CN108342634A - A kind of material and its preparation method and application of adjustable negative expansion coefficient - Google Patents

A kind of material and its preparation method and application of adjustable negative expansion coefficient Download PDF

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Publication number
CN108342634A
CN108342634A CN201710052433.5A CN201710052433A CN108342634A CN 108342634 A CN108342634 A CN 108342634A CN 201710052433 A CN201710052433 A CN 201710052433A CN 108342634 A CN108342634 A CN 108342634A
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mncoge
preparation
negative expansion
ball milling
residual stress
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CN108342634B (en
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沈斐然
胡凤霞
匡皓
梁飞翔
乔凯明
李佳
刘瑶
王晶
孙继荣
沈保根
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Institute of Physics of CAS
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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
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F3/02—Compacting only
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • 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
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)

Abstract

The present invention provides a kind of material and its preparation method and application of adjustable negative expansion coefficient, the material is MnCoGe bases and MnNiGe based alloys, the material realizes the introducing of residual stress and defect by high-energy ball milling, while the grain size for controlling material is 0.3~200 μm.The present invention introduces residual stress and different degrees of fault of construction by high-energy ball milling, while controlling particle size, it can be achieved that the negative expansion behavior being continuously adjusted in MnCoGe bases or MnNiGe based alloy single metal materials and ultra low heat expansion.The heat conduction of bonded particulate moulding material of the present invention, conduction, mechanical property can substantially be adjusted by parameters such as binder, the moulding process of selection different characteristics, therefore material of the present invention all has important practical value to the preparation of high-precision optical instrument, low-temperature coefficient mechanical part.

Description

A kind of material and its preparation method and application of adjustable negative expansion coefficient
Technical field
The present invention relates to a kind of adjustable negative expansion coefficient and material for realizing ultra low heat expansion and preparation method thereof and Using.
Background technology
Thermal expansion effects refer to the effect that object volume changes with the change of temperature, and coefficient of thermal expansion is for weighing heat Volume change amplitude caused by bulking effect.Most solid material tools have plenty of positive thermal expansion effects, i.e., in temperature It rises, material expansion；Only a few solid material has negative expansion effect.
However in practical applications, many high-precision optical instruments, low-temperature coefficient mechanical part etc. generally require Use the material with accurate coefficient of thermal expansion even zero thermal expansion coefficient.At present people obtain having accurate coefficient of thermal expansion or The method of person's zero thermal expansion coefficient material be will the material with the positive coefficient of expansion and the material with negative thermal expansion coefficient it is simply multiple It is combined.Therefore, the operation temperature area for expanding negative expansion material is most important.
There is existing a few classes the material of negative expansion to include commercialized ZrW2O8Series material, and new report in the recent period CuO nano particles, the ScF in road3, anti-perovskite structure manganese nitrogen compound, PbTiO3Based compound, (Bi, La) NiO3、La (Fe,Si)13Deng.The negative expansion coefficient majority of these new materials can not be adjusted substantially, and operation temperature area relative narrower, mechanics, Heat conduction, electric conductivity are also to be improved.
In addition to compound system, people have also discovered several pure metals with ultra low heat expansion even zero thermal expansion effect, example Such as：Carbon nanomaterial.Since modern industry is to the urgent and widespread demand of ultra low heat expansion, even Zero-expansion material, hair Now and prepare with adjustable the coefficient of thermal expansion even new material of ultra low heat expansion with important practical usage.
In recent years, a kind of have Ni2Ternary MM ' the X-alloy systems of In type hexagonal structures cause the extensive pass of people Note, this material have without diffusion geneva structural phase transition, i.e., from the Ni of high temperature2In type (space groups：P63/ mmc) hexagonal structure Austria Family name's body parent phase is transformed into the TiNiSi type (space groups of low temperature：Pnma) the martensitic phase of orthohormbic structure, in phase transition process along with Huge negative expansion effect.As one of the member of MM ' X series alloys family, the MnCoGe just divided and MnNiGe alloy materials Also there is material the martensitic traoformation with huge negative expansion effect, martensitic structure phase transition temperature to be located at TstruFor 400~ 500K。
Invention content
There is Ni for above-mentioned2Ternary MM ' the X-alloy systems of In type hexagonal structures, research find through vacancy and draw Enter element substitution, martensitic structure phase transition temperature is adjusted, makes TstruTo low temperature movement and close to room temperature, phase transformation is happened at paramagnetic Between austenite parent phase and ferromagnetic or antiferromagnetic geneva phase, to occur while realizing magnetic phase transition and structural phase transition, i.e., magnetic is total Structural phase transition, the adjoint lattice negative expansion maximum of phase transition process have been more than the other materials of report up to Δ V/V~3.9% Lattice dilatation.
