CN107385305B - A kind of alloy material and preparation method thereof with negative expansion property - Google Patents

A kind of alloy material and preparation method thereof with negative expansion property Download PDF

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CN107385305B
CN107385305B CN201710583329.9A CN201710583329A CN107385305B CN 107385305 B CN107385305 B CN 107385305B CN 201710583329 A CN201710583329 A CN 201710583329A CN 107385305 B CN107385305 B CN 107385305B
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powder
sample
negative
alloy material
expansion property
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CN107385305A (en
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孙莹
赵文君
王聪
卢会清
王蕾
史可文
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Beihang University
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Beihang University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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

Abstract

Most materials have positive hot expansion property in nature, i.e., in certain temperature range, as the temperature rises, material is in a certain direction or multiple directions expand.In practical engineering applications, the stability of engineering component, precision, service life etc. are had a very big impact.Negative thermal expansion material is a kind of good swelling inhibitor, can be used to reconcile positive thermal expansion, improve engineering component precision and service life etc..The present invention provides a kind of solid metal alloy material and preparation method thereof with negative expansion property, can be used as swelling inhibitor materials'use, such alloy material has negative expansion property, chemical general formula MnNi in certain temperature section1‑xFexGe/Cu or Mn1‑yFeyNiGe/Cu (0≤x≤1,0≤y≤1).Such as MnNi0.90Fe0.10Ge/35wt%Cu alloy material has negative expansion property in 176K < T < 247K, and thermal expansion coefficient is -56.7357 × 10‑6K‑1。

