MM'X-Y METAL COMPOSITE FUNCTIONAL MATERIAL AND PREPARATION METHOD THEREOF

Abstract

An MMXY metal composite functional material and a preparation method thereof; an MMXY metal composite functional material, comprising the following components in percentage by volume: A% of M.sub.aM.sub.bX.sub.c and B% of Y, wherein each of M and M is any one element of a transition group or an alloy of more than one element, X is any one element of IIIA group or IVA group or an alloy of more than one element, and Y is any one element of IB group, IIB group, IIA group or IVA group, or an alloy of more than one element, wherein the value range of a, b and c is 0.8-1.2, and the sum of A% and B% is 100%; the material is prepared through smelting, annealing, crushing, mixing, pressing and curing, etc.; the mechanical performance of the MMXY metal composite functional material prepared according to the present invention is far higher than the traditional MMX material; the prepared MMXY metal composite functional material has an ideal magnetothermal effect, thus can be used as a magnetic refrigeration material; the method can prepare MMXY metal composite functional materials with any size and shape according to actual requirements; the method is simple, and can be easily operated and realized.

Claims

1. An MMXY metal composite functional material, comprising the following components in percentage by volume: A% of M.sub.aM.sub.bX.sub.c and B% of Y, wherein each of M and M is any one element of a transition group or an alloy of more than one element, X is any one element of IIIA group or IVA group or an alloy of more than one element, and Y is any one element of IB group, IIB group, IIA group or IVA group, or an alloy of more than one element, wherein the value range of a, b and c is 0.8-1.2, and the sum of A% and B% is 100%.

2. The MMXY metal composite functional material of claim 1, wherein A% is 50%-95%, and B% is 5%-50%.

3. The MMXY metal composite functional material of claim 1, wherein A% is 60%-90%, and B% is 10%-40%.

4. A preparation method of the MMXY metal composite functional material, comprising the steps of: 1) Preparing raw materials according to the chemical formula of M.sub.aM.sub.bX.sub.c; 2) Feeding the prepared raw materials into a smelting furnace, vacuuming the furnace and cleansing the furnace by argon; subsequently, smelting the prepared raw materials under the protection of argon, thereby obtaining the M.sub.aM.sub.bX.sub.c alloy; 3) Vacuuming and annealing the M.sub.aM.sub.bX.sub.c alloy; 4) Respectively crushing and grinding the vacuumed and annealed M.sub.aM.sub.bX.sub.c alloy and Y material; after screening, obtaining powders; 5) Respectively measuring out the powder of M.sub.aM.sub.bX.sub.c alloy with a volume percentage of A%, and the powder of Y material with a volume percentage of B%; subsequently, mixing them uniformly; 6) Adopting a pressing formation method to press the uniformly mixed powder under magnetic field, thereby obtaining the formed material; 7) Curing the formed material, thereby obtaining the MMX metal composite functional material.

5. The preparation method of the MMXY metal composite functional material of claim 4, wherein when M or M is Mn, Mn is excessively added according to the atomic ratio of 1%-10% for compensating its volatile and burning losses during the preparation process, thereby obtaining the single phase.

6. The preparation method of the MMXY metal composite functional material of claim 4, wherein when M or M is Mn, Mn is excessively added according to the atomic ratio of 2%-5%.

7. The preparation method of the MMXY metal composite functional material of claim 4, wherein the pressure in the smelting furnace is controlled to be smaller than or equal to 310.sup.3 Pa after being vacuumed, wherein the smelting temperature is higher than 1300 C., and the smelting time is 0.5-10 minutes.

8. The preparation method of the MMXY metal composite functional material of claim 4, wherein the pressure in the smelting furnace is 210.sup.3-310.sup.3 Pa after being vacuumed, wherein the smelting temperature is 1300-1700 C., and the smelting time is 2-3 minutes.

9. The preparation method of the MMXY metal composite functional material of claim 4, wherein the vacuuming and annealing temperature is 600-1100 C., and the time is 1-30 days.

10. The preparation method of the MMXY metal composite functional material of claim 4, wherein the vacuuming and annealing temperature is 700-900 C., and the time is 5-15 days.

11. The preparation method of the MMXY metal composite functional material of claim 4, wherein the crushing method comprises one or any combination of the following methods including grinding, vibration grinding, rolling grinding, ball milling and jet milling, etc., wherein the screen is a standard screen with a mesh size greater than 10 mesh, and the particle size of the powder is smaller than 2 mm.

12. The preparation method of the MMXY metal composite functional material of claim 4, wherein the screen is a standard screen with a mesh size of 100-300 mesh, and the particle size of the powder is 0-0.2 mm.