The nearest research work of inventor shows the co-structured phase transformation of the magnetic of such material system to hydrostatic pressing, residual stress Extremely sensitive, hydrostatic pressing can drive the co-structured phase transformation of the magnetic of system substantially to be moved to low temperature, to generate huge piezocaloric effect.Into one It walks studies have shown that MnCoGe bases and MnNiGe base alloy materials are since big volume expansion all has frangible feature.Granular powder The residual stress changed, grind, introduced in bonding process can be such that the co-structured transition temperature area of magnetic substantially broadens, while with residual stress Introducing and granularity reduction, a large amount of hexagonal austenite parent phases lose martensitic traoformation, keep hexagonal structure to low temperature.Invention People is largely introduced stress by high-energy ball milling, generates defect and adjust granularity and realize the controllable adjustment of negative expansion coefficient And ultra low heat expansion, it is of great significance for practical application.
The present inventor is had found by furtheing investigate, for MnCoGe bases and the MnNiGe bases in vacancy and element doping Alloy material Mn1-xInxCoGe、MnCo1-yInyGe、MnCoGe1-zInz、MnCoGe1-w、MnCo1-xCrxGe、Mn1-uFeuNiGe and MnNi1-tFetGe is largely introduced stress and defect by high-energy ball milling and adjusts particle size, can be regulated and controled it and be thermally expanded system Number.This is the residual stress, defect and particle size pair for studying introducing in MnCoGe bases and MnNiGe base alloy materials for the first time The influence of its thermal expansion behavior, discovery are born with the introducing of residual stress, the reduction of defect increased with particle size, material Expansion behavior is continuously adjustable, and under suitable particle size, can realize ultra low heat expansion in wide warm area.
Therefore, the purpose of the present invention is to provide a kind of adjustable negative expansion coefficient and the material of ultra low heat expansion can be realized Material and preparation method thereof and the material high-precision optical instrument, low-temperature coefficient the precision equipments such as machinery in answer With.
In order to help to understand the present invention, some terms are defined below.Other terms used herein have this hair The bright normally understood meaning of those of ordinary skill in the related art.
Unless otherwise stated, the term as used herein Mn1-xInxCoGe、MnCo1-yInyGe、MnCoGe1-zInz、 MnCoGe1-w、MnCo1-vCrvGe、Mn1-uFeuNiGe and MnNi1-tFetCorresponding " the Ni of Ge2In types structure " refers to that space group is P63The structure of/mmc, " TiNiSi types structure " refer to the structure that space group is pnma.
High-energy ball milling of the present invention refers to the rotation or vibration using ball milling, and hard sphere is made to carry out strongly raw material It hits, grind and stirs, the method that material disintegrating is nano-scale particle.High-energy ball milling is also referred to as mechanical force and chemical.
The purpose of the present invention is what is realized by the following technical solutions.
The present invention provides a kind of material of adjustable negative expansion coefficient, the chemical composition of the material is Mn1- xInxCoGe、MnCo1-yInyGe、MnCoGe1-zInz、MnCoGe1-w、MnCo1-vCrvGe、Mn1-uFeuNiGe or MnNi1- tFetGe wherein, 0.01≤x≤0.03,0.015≤y≤0.03,0.01≤z≤0.015,0.01≤w≤0.04,0.01≤v≤ 0.03,0.08≤u≤0.26,0.10≤t≤0.27；Wherein, the material realizes residual stress and defect by high-energy ball milling Introducing, while control material grain size be 0.3~200 μm.
According to material provided by the invention, wherein the coefficient of thermal expansion of the material ranging from+8.0 × 10-7/ K to -100 ×10-6/K.The temperature range of the negative expansion of the material is 80~350K.
The present invention also provides the preparation method of the material of above-mentioned adjustable negative expansion coefficient, this method includes following step Suddenly：
1) chemical formula preparation raw material is pressed；
2) prepared raw material in step 1) is put into electric arc furnaces, is vacuumized, and melting under vacuum conditions, closed Ingot；
3) the melted alloy pig of step 2) is annealed under vacuum conditions, then natural cooling, is had to prepare The alloy material of the chemical composition；
4) alloy material made from step 3) is subjected to high-energy ball milling, obtains the particle that grain size is 0.3~200 μm, simultaneously Introduce residual stress and defect.
According to preparation method provided by the invention, wherein the condition of the high-energy ball milling includes：Ball material mass ratio 1~20: 1, Ball-milling Time is 1 minute to 150 hours.
According to preparation method provided by the invention, wherein raw material Mn, Co, Ge, In, Cr, Fe, Ni all can be commercially available Simple substance element, purity is usually not less than 98.5wt%.
According to preparation method provided by the invention, specifically, the step 2) may include：It will be prepared in step 1) Raw material is put into electric arc furnaces, is evacuated to vacuum degree and is less than 1 × 10-2Pa, arc Starting Arc obtain alloy pig, and each alloy pig exists Melt back 1~6 time at 1000~3000 DEG C.
According to preparation method provided by the invention, specifically, the step 3) may include：By the conjunction that step 2) is melted Ingot is less than 1 × 10 in 700~900 DEG C, vacuum degree-3It anneals 4~10 days under conditions of Pa, then furnace cooling.