Description

A kind of alloy material and preparation method thereof with negative expansion property
Technical field:
The present invention provides a kind of solid metal alloy material and preparation method thereof with negative expansion property, can be used as Swelling inhibitor materials'use has potential application in fields such as aerospace, precision instruments.
Background technique:
Most materials have positive hot expansion property in nature, i.e., in certain temperature range, with temperature It increases, material is in a certain direction or multiple directions expand.In practical engineering applications, to the stability of engineering component, Precision, service life etc. have a very big impact.Negative thermal expansion material is a kind of good swelling inhibitor, can be used to adjust With positive thermal expansion, engineering component precision and service life etc. are improved.
Up to the present, scientist has found negative in the material systems such as oxide, intermetallic compound, metal alloy Hot expansion property.The overwhelming majority has the ferroelectric material of negative expansion property, and the warm area that negative expansion occurs is all very wide, still The coefficient of expansion but very little, such as Pb (Ti0.75Zr0.25)O3The temperature range that negative expansion occurs is RT-728K, linear expansion coefficient αlIt is -1.1 × 10-6K-1；In magnetic material, although it is sent out as anti-perovskite structural compounds have the biggish coefficient of expansion The temperature range of raw negative expansion phenomenon is narrow, or due to above/below actual use temperature range, such as Mn3Zn0.5Sn0.5N The linear expansion coefficient of compound has reached -45 × 10-6K-1, but its temperature that negative expansion occurs is higher than 100 DEG C, is 381- 428K；Mn3Zn0.3Sn0.7N negative expansion warm area has been up to 447K, but its negative expansion warm area only has 10K；Mn3GaN compound The temperature range that negative expansion effect occurs is 348K < T < 361K.These all seriously limit its performance and application.In addition, from The practicability of material sets out, and the negative thermal expansion material of research and development metal class is very with practical value.
MM'X (M, M' are transition element, X Si, Ge, Sn etc.) ternary alloy three-partalloy class material has multifarious crystal knot Structure and magnetic structure, such material are always the research of basic structure and magnetic material, ferromagnetic shape memory alloys and magneto-caloric material Object, wherein MnNiGe is a system by primary study.Pass through the research to such material, it has been found that MnNiGe body Be alloy have negative expansion phenomenon, by with other metal mixeds, the adjustable alloy material of hot expansion property can be obtained, this Class material is potentially to can be applied to actual negative thermal expansion material.
Summary of the invention
The base material that the invention is related to is a kind of ternary-alloy material MnNiGe, by the position Mn or the position Ni into Row part Fe element substitution, general structure MnNi1-xFexGe or Mn1-yFeyNiGe, by Mn (manganese), Fe (iron), Ni (nickel) Constituted with four kinds of metallic elements such as Ge (germanium), atom ratio 1:(1-x): x:1 or (1-y): y:1:1.By base material It is mixed with the Ni metal (copper) of different quality ratio, it is MnNi that chemical general formula, which can be made,1-xFexGe/Cu or Mn1-yFeyNiGe/Cu Metal alloy compositions.Wherein, x, y are the numerical value between 0-1.Alloy material obtained has negative heat swollen in a certain range Swollen characteristic.
The preparation process of such negative expansion metal alloy compositions is as follows:
Step 1: according to stoichiometric ratio, with electronic balance (0.0001g) weigh respectively high-purity manganese powder, iron powder, nickel powder and Germanium powder is placed in mortar and is fully ground 1-2h；
Step 2: the metal powder mixture after above-mentioned be fully ground is pressed into bulk using tablet press machine and corresponding mould Solid；
Step 3: blocks of solid obtained in step 2 is sealed to vacuum sealing tube system spare in vitreosil pipe；
Step 4: the quartz ampoule equipped with sample being placed in Muffle furnace, fully calcined 60-150h at 500-1200 DEG C, Calcined sample is taken out spare；