13. The preparation method of the MMXY metal composite functional material of claim 4, wherein the pressing formation is to press the powder into a required size or shape through a rolling method, a mold pressing method, an extrusion method, a powder injection forming method or a discharge plasma sintering method, wherein during the process of the pressing formation, the pressure is 300-1500 Mpa, the temperature is 0-900 C., the time is 1-240 minutes and the intensity of the magnetic field is 0-5 T.

14. The preparation method of the MMXY metal composite functional material of claim 4, wherein during the process of the pressing formation, the pressure is 600-1000 MPa, the temperature is 0-500 C., the time is 5-60 minutes and the intensity of the magnetic field is 0-2 T.

15. The preparation method of the MMXY metal composite functional material of claim 4, wherein the curing temperature is 0-900 C. and the curing time is 1-15 days.

16. The preparation method of the MMXY metal composite functional material of claim 4, wherein the curing temperature is 0-500 C. and the curing time is 2-7 days.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0036] To clearly expound the technical solution of the present invention, the drawings and embodiments are hereinafter combined to illustrate the present invention. Obviously, the drawings are merely some embodiments of the present invention and those skilled in the art can associate themselves with other drawings without paying creative labor.

[0037] FIG. 1 is a topography diagram of the smelted Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 prepared according to embodiment 1 of the present invention;

[0038] FIG. 2 is a topography diagram of the smelted 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material prepared according to embodiment 1 of the present invention;

[0039] FIG. 3 is a stress-strain curve graph of the 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material prepared according to embodiment 1 of the present invention;

[0040] FIG. 4 is a diagram showing the temperature dependence of S of the 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material prepared according to embodiment 1 of the present invention in different magnetic fields;

[0041] FIG. 5 is a stress-strain curve graph of the 75% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+25% In metal composite functional material prepared according to embodiment 2 of the present invention;

[0042] FIG. 6 is a stress-strain curve graph of the 80% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+20% In metal composite functional material prepared according to embodiment 3 of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

[0043] Drawings and detailed embodiments are combined hereinafter to elaborate the technical principles of the present invention.

Embodiment 1

[0044] As shown in FIGS. 1-4, the present invention discloses a 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material and a preparation method thereof.

[0045] The preparation method of the 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material, comprising the steps of: [0046] 1) Preparing raw materials according to the chemical formula of Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5, wherein the raw materials are commercially available metals including Mn, Fe, Ni, Si and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 5% for compensating its volatile and burning losses during the preparation process; [0047] 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 210.sup.3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1500 C. for 3 minutes under the protection of argon, thereby obtaining the cast ingot Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5; [0048] 3) Placing the Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 into a quartz tube with a vacuum degree of 510.sup.3 Pa, and annealing at a temperature of 850 C. for 7 days; [0049] 4) Respectively crushing and grinding the vacuumed and annealed Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 and metal In by using an agate mortar, and screening out the irregular powder with a size smaller than 0.1 mm according to the screening standard of 150-mesh; [0050] 5) Respectively measuring out the Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 powder with a volume percentage of 70%, and the In powder with a volume percentage of 30%; subsequently, mixing them uniformly; [0051] 6) Pressing the uniformly mixed powder at the condition of 150 C. and 900 MPa for 5 minutes under zero magnetic field, thereby obtaining a cylindrical 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material with a diameter of 10 mm; [0052] 7) Curing at a temperature of 150 C. for 7 days, thereby obtaining the 70% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+30% In metal composite functional material, namely, the product of this embodiment.

[0053] The morphology of the smelted Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 sample prepared in embodiment 1 is shown in FIG. 1. As can be seen from FIG. 1, after a traditional smelting process, the sample undergoes a martensitic transition when being cooled from a high temperature to a room temperature. The sample is crumbled due to the huge internal stress generated in the transition process, making the forming and mechanical machining become extremely difficult. The application range of the functional material is thus greatly limited. The morphology of the product of embodiment 1 is shown in FIG. 2. As can be seen, it can be easily formed and processed, effectively solving the prior technical problems.

[0054] For the mechanical performance of the traditional crumbled MMX alloy is extremely poor, the stress-strain curve test cannot be carried out. In contrast, the mechanical performance of the product prepared in embodiment 1 is remarkably improved so that the test can be easily performed. The stress-strain curve of the prepared product can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 3, after being tested, the compressive strength of the prepared product is 45 MPa, and the corresponding strain is 9.2%.