According to preparation method provided by the invention, specifically, the step 4) may include：By material made from step 3) Agate pot is packed into protection gas (such as high-purity argon gas), and according to ball material mass ratio 1:1~20:1 is put into agate ball, in high energy ball Ball milling in grinding machine obtains the material powder that grain size is 0.3~200 μm.
For the MnCoGe bases of vacancy made from the above method and element doping and MnNiGe base alloy material systems, this hair Bright inventor is further introduced into residual stress by bonding, and tabletting is made in material powder.Therefore, in preferred embodiment In, preparation method of the invention further includes following steps：
5) material powder made from step 4) is uniformly mixed with organic binder, then instills organic solvent and stirs evenly, It is then placed in baking oven drying；
6) curing agent is added into the material after drying, is uniformly mixed, tabletting is then made, and cured.
Specifically, in the step 5), the quality of the organic binder can be material powder quality 1~ 20%.In the step 6), the quality of the curing agent can be 8~15% of organic binder quality in step 5).
According to preparation method provided by the invention, specifically, the tabletted process of the step 6) may include：It will Mixed powder is put into tabletting grinding tool (shape, the size foundation of mold prepare the actual needs of material), places into oil Press applies the pressure of 0.1~3GPa, and the pressing time is 1~30 minute.According to preparation method provided by the invention, specifically, The solidification process of the step 6) may include：By manufactured tabletting be put into vacuum annealing furnace solidification, solidification temperature be 100~ 300 DEG C, hardening time is 20 minutes to 2 hours, is less than 1 × 10 in vacuum degree-3Cured under conditions of Pa.
The present invention also provides a kind of method of the negative expansion coefficient of adjusting MnCoGe bases and MnNiGe base alloy materials, This method includes that the grain size realized the introducing of residual stress and defect by high-energy ball milling, while controlling material is 0.3~200 μ m。
The present invention also provides a kind of method for the MnCoGe bases and MnNiGe base alloy materials obtaining zero thermal expansion, this method Include the introducing of residual stress and defect being realized by high-energy ball milling, while it is 0.3~200 μm to control the grain size of material.
The present invention also provides the material of the adjustable negative expansion coefficient or according to material made from the method for the present invention Expect high-precision optical instrument, low-temperature coefficient mechanical part equipment in application.
Compared with prior art, advantage of the invention is that：With Ni2The MnCoGe bases and MnNiGe of In type hexagonal structures Base alloy material has preferable negative expansion performance.But its structural phase transition is shown to stress extreme sensitivity.The present invention passes through High-energy ball milling introduces residual stress and different degrees of fault of construction, while controlling particle size, is realized for the first time to MnCoGe Base and MnNiGe base alloy material negative expansion behavior controllable adjustments, discovery is with the introducing of residual stress, the big volume production of defect The negative expansion behavior of raw and particle size reduction, material is continuously adjustable, and under suitable particle size, can be in wide warm area It realizes ultra low heat expansion, i.e., the continuously adjustable or even zero thermal expansion of negative expansion behavior can be achieved in same material.It has been reported Negative expansion materials most does not have this feature, this is one of the advantage of the present invention.Secondly, bonded particulate moulding material of the present invention Heat conduction, conduction, mechanical property can be big by the binder (such as Ag epoxy resin) of selection different characteristics, moulding process parameter Range is adjusted, thus the present invention for MnCoGe bases and MnNiGe base alloy materials in high-precision optical instrument, low temperature system Application in the equipment such as several mechanical parts has important practical significance.
Description of the drawings
Hereinafter, carry out the embodiment that the present invention will be described in detail in conjunction with attached drawing, wherein：
Fig. 1 is Mn made from embodiment 11-xInxThe room temperature X measured before CoGe (x=0.01,0.03) bulk sample cohesive X ray diffraction (XRD) collection of illustrative plates；
Fig. 2 is MnCo made from embodiment 21-yInyThe room temperature X measured before Ge (y=0.015,0.03) bulk sample cohesive X ray diffraction (XRD) collection of illustrative plates；
Fig. 3 is MnCoGe made from embodiment 41-wThe room temperature X-ray measured before (w=0.01,0.04) bulk sample cohesive Diffraction (XRD) collection of illustrative plates；
Fig. 4 is Mn made from embodiment 61-uFeuThe room temperature X measured before NiGe (u=0.08,0.10) bulk sample cohesive X ray diffraction (XRD) collection of illustrative plates；
Fig. 5 is MnNi made from embodiment 71-tFetThe room temperature X measured before Ge (t=0.20,0.23) bulk sample cohesive X ray diffraction (XRD) collection of illustrative plates；