Step 5: calcined sample is taken out, and according to the chemical quality ratio of 1%-100%, uses electronic balance (0.0001g) weighs copper powder, and copper powder and sample are placed in mortar and are fully ground 1-1.5h, makes the two uniformly mixing；
Step 6: using tablet press machine and corresponding mould that pressed by powder mixed uniformly in above-mentioned steps five is solid at bulk Body；
Step 7: blocks of solid obtained in step 2 is sealed to vacuum sealing tube system spare in vitreosil pipe；
Step 8: the quartz ampoule equipped with sample being placed in Muffle furnace, fully calcined 10-150h at 300-1200 DEG C, Calcined sample is taken out spare；So far, metal alloy compositions preparation is completed.
Wherein, the purity of the powders such as raw material Mn, Ni, Fe, Ge, Cu is 99.99%；
Wherein, described in step 2 and step 6 " corresponding mould " can be any mould for meeting technique desired size Tool；
By above step, it is prepared for MnNi1-xFexGe or Mn1-yFeyThe metal alloy compositions of NiGe and copper.The portion of preparation The thermal expansion coefficients evidence of metal alloy compositions is divided to be shown in Table 1.
Negative thermal expansion alloy material prepared by the present invention has the advantage that
(1) linear expansion coefficient is larger, and the temperature range that negative expansion occurs is larger；
(2) can regulate and control the temperature range and linear expansion coefficient of negative expansion occurs by the content of control base material；
(3) this alloy material is metal material.
Detailed description of the invention
The thermal expansion coefficient of 1 alloy part material of table
Ingredient Thermalexpansioncoefficientαl(×10-6K-1) Temperature range (K)
Mn0.90Fe0.10NiGe -285.2288 192-305
Mn0.90Fe0.10NiGe/35%Cu -26.1572 167-290
MnNi0.90Fe0.10Ge -1167.0926 246-305
MnNi0.90Fe0.10Ge/35%Cu -56.7357 176-247
Mn0.84Fe0.16NiGe/20%Cu -13.2674 124-195
Fig. 1 MnNi0.90Fe0.10Ge/35wt%Cu alloy material thermal expansion figure
Specific embodiment
Below with MnNi0.90Fe0.10Illustrate for the preparation of Ge/35wt%Cu, is merely to illustrate the present invention, not for The limitation present invention.
The present invention is a kind of metallic composite with negative expansion property, prepares the composite wood using solid sintering technology Material.Base material is MnNi0.90Fe0.10Ge, preparation process are as follows:
Step 1: it according to the stoichiometric ratio of Mn:Fe:Ni:Ge=1:0.90:0.10:1, is weighed respectively with electronic balance 3.5446gMn powder, 3.4082gNi powder, 0.3603gFe powder and 4.6868gGe powder are placed in agate mortar, are fully ground 1.5h being uniformly mixed powder；
Step 2: the metal powder being uniformly mixed is pressed by the common cylinder pattern for being 15mm with diameter tool with tablet press machine Height is about the cylindric block of 2.5mm；
Step 3: above-mentioned cylindrical metal block is sealed in vitreosil pipe with vacuum sealing tube system；
Step 4: packaged quartz ampoule is placed in Muffle furnace, and temperature-rise period is arranged: being risen to 1.5h from room temperature 350 DEG C, 900 DEG C are warming up in 350 DEG C of constant temperature 0.5h, then with 3h, in 900 DEG C of constant temperature 80h, last cooled to room temperature；
So far, base material MnNi0.90Fe0.10Ge preparation is completed.
Step 5: according to MnNi0.90Fe0.10The mass ratio of Ge:Cu=65:35, is weighed with electronic balance and is weighed respectively 2.2750g MnNi0.90Fe0.10The Cu powder of Ge and 1.2250g, and be placed in agate mortar and be fully ground 1h, make Cu powder with MnNi0.90Fe0.10Ge is uniformly mixed；
Step 6: the powder that step 5 is uniformly mixed is placed in the mold of specific dimensions, is pressed into size with tablet press machine For the strip block of 25mm*5mm*5mm；
Step 7: strip block described in step 6 is sealed into vitreosil pipe with vacuum sealing tube system；
Step 8: above-mentioned packaged quartz ampoule is placed in Muffle furnace, and temperature-rise period is arranged: using 2.5h from room temperature liter To 200 DEG C, 500 DEG C are warming up in 200 DEG C of constant temperature 2.0h, then with 3h, in 500 DEG C of constant temperature 10h, last cooled to room temperature；
So far, this material preparation is completed.
As shown in Figure 1, the linear expansion coefficient that present case implements the metal alloy compositions of preparation is -56.7357 × 10-6K-1, The temperature range that negative expansion occurs is 176K-247K.

