CN103265269B - Novel negative thermal expansion material SrEr2O4-NiO-SrO and preparation method thereof - Google Patents

Novel negative thermal expansion material SrEr2O4-NiO-SrO and preparation method thereof Download PDF

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CN103265269B
CN103265269B CN201310238773.9A CN201310238773A CN103265269B CN 103265269 B CN103265269 B CN 103265269B CN 201310238773 A CN201310238773 A CN 201310238773A CN 103265269 B CN103265269 B CN 103265269B
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thermal expansion
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negative thermal
expansion material
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CN103265269A (en
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晁明举
付林杰
陈贺
梁二军
刘献省
刘亚明
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Zhengzhou University
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Abstract

The invention belongs to the field of inorganic non-metal materials and relates to a negative thermal expansion material SrEr2O4-NiO-SrO and a preparation method thereof. The invention provides a novel negative thermal expansion material SrEr2O4-NiO-SrO which is synthesized by sintering Er2O3, Sr2O3/SrO/Sr(NO3)2, and Ni2O3 as raw materials through adopting a solid phase method according to the mole ratio of Er:Sr:Ni being (1-x):x:1, wherein x is more than 0 and smaller than 1, preferably 0.7-0.9. The invention also provides a preparation method of the novel negative thermal expansion material SrEr2O4-NiO-SrO. The prepared novel negative thermal expansion material is large in negative thermal expansion coefficient and has a wide temperature zone; the raw materials are easily available and low in cost; the preparation method is simple, short in period, and pollution-free; the negative thermal expansion property can be regulated by adjusting the sintering temperature and raw material proportion, and the novel negative thermal expansion material SrEr2O4-NiO-SrO has good industrialization application prospects.