Fig. 6 is MnCoGe made from embodiment 31-zInz(z=0.01) the room temperature X-ray measured before bulk sample cohesive is spread out Penetrate (XRD) collection of illustrative plates；
Fig. 7 is MnCoGe made from embodiment 31-zInz(z=0.01) 4 particle sizes sample (10~20 μm, 5~ 10 μm, 1~2 μm, 0.3~1 μm) bond before X-ray diffraction (XRD) collection of illustrative plates under the 35K that measures；
Fig. 8 is MnCoGe made from embodiment 31-zInz(z=0.01) 4 particle sizes sample (10~20 μm, 5~ 10 μm, 1~2 μm, 0.3~1 μm) bond before dynamic X-ray diffraction (XRD) the data refine gained in 35K to 355K that measures Phase Proportion variation with temperature curve；
Fig. 9 is MnCoGe made from embodiment 31-zInz(z=0.01) 5 particle sizes sample (100~200 μm, 10 ~20 μm, 5~10 μm, 1~2 μm, 0.3~1 μm) bond before pyromagnetic (M-T) curve of the cooling under the magnetic fields 0.01T that measures；
Figure 10 is MnCoGe made from embodiment 31-zInz(z=0.01) sample cohesive that particle size is 10~20 μm The full resolution pricture of preceding scanning electron microscope (SEM) image measured at room temperature, high resolution transmission electron microscopy (TEM) With the image K-M for coming from Fourier transformation.It is the non crystalline structure of defect composition in encircled in full resolution pricture；
Figure 11 is MnCoGe made from embodiment 31-zInz(z=0.01) before the sample cohesive that particle size is 1~2 μm The full resolution pricture of scanning electron microscope (SEM) image, high resolution transmission electron microscopy (TEM) for measuring at room temperature and Come from the image K-M of Fourier transformation.It is the non crystalline structure of defect composition outside encircled in full resolution pricture；
Figure 12 is MnCoGe made from embodiment 31-zInz(z=0.01) sample cohesive that particle size is 0.3~1 μm The full resolution pricture of preceding scanning electron microscope (SEM) image measured at room temperature, high resolution transmission electron microscopy (TEM) With the image K-M for coming from Fourier transformation.It is the non crystalline structure of defect composition outside encircled in full resolution pricture；
Figure 13 is Mn made from embodiment 11-xInxThe linear negative expansion that CoGe (x=0.03) bulk measures after bonding is with temperature Degree variation (Δ L/L-T) curve；
Figure 14 is MnCoGe made from embodiment 41-w(w=0.01) the linear negative expansion that bulk measures after bonding is with temperature Change (Δ L/L-T) curve；
Figure 15 is MnCo made from embodiment 51-vCrvThe linear negative expansion that Ge (v=0.02) bulk measures after bonding is with temperature Degree variation (Δ L/L-T) curve；
Figure 16 is Mn made from embodiment 61-uFeuThe linear negative expansion that NiGe (u=0.10) bulk measures after bonding is with temperature Degree variation (Δ L/L-T) curve；
Figure 17 is MnCoGe made from embodiment 30.99In0.015 particle size ranges sample (100~200 μm, 10~ 20 μm, 2~5 μm, 1~2 μm, 0.3~1 μm) bond after the linear negative expansion that measures vary with temperature (Δ L/L-T) curve, with And its after (0.3~1 μm) bonding of smallest particles sample sizes press sheet compression outside drawing；
Figure 18 is MnCoGe made from embodiment 30.99In0.01It is surveyed after (0.3~1 μm) bonding of sample of smallest particles size The compression stress obtained strains (P- Δ L) curve.
Specific implementation mode
The present invention is further described in detail With reference to embodiment, the embodiment provided is only for explaining The bright present invention, the range being not intended to be limiting of the invention.
The raw material that is used in embodiment and equipment are described as follows：
1) raw materials used Mn, Co, Ge, In, Cr, Ni, Fe are commercialization simple substance elements in the embodiment of the present invention.Mn purity For 99.9wt%, it is purchased from the bicyclic chemical reagent factory in Beijing；(purity is by Co (purity 99.999wt%), Ge 99.999wt%), In (purity 99.999wt%), Cr (purity 99.999wt%), Ni (purity 99.999wt%), Fe (purity 99.999wt%) is purchased from Beijing Non-Ferrous Metal Research General Academy.
2) electric arc furnaces used in produces for Beijing WuKe opto-electrical Technology Co., Ltd, model：WK-II type non-consumable vacuum arcs Stove；Cu target X-ray diffractometers produce for Rigaku companies, model：RINT2400；Dynamic X-ray diffraction instrument is PHILIPS companies Production, model：X'Pert PRO；Superconductive quantum interference vibrating specimen magnetometer (MPMS (SQUID) VSM) is Quantum Design (USA) company produces, model MPMS (SQUID) VSM；High-resolution Lorentz transmission electron microscope is JEOL companies Production, model：LM-2100F；Scanning electron microscope produces for Hitachi companies, model：S4800；High-resolution foil gauge It is produced for Japanese republicanism group (KYOWA), model：The uniaxial general foil gage of KFG-02-120-C1-16 types；Ball mill is The new tech mechanical ＆ electrical equipment factory production in Shenyang City, model：GN-2 type high energy ball mills；Organic adhesive " ultra-fine epoxy resin powder End " and curing agent used " ultra-fine latency Q curing agent " are purchased from GuangZhou, China city Xin Xi chemical metallurgies Co., Ltd；Oil Press produces for Tianjin Keqi High Technology Corp., model：769YP-24B.
