CN104843663A - Negative expansion material ZrScMo2PO12 and solid-phase sintering synthesis method thereof - Google Patents
Negative expansion material ZrScMo2PO12 and solid-phase sintering synthesis method thereof Download PDFInfo
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- CN104843663A CN104843663A CN201510179827.8A CN201510179827A CN104843663A CN 104843663 A CN104843663 A CN 104843663A CN 201510179827 A CN201510179827 A CN 201510179827A CN 104843663 A CN104843663 A CN 104843663A
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Abstract
The present invention provides a novel negative expansion material ZrScMo2PO12 and a solid-phase sintering synthesis method thereof, wherein the negative expansion material is characterized in that the molecular formula is ZrScMo2PO12. The solid-phase sintering synthesis method comprises: adopting ZrO2, Sc2O3, MoO3 and NH4H2PO4 as raw materials, weighing the raw materials according to the stoichiometric ratio Zr:Sc:Mo:P of 1:1:2:1 in the target product ZrScMo2PO12, carrying out grinding mixing, directly sintering or sintering after sheet pressing, and naturally cooling to obtain the target product, wherein the sintering conditions comprise that the temperature is 800-980 DEG C, the time is 4-8 h, the pressure is the atmospheric pressure, and the atmosphere is air. The present invention provides the novel negative expansion material with the molecular formula ZrScMo2PO12a, wherein the novel negative expansion material has the negative thermal expansion property in a wide temperature region and has the engineering application value, and the method has characteristics of cheap raw materials and simple sintering process, and is suitable for mass production.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, particularly a kind of molecular formula is ZrScMo
2pO
12novel negative expanding material and solid state sintering synthetic method.
Background technology
Expanding with heat and contract with cold is the general and thorny phenomenon of one of occurring in nature, due to heat effect without time ubiquitous, for the device under accurate device and extreme condition, usually the control of outside constant temp or very complicated structure design must be adopted to compensate, not only increase the complicacy of the volume of system, weight and processing, also make cost increase simultaneously.To expand with heat and contract with cold and thermal stresses that expansion coefficient mismatch produces or thermal shocking often can cause material or device fatigue, degradation, provisional or eventual failure, rupture and come off, cause a large amount of wastes even catastrophic effect of materials and devices thus.Along with the development of the new and high technologies such as space technology, the high-accuracy laser technology of superpower, Solid Oxide Fuel Cell, new challenge is proposed to materials and devices performance under extreme conditions.And the negative thermal expansion material of the excellent performance of wide warm area is design and prepare zero thermal expansion and coefficient of expansion controllable material, solve the key point of many difficult problems in modern science and technology.Although found some negative thermal expansion materials in the recent decade, the problem that in these materials, many existence are such or such, has restricted its application.As ZrW
2o
8be at room temperature metastable phase material, poor stability, easily decomposes with other materials compound tense, and undergoes phase transition at about 150 DEG C and change with the coefficient of expansion; ZrV
2o
7be at room temperature super cell's structure of 3 × 3 × 3, there is huge thermal expansivity, only just change the normal configuration of 1 × 1 × 1 at more than 373K into, show negative expansion; A
2m
3o
12(A=3 valency transition metal or rare earth; M=W or Mo) series material only has orthorhombic phase just to have negative expansion character.In general, A is worked as
3+time ionic radius less (as A=Al, Fe, Cr, In), under room temperature, crystallization is monoclinic phase, only has and is at high temperature just converted into orthohormbic structure; Work as A
3+time ionic radius comparatively large (A=Lu, Yb, Y), although be orthohormbic structure under room temperature, having is more by force water-absorbent, only along with after temperature raises and lose crystal water completely, just shows negative heat expansion characteristics.Absorption and the release of crystal water cause the huge pucker & bloat of material simultaneously, its mechanical property is deteriorated, restrict its application (E.J.Liang, Negative thermalexpansion materials and their applications:a survey of recent patents, Rec.Pat.Mater.Sci.3 (2010) 106-28).Some fluorochemicals of nearest discovery also have negative expansion character, but most just there is negative expansion at quite low temperatures, we show the test of some fluorochemicals, can react, lose negative expansion character when fluorochemical is heated under air ambient with the O in air.The Suzuki etc. of Japan in 2004 has synthesized HfMgW first
3o
12negative thermal expansion material, but study discovery afterwards, HfMgW
3o
12at room temperature crystallization is monocline, only after more than 400K changes orthorhombic phase into, just shows negative expansion, and its negative expansion coefficient is-1.2 × 10
-6k
-1(A.M.Gindhart, C.Lind, M.Green, Polymorphism in thenegative thermal expansion material magnesium hafnium tungstate, J.Mater.Res., 23 (2008) 210); And HfMgMo
3o
12then show positive swelling properties, the coefficient of expansion is 1.02 × 10
-6k
-1(B.A.Marinkovic, P.M.Jardim, M.Ari, R.R.de Avillez, F.Rizzol, F.F.Ferreira, Lowpositive thermal expansion in HfMgMo
3o
12, Phys.Stat.Sol. (b), 245,11 (2008) 2514); Song Wenbo etc. are recently reported ZrMgMo
3o
12and ZrMgW
3o
12negative expansion character (W.B.Song, E.J.Liang, X.S.Liu, Z.Y.Li, B.H.Yuan, J.Q.Wang, A negative thermalexpansion material of ZrMgMo
3o
12, Chin.Phys.Lett., 30 (12), 126502,2013); F.Li, X.Liu, W.Song, B.Yuan, Y.Cheng, H.Yuan, F.Cheng, M.Chao, E.J Liang, Phasetransition, crystal water and low thermal expansion behavior ofAl
2-2x(ZrMg)
xw
3o
12n (H
2o), J.Solid State Chem.218 (2014) 15-22), but find ZrMgW
3o
12also there is stronger water-absorbent.The AMgM of current report
3o
12(A=Zr, Hf; M=W or Mo) structured material only has above-mentioned four.
