of the preferred embodiment of the present invention, and it should be understood that there are other embodiments of the present invention, such as changing the sintering process parameters, such as temperature, pressure, sintering time, diameter of the mold, etc., in the above embodiments, which can be easily implemented by those skilled in the art.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.

Claims (3)

1. A method for regulating and controlling the expansion coefficient of a light compact near-zero expansion metal matrix composite material is characterized by comprising the following steps:
adopting a negative expansion material Mn3(MnxZnySnz) The N powder and the metal matrix powder are used as raw materials, and the metal matrix is any one of metal powders of pure aluminum, pure copper, pure titanium, aluminum alloy, magnesium alloy, titanium alloy and copper alloy; the negative expansion material Mn3(MnxZnySnz) N powder, x + y + z being 1;
adding Mn as negative expansion material3(MnxZnySnz) Mixing N powder with the metal matrix powder to obtain mixed powder;
adjusting the ratio of the negative expansion material powder to the metal matrix powder, and/or adjusting the negative expansion material powderExpansion material Mn3(MnxZnySnz) The particle size of the N powder is large, and the light compact near-zero expansion metal matrix composite material is obtained; wherein:
the negative expansion material powder accounts for 1-50% of the total volume of the metal matrix composite material, and the metal matrix powder accounts for 99-50% of the total volume of the metal matrix composite material;
the negative expansion material Mn3(MnxZnySnz) The particle size of the N powder is adjusted within less than 150 mu m;
the method further comprises the following steps: preparing the negative expansion material Mn with different grade grain diameters3(MnxZnySnz) N powder is used as a raw material, wherein: subjecting the block to negative expansion material Mn3(MnxZnySnz) Ball-milling N on a vacuum ball mill to prepare the negative expansion material Mn3(MnxZnySnz) Screening N powder into three grades of less than 40 microns, 40-75 microns and 75-150 microns;
the method further comprises the following steps: putting the mixed powder with the adjusted proportion and particle size into a hot pressing furnace for hot pressing and sintering to obtain a light compact near-zero expansion metal matrix composite material; the hot-pressing sintering is carried out, wherein: the sintering temperature is 300-.
2. The method for regulating and controlling the expansion coefficient of the light-weight compact near-zero expansion metal matrix composite material as claimed in claim 1, wherein the negative expansion material Mn is used3(MnxZnySnz) Mixing N powder with the metal matrix powder to obtain mixed powder, wherein: the powder mixing time is 5-30 hours, and the rotating speed is 100-200 r/min.
3. The method for regulating and controlling the expansion coefficient of the light dense near-zero expansion metal matrix composite material according to any one of claims 1-2, wherein the particle size of the metal matrix powder is 5-30 μm.
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