Claims (3)

1. a kind of alloy material with negative expansion property can be used as swelling inhibitor use, it is characterised in that:
Such alloy material has negative expansion property in certain temperature section, described to have negative expansion property alloy material For MnNi0.90Fe0.10Ge/35%Cu or Mn0.84Fe0.16NiGe/20%Cu or Mn0.90Fe0.10NiGe/35%Cu；
It is prepared using solid phase reaction sintering method, preparation step is as follows:
Step 1: according to stoichiometric ratio, high-purity 4N manganese powder, iron powder, nickel powder and germanium are weighed respectively with electronic balance 0.0001g Powder is placed in mortar and is fully ground 1-2h；
Step 2: the metal powder mixture after above-mentioned be fully ground is pressed into bulk admittedly using tablet press machine and corresponding mould Body；
Step 3: blocks of solid obtained in step 2 is sealed to vacuum sealing tube system spare in vitreosil pipe；
Step 4: the quartz ampoule equipped with sample is placed in Muffle furnace, fully calcined 60-150h at 500-1200 DEG C will be forged Sample after burning takes out spare；
Step 5: calcined sample is taken out, and according to the chemical quality ratio of 1%-100%, is weighed with electronic balance 0.0001g Copper powder and sample are placed in mortar and are fully ground 1-1.5h by copper powder, make the two uniformly mixing；
Step 6: using tablet press machine and corresponding mould by pressed by powder mixed uniformly in above-mentioned steps five at blocks of solid；
Step 7: blocks of solid obtained in step 2 is sealed to vacuum sealing tube system spare in vitreosil pipe；
Step 8: the quartz ampoule equipped with sample is placed in Muffle furnace, fully calcined 10-150h at 300-1200 DEG C will be forged Sample after burning takes out spare；So far, swelling inhibitor preparation is completed；
Wherein, the purity of raw material Mn, Ni, Fe, Ge, Cu powder is 99.99%；
Wherein, described in step 2 and step 6 " corresponding mould " is any mold for meeting technique desired size；
By above step, it is prepared for MnNi0.90Fe0.10Ge or Mn0.84Fe0.16NiGe or Mn0.90Fe0.10The conjunction of NiGe and Cu copper Golden material.
2. a kind of alloy material with negative expansion property according to claim 1, it is characterised in that: described with negative The alloy material of hot expansion property is MnNi0.90Fe0.10Ge/35wt%Cu composite material has negative heat swollen in 176K < T < 247K Swollen property, thermal expansion coefficient are -56.7357 × 10-6K-1。
3. a kind of preparation method of alloy material with negative expansion property according to claim 1, it is characterised in that:
It is prepared using solid phase reaction sintering method, preparation step is as follows:
Step 1: according to stoichiometric ratio, high-purity 4N manganese powder, iron powder, nickel powder and germanium are weighed respectively with electronic balance 0.0001g Powder is placed in mortar and is fully ground 1-2h；
Step 2: the metal powder mixture after above-mentioned be fully ground is pressed into bulk admittedly using tablet press machine and corresponding mould Body；
Step 3: blocks of solid obtained in step 2 is sealed to vacuum sealing tube system spare in vitreosil pipe；
Step 4: the quartz ampoule equipped with sample is placed in Muffle furnace, fully calcined 60-150h at 500-1200 DEG C will be forged Sample after burning takes out spare；
Step 5: calcined sample is taken out, and according to the chemical quality ratio of 1%-100%, is weighed with electronic balance 0.0001g Copper powder and sample are placed in mortar and are fully ground 1-1.5h by copper powder, make the two uniformly mixing；
Step 6: using tablet press machine and corresponding mould by pressed by powder mixed uniformly in above-mentioned steps five at blocks of solid；
Step 7: blocks of solid obtained in step 2 is sealed to vacuum sealing tube system spare in vitreosil pipe；
Step 8: the quartz ampoule equipped with sample is placed in Muffle furnace, fully calcined 10-150h at 300-1200 DEG C will be forged Sample after burning takes out spare；So far, swelling inhibitor preparation is completed；
Wherein, the purity of raw material Mn, Ni, Fe, Ge, Cu powder is 99.99%；
Wherein, described in step 2 and step 6 " corresponding mould " is any mold for meeting technique desired size；
By above step, it is prepared for MnNi0.90Fe0.10Ge or Mn0.84Fe0.16NiGe or Mn0.90Fe0.10The conjunction of NiGe and Cu copper Golden material.
CN201710583329.9A 2017-07-18 2017-07-18 A kind of alloy material and preparation method thereof with negative expansion property Active CN107385305B (en)

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CN115216676B (en) * 2021-04-20 2024-01-26 中国科学院物理研究所 Anisotropic negative thermal expansion material and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104775045A (en) * 2015-03-27 2015-07-15 江苏大学 Preparation method for Cu-based composite material based on negative thermal expansion particles
CN105568108A (en) * 2014-10-09 2016-05-11 中国科学院物理研究所 Method for maintaining strong magnetic co-structure phase change of MnNiGe base material, and applications thereof
CN105624514A (en) * 2014-10-29 2016-06-01 中国科学院物理研究所 Negative expansion material, and preparation method and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105568108A (en) * 2014-10-09 2016-05-11 中国科学院物理研究所 Method for maintaining strong magnetic co-structure phase change of MnNiGe base material, and applications thereof
CN105624514A (en) * 2014-10-29 2016-06-01 中国科学院物理研究所 Negative expansion material, and preparation method and application thereof
CN104775045A (en) * 2015-03-27 2015-07-15 江苏大学 Preparation method for Cu-based composite material based on negative thermal expansion particles

Non-Patent Citations (1)

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Title
Magnetocaloric effect and negative thermal exmansion in hexagonal Fe doped MnNiGe compounds with a magnetoelastic AFM-FM-like transition;Kun Xu等;《SCIENTIFIC REPORTS》;20170130;第1-2页

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