The material that occurring in nature has the unusual character of pyrocondensation cold expanding is few, and the negative thermal expansion material of current synthetic is also very limited, and the negative thermal expansion material with the excellent performance that engineer applied is worth is then less.Therefore, research and develop a kind of low cost, be applicable to large-scale production, the novel negative expanding material and preparation method thereof of excellent property is significant.
Summary of the invention
The object of this invention is to provide a kind of novel negative expanding material ZrScMo
2pO
12and solid state sintering synthetic method.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of negative expansion material, it is characterized in that, its molecular formula is: ZrScMo
2pO
12.
The solid state sintering synthetic method of above-mentioned negative expansion material, is characterized in that, comprising: with ZrO
2, Sc
2o
3, MoO
3and NH
4h
2pO
4for raw material, according to target product ZrScMo
2pO
12middle stoichiometric ratio Zr: Sc: Mo: P=1: 1: 2: 1 takes raw material, ground and mixed, and directly or after compressing tablet sinter, naturally cooling obtains target product; Wherein, sintering condition is: temperature is 800-980 DEG C, and the time is 4-8h, and pressure is normal pressure, and atmosphere is air.
Beneficial effect of the present invention is:
1. the invention provides a kind of molecular formula is ZrScMo
2pO
12novel negative expanding material, it has negative expansion character at wide warm area, have engineer applied be worth.
2. raw materials is cheap, and sintering process is simple and easy.In atmospheric air, sinter 800-980 DEG C, sintering time is 4-8h, is applicable to batch production.
Accompanying drawing explanation
Fig. 1 is the ZrScMo of embodiment 1-3 synthesis
2pO
12xRD figure spectrum;
Fig. 2 is the ZrScMo of embodiment 1-3 synthesis
2pO
12the relative length variation with temperature graph of a relation of pottery.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
A kind of negative expansion material, its molecular formula is: ZrScMo
2pO
12, its solid state sintering synthetic method is: with analytical pure ZrO
2, Sc
2o
3, MoO
3and NH
4h
2pO
4for raw material, according to target product ZrScMo
2pO
12middle stoichiometric ratio Zr: Sc: Mo: P=1: 1: 2: 1 takes raw material, is put into ground and mixed 2h in mortar, will be pressed into the right cylinder of diameter 10mm, high 10mm under the pressure of powder single shaft direction tabletting machine 300MPa.Arranging high temperature process furnances makes it be warming up to sintering temperature 850 DEG C, the corundum crucible that sample is housed is put into tube furnace at a sintering temperature, sinters 8h in atmospheric air, in atmosphere naturally cooling.The XRD figure spectrum material phase analysis that product is corresponding is shown in curve (a) in Fig. 1, composes storehouse and contrasts, do not occur peak and the impurity peaks of raw material in XRD figure spectrum with XRD figure, shows that the sample prepared is the ZrScMo of pure orthorhombic phase structure
2pO
12.
Embodiment 2
A kind of negative expansion material, its molecular formula is: ZrScMo
2pO
12, its solid state sintering synthetic method is similar to embodiment 1, and difference from Example 1 is: arrange high temperature process furnances and make it be warming up to sintering temperature 900 DEG C, sintering time is 6h.The XRD figure spectrum material phase analysis that product is corresponding is shown in curve (b) in Fig. 1, composes storehouse and contrasts, do not occur the peak of raw material and possible intermediate product ZrP in XRD figure spectrum with XRD figure
2o
7deng impurity peaks, show that the sample prepared is the ZrScMo of pure orthorhombic phase structure
2pO
12.
