CN107385305A - A kind of alloy material with negative expansion property and preparation method thereof - Google Patents
A kind of alloy material with negative expansion property and preparation method thereof Download PDFInfo
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- CN107385305A CN107385305A CN201710583329.9A CN201710583329A CN107385305A CN 107385305 A CN107385305 A CN 107385305A CN 201710583329 A CN201710583329 A CN 201710583329A CN 107385305 A CN107385305 A CN 107385305A
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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
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- 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
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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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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Abstract
Most materials have positive hot expansion property in nature, i.e., in certain temperature range, with the rise of temperature, material expands in some direction or multiple directions.In practical engineering application, stability, precision, service life of engineering component etc. are had a very big impact.Negative thermal expansion material is a kind of good swelling inhibitor, can be used for reconciling positive thermal expansion, improve engineering component precision and service life etc..The present invention provides a kind of solid metal alloy material with negative expansion property and preparation method thereof, can be used as swelling inhibitor materials'use, such alloy material has negative expansion property in certain temperature section, and its chemical general formula is MnNi1‑xFexGe/Cu or Mn1‑yFeyNiGe/Cu (0≤x≤1,0≤y≤1).Such as MnNi0.90Fe0.10Ge/35wt%Cu alloy materials are in 176K<T<247K has negative expansion property, and its thermal coefficient of expansion is 56.7357 × 10‑6K‑1。
Description
Technical field：
The present invention provides a kind of solid metal alloy material with negative expansion property and preparation method thereof, can conduct
Swelling inhibitor materials'use, there is potential application value in fields such as Aero-Space, precision instruments.
Background technology：(foreword)
Most materials have positive hot expansion property in nature, i.e., in certain temperature range, with temperature
Rise, material expand in some direction or multiple directions.In practical engineering application, stability to 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 for adjusting
With positive thermal expansion, engineering component precision and service life etc. are improved.
Up to the present, scientist is found that 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 of negative expansion occurs all very extensively in it, still
The coefficient of expansion but very little, such as Pb (Ti0.75Zr0.25)O3The temperature range that negative expansion occurs is RT-728K, its linear expansion coefficient
αlFor -1.1 × 10-6K-1；In magnetic material, although if anti-perovskite structural compounds are with the larger coefficient of expansion, its hair
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 occur negative expansion temperature be higher than 100 DEG C, be 381-
428K； Mn3Zn0.3Sn0.7N negative expansion warm areas have been up to 447K, but its negative expansion warm area only has 10K； Mn3GaN chemical combination
The temperature range that negative expansion effect occurs for thing is 348K<T<361K.These all seriously limit its performance and application.In addition,
From the practicality of material, 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 bodies
Be that alloy has negative expansion phenomenon, by with other metal mixeds, the adjustable alloy material of hot expansion property can be obtained, this
Class material is can be potentially applied to actual negative thermal expansion material.
The content of the invention
The base material that the invention is related to is a kind of ternary-alloy material MnNiGe, by Mn positions or Ni positions
Part Fe element substitutions are carried out, its general structure is MnNi1-xFexGe or Mn1-yFeyNiGe, by Mn (manganese), Fe (iron), Ni
Four kinds of metallic elements such as (nickel) and Ge (germanium) are formed, and its atom ratio is 1:(1-x):x:1 or (1-y):y:1:1.By substrate
Material and different quality than Ni metal (copper) mix, 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.Obtained alloy material is within the specific limits
With negative heat expansion characteristics.
The preparation process of such negative expansion metal alloy compositions is as follows：
Step 1：According to stoichiometric proportion, with electronic balance (0.0001g) weigh respectively high-purity manganese powder, iron powder, nickel powder and
Germanium powder, is positioned among 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：The blocks of solid obtained in step 2 is sealed to vacuum sealing tube system standby in vitreosil pipe；
Step 4：Quartz ampoule equipped with sample is placed in Muffle furnace, fully calcined 60-150h at 500-1200 DEG C,
Sample after calcining is taken out standby；
Step 5：Sample after calcining is taken out, according to 1%-100% chemical quality ratio, uses electronic balance
(0.0001g) weighs copper powder, and copper powder and sample are placed in mortar and are fully ground 1-1.5h, the two is uniformly mixed；
Step 6：It is with corresponding mould that mixed uniformly pressed by powder in above-mentioned steps five is into block solid using tablet press machine
Body；
Step 7：The blocks of solid obtained in step 2 is sealed to vacuum sealing tube system standby in vitreosil pipe；
Step 8：Quartz ampoule equipped with sample is placed in Muffle furnace, fully calcined 10-150h at 300-1200 DEG C,
Sample after calcining is taken out standby；So far, prepared by metal alloy compositions completes.
Wherein, the purity of the powder such as raw material Mn, Ni, Fe, Ge, Cu is 99.99%；
Wherein, " corresponding mould " described in step 2 and step 6 can be any mould for meeting technological requirement size
Tool；
By above step, MnNi is prepared for1-xFexGe or Mn1-yFeyNiGe and copper metal alloy compositions.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 advantages below：
(1) linear expansion coefficient is larger, and the temperature range that negative expansion occurs is larger；
(2) by controlling the content of base material to regulate and control the temperature range and linear expansion coefficient of negative expansion occurs；
(3) this alloy material is metal material.