MnCoGe bases and the preparation method of MnNiGe base alloy materials are as follows in embodiment：
1) respective element, dispensing are weighed by chemical formula.
2) the prepared raw material of step 1) is respectively put into electric arc furnaces, is evacuated to 3 × 10-3More than pa, in vacuum ring Under border, arc Starting Arc, melt back 3 times, smelting temperature is 2000 DEG C.It is cooling in copper crucible to be cast after melting State alloy pig.
3) alloy pig that step 2) prepares is wrapped with metal molybdenum sheet respectively, is sealed in (vacuum degree in vitreosil pipe It is 1 × 10-4Pa), after annealing 6 days at 875 DEG C, break quartz ampoule, alloy material after furnace cooling to room temperature.
4) material made from step 3) is packed into agate pot under protection of argon gas, and according to ball material mass ratio 1:1~20:1 It is put into agate ball.Then the ball milling in high energy ball mill is obtained by control ratio of grinding media to material, Ball-milling Time containing different stress point The particle of cloth, different structure degree of imperfection, particle size range from 200 μm to 0.3 μm.Ball-milling Time is 1 minute~150 hours, Wherein 100~200 μm of particle size, 10~20 μm, 5~10 μm, 2~5 μm, 1~2 μm, corresponding to 0.3~1 μm of particle Ball-milling Time is followed successively by：1 minute, 2 hours, 6 hours, 40 hours, 60 hours, 120 hours.
For Mn1-xInxCoGe series alloy material systems are further introduced into residual stress by bonding, prepare tabletting Method is as follows：
5) epoxide-resin glue that quality is dusty material quality 1~10% is added into dusty material made from step 4), Acetone soln is instilled later until not crossing sample and stirring evenly, and is then dried in an oven；
6) the ultra-fine latency Q curing agent for the 8-15% that quality is epoxide-resin glue quality is put into the material of drying, It is uniformly mixed；
Mixed dusty material 135mg is weighed, is put into the cylindrical carbon compound tabletting grinding tool of diameter 5mm, places into Tablet press machine, applies the pressure of 0.1~3GPa, and tabletting is made in 1~30 minute in compacting；
Manufactured tabletting is put into vacuum annealing furnace and is cured, is less than 1 × 10 in vacuum degree-3Under conditions of Pa, 100~ At 300 DEG C, solidification 20 minutes by 2 hours to obtain the final product.
Embodiment 1
The group of MnCoGe sills becomes：Mn1-xInxCoGe (x=0.01,0.03), the ball material mass ratio in step 4) are 1:1, step 5) epoxy resin glue is 5%, curing agent ratio 8%, and the condition suppressed in step 6) is：Apply the pressure of 1.3GPa Power, compacting 5 minutes, cured condition are：Cure 1.5 hours at 250 DEG C.
Embodiment 2
The group of MnCoGe sills becomes：MnCo1-yInyGe (y=0.015,0.03), the ball material mass ratio in step 4) It is 5:1, step 5) epoxy resin glue is 10%, curing agent ratio 12%, and the condition suppressed in step 6) is：Apply 0.1GPa Pressure, compacting 1 minute, cured condition is：Cure 2 hours at 100 DEG C.
Embodiment 3
The group of MnCoGe sills becomes：MnCoGe1-zInz(z=0.01), the ball material mass ratio in step 4) is 10:1, Step 5) epoxy resin glue is 4%, curing agent ratio 12%, and the condition suppressed in step 6) is：The pressure of application 1.5GPa, Compacting 20 minutes, cured condition are：Cure 1 hour at 170 DEG C.
Embodiment 4
The group of MnCoGe sills becomes：MnCoGe1-w(w=0.01), the ball material mass ratio in step 4) is 15:1, step Rapid 5) epoxy resin glue is 8%, curing agent ratio 12%, and the condition suppressed in step 6) is：Apply pressure, the pressure of 0.5GPa System 30 minutes, cured condition are：Cure 1 hour at 200 DEG C.
Embodiment 5
The group of MnCoGe sills becomes：MnCo1-vCrvGe (v=0.02), the ball material mass ratio in step 4) are 20:1, Step 5) epoxy resin glue is 4%, curing agent ratio 12%, and the condition suppressed in step 6) is：Apply pressure, the pressure of 1GPa System 10 minutes, cured condition are：Cure 1 hour at 150 DEG C.
Embodiment 6
The group of MnNiGe sills becomes：Mn1-uFeuNiGe (u=0.08,0.10), the ball material mass ratio in step 4) are 8:1, step 5) epoxy resin glue is 3.5%, curing agent ratio 12%, and the condition suppressed in step 6) is：Apply 1.5GPa Pressure, compacting 10 minutes, cured condition is：Cure 50 minutes at 170 DEG C.
Embodiment 7
The group of MnNiGe sills becomes：MnNi1-tFetGe (t=0.20,0.23), the ball material mass ratio in step 4) are 12:1, step 5) epoxy resin glue is 1%, curing agent ratio 15%, and the condition suppressed in step 6) is：Apply the pressure of 3GPa Power, compacting 15 minutes, cured condition are：Cure 20 minutes at 300 DEG C.