Embodiment 3
A kind of negative expansion material, its molecular formula is: ZrScMo
2pO
12, its solid state sintering synthetic method is similar to embodiment 1, and difference from Example 1 is: arrange high temperature process furnances and make it be warming up to sintering temperature 950 DEG C, sintering time is 5h.The XRD figure spectrum material phase analysis that product is corresponding is shown in curve (c) in Fig. 1, composes storehouse and contrasts, do not occur the peak of raw material and possible intermediate product ZrP in XRD figure spectrum with XRD figure
2o
7deng impurity peaks, show that the sample prepared is the ZrScMo of pure orthorhombic phase structure
2pO
12.
Linear thermal expansion test experiments
ZrScMo prepared by embodiment 1,2 and 3
2pO
12pottery relative length is shown in Fig. 2 (a), (b) and (c) with the change curve of probe temperature, and all embodiments all show ZrScMo
2pO
12pottery has negative expansion character.ZrScMo is calculated with the change curve of probe temperature according to relative length
2pO
12coefficient of linear expansion is respectively-1.33 × 10
-6dEG C
-1(room temperature ~ 400 DEG C) ,-1.88 × 10
-6dEG C
-1(room temperature ~ 600 DEG C) ,-2.59 × 10
-6dEG C
-1(room temperature ~ 600 DEG C).
Claims (2)
1. a negative expansion material, is characterized in that, its molecular formula is: ZrScMo
2pO
12.
2. the solid state sintering synthetic method of negative expansion material according to claim 1, is characterized in that, comprising: with ZrO
2, Sc
2o
3, MoO
3and NH
4h
2pO
4for raw material, according to target product ZrScMo
2pO
12middle stoichiometric ratio Zr: Sc: Mo: P=1: 1: 2: 1 takes raw material, ground and mixed, and directly or after compressing tablet sinter, naturally cooling obtains target product; Wherein, sintering condition is: temperature is 800-980 DEG C, and the time is 4-8h, and pressure is normal pressure, and atmosphere is air.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019167924A1 (en) * | 2018-02-27 | 2019-09-06 | 国立大学法人東京工業大学 | Negative thermal expansion material, composite material, and method for producing negative thermal expansion material |
| CN112390642A (en) * | 2020-12-01 | 2021-02-23 | 郑州大学 | Negative thermal expansion material Cu2V2-xPxO7And method for preparing the same |
Citations (2)
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|---|---|---|---|---|
| CN101891470A (en) * | 2010-06-21 | 2010-11-24 | 郑州大学 | Sintering and synthesizing method of negative thermal expansion material Zr2P2MO12 |
| CN104119076A (en) * | 2014-07-11 | 2014-10-29 | 郑州大学 | A novel negative expansion material and a solid-phase sintering synthetic method thereof |
-
2015
- 2015-04-16 CN CN201510179827.8A patent/CN104843663A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891470A (en) * | 2010-06-21 | 2010-11-24 | 郑州大学 | Sintering and synthesizing method of negative thermal expansion material Zr2P2MO12 |
| CN104119076A (en) * | 2014-07-11 | 2014-10-29 | 郑州大学 | A novel negative expansion material and a solid-phase sintering synthetic method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019167924A1 (en) * | 2018-02-27 | 2019-09-06 | 国立大学法人東京工業大学 | Negative thermal expansion material, composite material, and method for producing negative thermal expansion material |
| KR20200125634A (en) * | 2018-02-27 | 2020-11-04 | 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 | Subthermal expansion material, composite material, and method of manufacturing subthermal expansion material |
| JPWO2019167924A1 (en) * | 2018-02-27 | 2021-03-18 | 国立大学法人東京工業大学 | Methods for manufacturing negative thermal expansion materials, composite materials, and negative thermal expansion materials |
| JP7017743B2 (en) | 2018-02-27 | 2022-02-09 | 国立大学法人東京工業大学 | Methods for manufacturing negative thermal expansion materials, composite materials, and negative thermal expansion materials |
| KR102655109B1 (en) | 2018-02-27 | 2024-04-04 | 고쿠리츠다이가쿠호진 토쿄고교 다이가꾸 | Subthermal expansion material, composite material, and method for producing subthermal expansion material |
| US11970396B2 (en) | 2018-02-27 | 2024-04-30 | Tokyo Institute Of Technology | Negative thermal expansion material, composite material, and method for producing negative thermal expansion material |
| CN112390642A (en) * | 2020-12-01 | 2021-02-23 | 郑州大学 | Negative thermal expansion material Cu2V2-xPxO7And method for preparing the same |
| CN112390642B (en) * | 2020-12-01 | 2023-01-31 | 郑州大学 | Negative thermal expansion material Cu 2 V 2-x P x O 7 And method for preparing the same |
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