[0055] After measuring the isothermal magnetization curve (M-H curve) of the prepared product by using a magnetic measurement system (Versalab Free Measurement System developed by Quantum Design, Inc.), the magnetic entropy change S can be calculated from the isothermal magnetization curve according to Maxwell's relation S=.sub.0.sup.H(M/T).sub.HdH . FIG. 4 shows the temperature dependence of S of the prepared product in different magnetic fields. As can be seen, when the transition temperature is near 311K, the maximum value of the magnetic entropy change appears. When the intensity of the magnetic field respectively varies from 0 to 1 T, 0 to 2 T, and 0 to 3 T, the maximum magnetic entropy change of the sample is respectively 4.5 J/kgK, 9.9 J/kgK, and 15.3 J/kgK. Presently, a magnetic field at intensity of 2 T can be obtained by utilizing the permanent magnet NdFeB. Therefore, the magnetic entropy changes of the material when the magnetic intensity varies from 0 to 2 T attracts more attentions. Under such a circumstance, the maximum value of the magnetic entropy change (9.9 J/kgK) of the prepared product is much greater than that (when the magnetic intensity is 2 T, the magnetic entropy change is 5.0 J/kgK) of the traditional room-temperature magnetic refrigeration material Gd. It means that the product of the aforesaid embodiment can be used as a better room-temperature functional material.

Embodiment 2

[0056] As shown in FIG. 5, the present invention discloses a 75% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+25% In metal composite functional material and a preparation method thereof. The preparation method of the 75% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+25% In metal composite functional material, comprising the steps of: [0057] 1) Preparing raw materials according to the chemical formula of Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5, wherein the raw materials are commercially available metals including Mn, Fe, Ni, Si and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 5% for compensating its volatile and burning losses during the preparation process; [0058] 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 2.510.sup.3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1700 C. for 2 minutes under the protection of argon, thereby obtaining the cast ingot Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5; [0059] 3) Placing the Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 into a quartz tube with a vacuum degree of 510.sup.3 Pa, and annealing at a temperature of 850 C. for 8 days; [0060] 4) Respectively crushing and grinding the vacuumed and annealed Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 and metal In by using an agate mortar, and screening out the irregular powder with a size smaller than 0.07 mm according to the screening standard of 200-mesh; [0061] 5) Respectively measuring out the Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 powder with a volume percentage of 75%, and the In powder with a volume percentage of 25%; subsequently, mixing them uniformly; [0062] 6) Pressing the uniformly mixed powder at the condition of 140 C. and 900 MPa for 10 minutes under zero magnetic field, thereby obtaining a cylindrical 75% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+25% In metal composite functional material with a diameter of 10 mm; [0063] 7) Curing at a temperature of 500 C. for 7 days, thereby obtaining the 75% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+25% In metal composite functional material.

[0064] The stress-strain curve of the 75% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+25% In metal composite material can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 5, after being tested, the compressive strength of the prepared product is 48 MPa, and the corresponding strain is 15.6%. Meanwhile, the magnetic test shows that the magnetothermal effect of the prepared product of embodiment 2 is better than that of the traditional room-temperature magnetic refrigeration material Gd.

Embodiment 3

[0065] As shown in FIG. 6, the present invention discloses an 80% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+20% In metal composite functional material and a preparation method thereof. The preparation method of the 80% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+20% In metal composite functional material, comprising the steps of: [0066] 1) Preparing raw materials according to the chemical formula of Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5, wherein the raw materials are commercially available metals including Mn, Fe, Ni, Si and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 3% for compensating its volatile and burning losses during the preparation process; [0067] 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 310.sup.3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1700 C. for 2 minutes under the protection of argon, thereby obtaining the cast ingot Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5; [0068] 3) Placing the Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 into a quartz tube with a vacuum degree of 510.sup.3 Pa, and annealing at a temperature of 750 C. for 15 days; [0069] 4) Respectively crushing and grinding the vacuumed and annealed Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5 and metal In by using an agate mortar, and screening out the irregular powder with a size smaller than 0.1 mm according to the screening standard of 150-mesh; [0070] 5) Respectively measuring out the Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0. 5 powder with a volume percentage of 80%, and the In powder with a volume percentage of 20%; subsequently, mixing them uniformly; [0071] 6) Pressing the uniformly mixed powder at the condition of 140 C. and 900 MPa for 6 minutes in zero magnetic field, thereby obtaining a cylindrical 80% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+20% In metal composite functional material with a diameter of 10 mm; [0072] 7) Curing at a temperature of 500 C. for 7 days, thereby obtaining the 80% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+20% In metal composite functional material.

[0073] The stress-strain curve of the 80% Mn.sub.0.6Fe.sub.0.4NiSi.sub.0.5Ge.sub.0.5+20% In metal composite material can be tested by using a WDW200D type microcomputer control universal material tester. As shown in FIG. 6, after being tested, the compressive strength of the prepared product is 41 MPa, and the corresponding strain is 14.9%.