Brief description of the drawings
The thermal coefficient of expansion of the alloy part material of table 1
| Composition | 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 figures
Embodiment
Below with MnNi0.90Fe0.10Illustrate exemplified by Ge/35wt%Cu preparation, be 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, and the composite wood is prepared using solid sintering technology
Material.Base material is MnNi0.90Fe0.10Ge, its preparation process are as follows：
Step 1：According to Mn:Fe:Ni:Ge=1:0.90:0.10:1 stoichiometric proportion, weighed respectively with electronic balance
3.5446g Mn powder, 3.4082g Ni powder, 0.3603g Fe powder and 4.6868g Ge powder are positioned in agate mortar, are fully ground
1.5h, it is well mixed powder；
Step 2：Have with a diameter of 15mm common cylinder pattern and be pressed into the metal dust being well mixed with tablet press machine
Highly it is about 2.5mm cylindric block；
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, temperature-rise period is set：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, finally naturally cools to room temperature；
So far, base material MnNi0.90Fe0.10Prepared by Ge completes.
Step 5：According to MnNi0.90Fe0.10Ge:Cu=65:35 mass ratio, is weighed with electronic balance and weighed respectively
2.2750g MnNi0.90Fe0.10Ge and 1.2250g Cu powder, and be positioned in agate mortar and be fully ground 1h, make Cu powder with
MnNi0.90Fe0.10Ge is well mixed；
Step 6：The powder that step 5 is well mixed is positioned in the mould of specific dimensions, size is pressed into tablet press machine
For 25mm*5mm*5mm strip block；
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, temperature-rise period is set：With 2.5h from room temperature
200 DEG C are risen to, 500 DEG C is warming up in 200 DEG C of constant temperature 2.0h, then with 3h, in 500 DEG C of constant temperature 10h, finally naturally cools to room
Temperature；
So far, prepared by this material completes.
As shown in figure 1, the linear expansion coefficient that present case implements the metal alloy compositions prepared is -56.7357 × 10-6 K-1, the temperature range that negative expansion occurs is 176K-247K.
Claims (4)
1. a kind of alloy material with negative expansion property, can be used as swelling inhibitor, it is characterised in that：
Such alloy material has negative expansion property in certain temperature section, and its chemical general formula is MnNi1-xFexGe/Cu or
Person Mn1-yFeyNiGe/Cu (0≤x≤1,0≤y≤1).Such as MnNi0.90Fe0.10Ge/35wt%Cu composites are in 176K<T<
247K has negative expansion property, and its thermal coefficient of expansion is -56.7357 × 10-6K-1。
A kind of 2. alloy material with negative expansion property according to claim 1, it is characterised in that：
The base material of the alloy material is MnNi1-xFexGe/Mn1-yFeyNiGe, by Mn, Ni, Fe, tetra- kinds of metallic element groups of Ge
Into its atom ratio point is than being 1:(1-x):x:1、(1-y):y:1:1.The preparation method of the alloy material includes the base material
Preparation method.
A kind of 3. alloy material with negative expansion property according to claim 1, it is characterised in that：
With the compound metal of substrate be Cu (copper) or with Cu (copper) similar in metal.
A kind of 4. preparation method of alloy material with negative expansion property according to claim 1, it is characterised in that：
Prepared using solid phase reaction sintering method, its preparation process is as follows：
Step 1：According to stoichiometric proportion, with electronic balance (0.0001g) weigh respectively high-purity (4N) manganese powder, iron powder, nickel powder and
Germanium powder, is positioned among 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：The blocks of solid obtained in step 2 is sealed to vacuum sealing tube system standby in vitreosil pipe；
Step 4：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 standby；
Step 5：Sample after calcining is taken out, according to 1%-100% chemical quality ratio, claimed with electronic balance (0.0001g)
Copper powder is taken, copper powder and sample are placed in mortar and are fully ground 1-1.5h, the two is uniformly mixed；
Step 6：Using tablet press machine and corresponding mould by mixed uniformly pressed by powder in above-mentioned steps five into blocks of solid；
Step 7：The blocks of solid obtained in step 2 is sealed to vacuum sealing tube system standby in vitreosil pipe；
Step 8：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 standby；So far, prepared by swelling inhibitor completes.
Wherein, the purity of the powder such as raw material Mn, Ni, Fe, Ge, Cu is 99.99%；
Wherein, " corresponding mould " described in step 2 and step 6 can be any mould for meeting technological requirement size；
By above step, MnNi is prepared for1-xFexGe or Mn1-yFeyNiGe and Cu (copper) alloy material.
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| CN201710583329.9A CN107385305B (en) | 2017-07-18 | 2017-07-18 | A kind of alloy material and preparation method thereof with negative expansion property |
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| CN201710583329.9A CN107385305B (en) | 2017-07-18 | 2017-07-18 | A kind of alloy material and preparation method thereof with negative expansion property |
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| CN107385305A true CN107385305A (en) | 2017-11-24 |
| CN107385305B CN107385305B (en) | 2019-08-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216676A (en) * | 2021-04-20 | 2022-10-21 | 中国科学院物理研究所 | Anisotropic negative thermal expansion material and preparation method and application thereof |
Citations (3)
| 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 |
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2017
- 2017-07-18 CN CN201710583329.9A patent/CN107385305B/en active Active
Patent Citations (3)
| 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)
| Title |
|---|
| KUN XU等: "Magnetocaloric effect and negative thermal exmansion in hexagonal Fe doped MnNiGe compounds with a magnetoelastic AFM-FM-like transition", 《SCIENTIFIC REPORTS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115216676A (en) * | 2021-04-20 | 2022-10-21 | 中国科学院物理研究所 | Anisotropic negative thermal expansion material and preparation method and application thereof |
| 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 |
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