Performance characterization
1, the characterization of crystal structure
Mn is determined using Cu target X-ray diffractometers1-xInxCoGe (x=0.01,0.03) bulk, MnCo1-yInyGe (y= 0.015,0.03) bulk, MnCoGe1-w(w=0.01,0.04) bulk, Mn1-uFeuNiGe (u=0.08,0.10) bulk, MnNi1-tFetGe (t=0.20,0.23) bulks and MnCoGe1-zInz(z=0.01) bulk sample room temperature X-ray diffraction (XRD) Collection of illustrative plates, it has been found that all samples have become phase.
Further, we determine the alternating temperature X-ray of the powder sample of the varying particle size of above-mentioned alloy material and spread out Penetrate (XRD) collection of illustrative plates.Fig. 7 provides typical component MnCoGe1-zInz(z=0.01) 4 particle sizes sample (10~20 μm, 5 ~10 μm, 1~2 μm, 0.3~1 μm) X-ray diffraction (XRD) collection of illustrative plates at a temperature of 35K.We carry out refine to collection of illustrative plates, as a result Show that particle size is 10~20 μm of sample, the ratio of hexagonal phase is 7% (35K)；The sample that particle size is 5~10 μm, The ratio of hexagonal phase is 14% (35K)；The ratio of the sample that particle size is 1~2 μm, hexagonal phase is 48% (35K)；Particle ruler Very little is 0.3~1 μm of sample, and the ratio of hexagonal phase is 55% (35K).Illustrate the reduction with particle size, is opened in low-temperature space Begin more and more austenite phases occur, it is clear that this partial austenitic has lost martensitic traoformation.In turn, we are scheming 8 provide typical sample MnCoGe1-zInz(z=0.01) 4 particle size ranges sample (10~20 μm, 5~10 μm, 1~2 μm, 0.3~1 μm) the refine data of dynamic X-ray diffraction (XRD) collection of illustrative plates under 35K to 355K temperature ranges.The results show that with The reduction of particle size, not only more and more austenites lose martensitic traoformation, but also remaining martensitic traoformation also by It gradually broadens, illustrates that the reduction of particle size can so that martensitic traoformation is unstable.
2, phase transformation characterizes
Utilize superconductive quantum interference vibrating specimen magnetometer【MPMS(SQUID)VSM】, we determine above-mentioned alloy material Pyromagnetic (M-T) curve of cooling of the sample of bulk and varying particle size under the magnetic fields 0.01T, cooling rate 2K/min. Fig. 9 provides typical sample MnCoGe1-zInz(z=0.01) 5 particle sizes sample (100~200 μm, 10~20 μm, 5 ~10 μm, 1~2 μm, 0.3~1 μm) pyromagnetic (M-T) curve of cooling under the magnetic fields 0.01T, cooling rate 2K/min.As a result Also show that becomes unstable as particle size reduces the co-structured phase transformation of magnetic.With the reduction of particle size, it is left to be located at 315K The right co-structured phase of magnetic becomes apparent broadening, it is often more important that, occur a new phase transformation at 266K, and with particle size Reduction, this phase transformation becomes more and more significant, this phase change location is just consistent with the Curie temperature of austenite.The result is further Confirm that the introducing with the reduction of particle size and residual stress and defect, a large amount of austenites lose martensitic traoformation.It is difficult to understand The broadening of magnetic phase transition comes from the short distance magnetic order caused by defect at family name's body Curie temperature.The 315K co-structured phase transformations of magnetic nearby The residualinternal stress that introduces during the Particle Breakage of broadening.
3, the result of scanning electron microscope and transmission electron microscope
Figure 10-12 gives utilizes scanning electron microscope (SEM) and high resolution transmission electron microscopy (TEM) at room temperature Observe typical sample MnCoGe1-zInz(z=0.01) sample (10~20 μm, 1~2 μm, 0.3~1 μm) of 3 kinds of particle sizes SEM image, high-resolution TEM image and the image K-M for coming from Fourier transformation.SEM image intuitively gives three The pattern and particle size range of kind particle size sample, respectively 10~20 μm, 1~2 μm and 0.3~1 μm.Transmitted electron The full resolution pricture of microscope (TEM) then intuitively gives the lattice structure of sample.For bulky grain sample (10~20 μm), Images of transmissive electron microscope shows that it is a mono-crystalline structures, and includes a small amount of defect, and electron diffraction diagram clearly demonstrates institute constituency Domain is orthogonal symmetry structure.For little particle sample (1~2 μm, 0.3~1 μm), images of transmissive electron microscope shows that it is nanocrystalline The mixing of grain and a large amount of amorphous phases, for 1~2 μm, 0.3~1 μm of particulate samples, average nanocrystalline grain size be respectively 15nm and 8nm, and pass through the analysis of multiple images of transmissive electron microscope, the ratio shared by non crystalline structure is respectively 35% (1~2 μm) and 55% (0.3~1 μm).Same method, MnCoGe1-zInz(z=0.01) particle size is 2~5 μm of sample, shared by non crystalline structure Ratio is 20%.Obviously, go deep into ball milling, particle size and crystallite dimension are all reducing, the stress that mechanical milling process introduces It generates a large amount of defects and makes the increasing proportion of non crystalline structure.In the electron diffraction diagram of little particle sample (1~2 μm, 0.3~1 μm) The disperse debye ring of appearance further illustrates that sample segment loses long range ordered structure (developing into amorphous phase), in debye ring Diffraction spot then illustrate coexisting for crystal phase.