Embodiment 4

[0074] The present invention discloses a 60% MnCoCu.sub.0.08Ge.sub.0.92+40% Sn metal composite functional material and a preparation method thereof. The preparation method of the 60% MnCoCu.sub.0.08Ge.sub.0.92+40% Sn metal composite functional material, comprising the steps of: [0075] 1) Preparing raw materials according to the chemical formula of MnCoCu.sub.0.08Ge.sub.0.92, wherein the raw materials are commercially available metals including Mn, Co, Cu and Ge with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 3% for compensating its volatile and burning losses during the preparation process; [0076] 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 210.sup.3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1600 C. for 3 minutes under the protection of argon, thereby obtaining the cast ingot MnCoCu.sub.0.8Ge.sub.0.92; [0077] 3) Placing the MnCoCu.sub.0.08Ge.sub.0.92 into a quartz tube with a vacuum degree of 510.sup.3 Pa, and annealing at a temperature of 800 C. for 15 days; [0078] 4) Respectively crushing and grinding the vacuumed and annealed MnCoCu.sub.0.08Ge.sub.0.92 and metal Sn by using a jet mill, and screening out the irregular powder with a size smaller than 0.05 mm according to the screening standard of 300-mesh; [0079] 5) Respectively measuring out the MnCoCu.sub.0.08Ge.sub.0.92 powder with a volume percentage of 60%, and the Sn powder with a volume percentage of 40%; subsequently, mixing them uniformly; [0080] 6) Pressing the uniformly mixed powder at the condition of room temperature and 960 MPa for 15 minutes in a magnetic field at intensity of 1.5 T, thereby obtaining a cylindrical 60% MnCoCu.sub.0.08Ge.sub.0.92+40% Sn metal composite functional material with a diameter of 10 mm; [0081] 7) Curing at a temperature of 500 C. for 7 days, thereby obtaining the 60% MnCoCu.sub.0.08Ge.sub.0.92+40% Sn metal composite functional material, namely, the product of this embodiment.

Embodiment 5

[0082] The present invention discloses a 75% Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1+25% InSn metal composite functional material and a preparation method thereof. The preparation method of the 75% Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1+25% InSn metal composite functional material, comprising the steps of: [0083] 1) Preparing raw materials according to the chemical formula of Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1, wherein the raw materials are commercially available metals including Mn, Go, Ge and Si with a purity higher than 99.9 wt. %, and Mn is excessively added according to the atomic ratio of 4% for compensating its volatile and burning losses during the preparation process; [0084] 2) Adopting an electric arc smelting method; feeding the prepared raw materials into a smelting furnace, vacuuming the smelting furnace until the pressure intensity reaches 310.sup.3 Pa, and cleansing the furnace by argon; subsequently, smelting the prepared raw materials at a temperature of 1400 C. for 3 minutes under the protection of argon, thereby obtaining the cast ingot Mn.sub.0.95COGe.sub.0.9Si.sub.0.1; [0085] 3) Placing the Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1 into a quartz tube with a vacuum degree of 510.sup.3 Pa, and annealing at a temperature of 900 C. for 5 days; [0086] 4) Respectively crushing and grinding the vacuumed and annealed Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1 and metal InSn by using a high energy ball mill, and screening out the irregular powder with a size smaller than 0.06 mm according to the screening standard of 250-mesh; [0087] 5) Respectively measuring out the Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1 powder with a volume percentage of 75%, and the InSn powder with a volume percentage of 25%; subsequently, mixing them uniformly; [0088] 6) Pressing the uniformly mixed powder at the condition of 800 C. and 600 MPa for 15 minutes in zero magnetic field, thereby obtaining a cylindrical 75% Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1+25% InSn metal composite functional material with a diameter of 10 mm; [0089] 7) Curing at a temperature of 500 C. for 7 days, thereby obtaining the 75% Mn.sub.0.95CoGe.sub.0.9Si.sub.0.1+25% InSn metal composite functional material, namely, the product of this embodiment.

[0090] The description of above embodiments allows those skilled in the art to realize or use the present invention. Without departing from the spirit and essence of the present invention, those skilled in the art can combine, change or modify correspondingly according to the present invention. Therefore, the protective range of the present invention should not be limited to the embodiments above but conform to the widest protective range which is consistent with the principles and innovative characteristics of the present invention. Although some special terms are used in the description of the present invention, the scope of the invention should not necessarily be limited by this description. The scope of the present invention is defined by the claims.