4, the measurement of negative expansion effect
To study, the introducing of residual stress, the increasing of defect, the reduction of grain size is to MnCoGe bases and MnNiGe based alloy samples The influence of the coefficient of thermal expansion of product, Figure 13-16 give Mn1-xInxThe press sheet compression of CoGe (x=0.03) bulk bonding, MnCoGe1-w(w=0.01) press sheet compression, the MnCo of bulk bonding1-vCrvGe (v=0.02) bulk bond press sheet compression and Mn1-uFeuStrain varies with temperature (Δ L/L-T) song in the temperature-fall period for the press sheet compression that NiGe (u=0.10) bulk bonds Line, cooling rate 2K/min, wherein it is considered that it is isotropism to bond obtained sample hot expansion property.Measurement result is aobvious Show that tabletting made from different bonding modes remains with preferable negative expansion performance.
Further, we bond and measure the strain of obtained material varying particle size powder sample with temperature Change (Δ L/L-T) curve.Typically, Figure 17 provides MnCoGe1-zInz(z=0.01) sample of 5 varying particle sizes (100~200 μm, 10~20 μm, 2~5 μm, 1~2 μm, 0.3~1 μm) strains vary with temperature (Δ L/L-T) curve, rate For 2K/min.Measurement result shows that maximum strain (Δ L/L) comes from the sample of (100~200 μm) bondings of maximum particle size Product are -10231 × 10-6, the temperature range that negative expansion occurs is 192K to 310K, and temperature is across 108K.With subtracting for particle size Small, maximum negative expansion is reducing, but the temperature window that negative expansion occurs broadens.For bulky grain sample (10~20 μm), Its maximum negative expansion (Δ L/L) is reduced to -6076 × 10-6, and temperature is across expanding to 154K (156K to 310K).It further decreases Particle size, maximum negative expansion further decrease, and the temperature window for thermally expanding generation further broadens.For little particle (2~ 5 μm, 1~2 μm) sample, the temperature range of negative expansion expands to the entire measurement warm area from 310K to 100K.According to evenly heat Coefficient of expansion relationship=(Δ L/L)/T, we calculate the thermal linear expansion coefficient of every curve, and wherein Δ L/L is max line Property negative expansion, T be negative expansion occur temperature window.The linear expansion coefficient of wherein 100~200 μm samples is -94.7 ×10-6/ K, warm area：192K-310K；The linear expansion coefficient of bulky grain sample (10~20 μm) is -39.5 × 10-6/ K, temperature Area：156K-310K；The linear expansion coefficient of little particle sample (2~5 μm) is -14.1 × 10-6/ K, warm area：100K-310K；It is small The linear expansion coefficient of particulate samples (1~2 μm) is -3.9 × 10-6/ K, warm area are 100K to 290K.
It is worth noting that, for the bond samples (0.3~1 μm) of particle size minimum, negative expansion disappears, and takes and generation Be super-low expansion coefficient positive expansion, the positive coefficient of expansion be+6.8 × 10-7/ K, warm area：200K-300K.
For this adjustable thermal expansion behavior dependent on granularity, the non crystalline structure in sample plays very important Effect, the little particle sample (1~2 μm, 0.3~1 μm) of significant proportion is occupied especially for non crystalline structure.For little particle Sample (0.3~1 μm), bond samples embody ultralow positive thermal expansion, however XRD refine data analyses obtain its nanocrystalline portion The negative expansion behavior that fission reveals still remains, it was demonstrated that the non crystalline structure coexisted has positive thermal expansion behavior.
So significantly [maximum negative expansion reaches for the adjusting of controllable thermal expansion behavior：α~-94.7 × 10-6/K(192K- 310K), ultra low heat expansion is close to zero thermal expansion：α~+6.8 × 10-7/ K (200K-300K)], illustrate that the material cannot be only used for Direct Zero-expansion material, and can be used for the compensation of various positive expanding material, including with the positive coefficient of expansion of superelevation Organic or plastic material (its positive coefficient of expansion be typically up to about 50~100 × 10-6/K)。
5, the mechanical property of bonded particulate measures
The heat conduction of bonded particulate moulding material of the present invention, conduction, mechanical property can pass through the bonding of selection different characteristics Agent (such as Ag epoxy resin), moulding process parameter are adjusted on a large scale.Typically, Figure 18 provides cohesive smallest particles sample (0.3 ~1 μm) compression stress strain (P- Δ L) curve, as a result, it has been found that, compression strength reaches 129MPa.
Based on the above results, for the MnCoGe bases of different component and MnNiGe based alloys, with High Energy Ball Milling Time Extend, granularity reduces, and coexisting for a large amount of amorphous phases and micron grain or nanocrystal occurs.By controlling Ball-milling Time, It can be achieved to be controllably introduced into residual stress and fault of construction.The amorphous phase that ball milling generates is presented positive expansion behavior, micron grain or Person's nanocrystal still maintains negative expansion behavior, but the introducing of residual stress and fault of construction makes the temperature window of negative expansion behavior Mouth substantially broadens.It these results suggest that, defect and residual stress can be introduced simultaneously by high-energy ball milling in same material and make Grain and crystallite dimension reduce to realize the continuously adjustable or even zero thermal expansion of negative expansion behavior.The negative expansion material having been reported Material is most not to have the characteristics of adjustable huge negative expansion and zero thermal expansion, this is one of advantage of this invention；Secondly, originally The heat conduction of invention bonded particulate moulding material, conduction, mechanical property can pass through binder (such as Ag epoxies of selection different characteristics Resin), the parameters such as moulding process adjust on a large scale, therefore the present invention for MnCoGe bases with MnNiGe base alloy materials high-precision Application in the equipment such as the optical instrument of degree, the mechanical part of low-temperature coefficient has important practical significance.

Claims (10)

1. the chemical composition of a kind of material of adjustable negative expansion coefficient, the material is Mn1-xInxCoGe、MnCo1- yInyGe、MnCoGe1-zInz、MnCoGe1-w、MnCo1-vCrvGe、Mn1-uFeuNiGe or MnNi1-tFetGe wherein, 0.01≤x ≤ 0.03,0.015≤y≤0.03,0.01≤z≤0.015,0.01≤w≤0.04,0.01≤v≤0.03,0.08≤u≤ 0.26,0.10≤t≤0.27；Wherein, the material realizes the introducing of residual stress and defect by high-energy ball milling, controls simultaneously The grain size of material is 0.3~200 μm.
2. material according to claim 1, wherein the coefficient of thermal expansion of the material ranging from+8.0 × 10-7/ K to- 100×10-6/K。
3. material according to claim 1 or 2, wherein the temperature range of the negative expansion of the material is 80~350K.
4. the preparation method of any one of claims 1 to 3 material, this method comprises the following steps：
1) chemical formula preparation raw material is pressed；
2) prepared raw material in step 1) is put into electric arc furnaces, is vacuumized, and melting under vacuum conditions, obtain alloy Ingot；
3) the melted alloy pig of step 2) is annealed under vacuum conditions, then natural cooling, to prepare with described The alloy material of chemical composition；
4) alloy material made from step 3) is subjected to high-energy ball milling, obtains the particle that grain size is 0.3~200 μm, introduces simultaneously Residual stress and defect.
5. preparation method according to claim 4, wherein the condition of the high-energy ball milling includes：Ball material mass ratio 1~ 20:1, Ball-milling Time is 1 minute~150 hours, it is preferable that the annealing temperature of step 3) is 700~900 DEG C, annealing time 4 ~10 days, vacuum degree was not less than 10-4Pa。
6. preparation method according to claim 4 or 5, wherein the method further includes following steps：
5) material powder made from step 4) is uniformly mixed with organic binder, then instills organic solvent and stirs evenly, then It is put into baking oven drying；
6) curing agent is added into the material after drying, is uniformly mixed, tabletting is then made, and cured.
7. preparation method according to claim 6, wherein in the step 5), the quality of the organic binder is The 1~20% of material powder quality；Preferably, in the step 6), the quality of the curing agent can be to have in step 5) The 8~15% of machine binder quality；Preferably, the pressure applied in step 6) is 0.1~3GPa, and the pressing time is 1~30 point Clock；Solidification temperature is 100~300 degrees Celsius, and hardening time is 20 minutes to 2 hours, and solidification vacuum degree is less than 1 × 10-3Pa。
8. a kind of method adjusting MnCoGe bases and the negative expansion coefficient of MnNiGe base alloy materials, this method includes passing through height Energy ball milling realizes the introducing of residual stress and defect, while the grain size for controlling material is 0.3~200 μm.
9. a kind of method for the MnCoGe bases and MnNiGe base alloy materials obtaining zero thermal expansion, this method include passing through high-energy ball milling The grain size realized the introducing of residual stress and defect, while controlling material is 0.3~200 μm.
10. the material of any one of claims 1 to 3 adjustable negative expansion coefficient or according in claim 4 to 7 Material made from any one the method high-precision optical instrument, low-temperature coefficient mechanical part equipment in application.
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CN114423820A (en) * 2019-07-23 2022-04-29 国立大学法人东京工业大学 Resin composition and resin molded article thereof
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

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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
CN106244835A (en) * 2016-08-22 2016-12-21 中国科学院合肥物质科学研究院 A kind of room temperature huge negative thermal expansion material of width warm area and preparation method thereof

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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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