Description

A kind of negative thermal expansion material SrEr 2o 4-NiO-SrO and preparation method thereof
Technical field
The invention belongs to field of inorganic nonmetallic material, relate to a kind of negative thermal expansion material and preparation method thereof.
Background technology
In field of engineering technology, the difference of differing materials thermal expansivity, even same material by surface to inner different depths because existing the thermal expansion that thermal gradient causes to distinguish, often cause thermal stresses.These thermal stresses usually can cause the performance index variation of material or device, as the systematic error of thermal dilatometer, high temperature furnace pipe or burner hearth occur crack or disconnection, winter water pipe or water tank bursting by freezing, space telescope focal length vary with temperature and cause that image quality declines, shoots high gun tube distortion and reduces scolding tin on shell hit rate, printed circuit board (PCB) and Copper Foil disengaging, laser apparatus and come off etc. because of the dispersing of thermal lensing effect outgoing beam, spacecraft thermofin.In order to reduce the thermal stresses between differing materials, improve the tolerance of the temperature variation of components and parts or material, explore thermal expansivity and be zero or approach zero material and just seem highly significant with necessary.
The most of materials of occurring in nature have the character of expanding with heat and contract with cold, but also have some materials in certain temperature range, to demonstrate the characteristic of pyrocondensation cold expanding, i.e. negative expansion, such as A 2o (A:Ag, Cu), BiNiO 3, AVO 5(A:Nb, Ta), ZrV 2o 7, AM 2o 8(A:Zr, Hf; M-W, Mo), A 2m 3o 12(A:Y, Yb, Sc etc.; M:W, Mo), CaZr 4p 6o 24, A (CN) 2(A:Cd, Zn), AF x(A:Sc, Zn; X:2,3) etc.At present, scientific research personnel has started to explore by negative thermal expansion material and positive compound controllable coefficient of thermal expansion or the Zero-expansion material prepared of thermal expansion material, also there is researchist to adopt part to substitute part ion in negative thermal expansion material to obtain the near-zero thermal expansion performance of single-material, reduce to greatest extent the thermal stresses of material, improve the heat shock resistance intensity of material.On the other hand, also can be in refrigerator or compressor of air conditioner for the strong material of negative expansion performance.Based on these important application, negative expansion material causes everybody attention gradually.But the research of negative expansion material also, still in the experimental exploration stage, is considered the problem such as preparation condition and environmental protection, can be little for the material of widespread use.
Therefore, research and develop that a kind of negative expansion performance is good, preparation process is simple, cost is lower, can be of great significance for the novel negative thermal expansion material tool of widespread use.
Summary of the invention
The object of the present invention is to provide that a kind of negative expansion performance is good, the simple novel negative thermal expansion material of preparation process SrEr 2o 4-NiO-SrO and preparation method thereof.
For achieving the above object, the following scheme of technology that the present invention takes.
A kind of novel negative thermal expansion material SrEr 2o 4-NiO-SrO, with Er 2o 3, SrCO 3/ SrO/Sr (NO 3) 2, Ni 2o 3for raw material, according to atomic molar than Er: Sr: Ni=1-x: x: 1 ratio adopts solid phase method sintering synthetic, wherein 0<x<1.
Described novel negative thermal expansion material SrEr 2o 4-NiO-SrO, x is preferably 0.7 ~ 0.9.
Described novel negative thermal expansion material SrEr 2o 4the preparation method of-NiO-SrO, comprises the steps:
(1) raw material is proportionally ground, it is mixed;
(2) will after the raw material drying mixing, carry out compressing tablet with tabletting machine;
(3) compressing tablet is put into High Temperature Furnaces Heating Apparatus and carried out sintering, first High Temperature Furnaces Heating Apparatus is warming up to 900～1000 ℃ and carries out first sintering, and sintering 2 ~ 4 hours continues to be subsequently warming up to 1200 ~ 1400 ℃ and carries out sintering for the second time, sintering 5 ~ 10 hours;
(4) High Temperature Furnaces Heating Apparatus naturally cooling obtains target product.
Described novel negative thermal expansion material SrEr 2o 4the preparation method of-NiO-SrO, in step (1), Er in raw material: Sr: Ni atomic molar is than being 1-x: x: 1, wherein 0< x<1.
Described novel negative thermal expansion material SrEr 2o 4the preparation method of-NiO-SrO, x is 0.7 ~ 0.9.
Described novel negative thermal expansion material SrEr 2o 4the preparation method of-NiO-SrO, in step (1), for raw material is mixed, preferably adds dehydrated alcohol to grind.
The novel negative thermal expansion material SrEr that the present invention is prepared 2o 4-NiO-SrO, negative expansion coefficient is large, wide temperature region; Raw materials source is wide, cost is low; Preparation method is simple, the cycle is short, pollution-free, can regulate and control the negative expansion character of product by sintering temperature and raw material ratio simultaneously, has good industrial applications prospect.
Accompanying drawing explanation
Novel negative thermal expansion material SrEr prepared by Fig. 1: embodiment 1 2o 4x-ray diffraction (XRD) collection of illustrative plates and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 2: embodiment 2 2o 4xRD figure spectrum and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 3: embodiment 3 2o 4xRD figure spectrum and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 4: embodiment 4 2o 4xRD figure spectrum and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 5: embodiment 5 2o 4xRD figure spectrum and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 6: embodiment 6 2o 4xRD figure spectrum and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 7: embodiment 7 2o 4xRD figure spectrum and the material phase analysis of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 8: embodiment 3 2o 4scanning electron microscope (SEM) picture of-NiO-SrO;
Novel negative thermal expansion material SrEr prepared by Fig. 9: embodiment 3 2o 4heat analysis-thermogravimetric curve (DSC-TG) test of-NiO-SrO;
The novel negative thermal expansion material SrEr of Figure 10: embodiment 2～5 preparations 2o 4the relative length variation with temperature curve of-NiO-SrO, wherein embodiment 2, embodiment 3, embodiment 4, embodiment 5 corresponding curve a, b, c, d respectively;
The novel negative thermal expansion material SrEr of Figure 11: embodiment 7,6,4,1 preparation 2o 4the relative length variation with temperature curve of-NiO-SrO, wherein embodiment 7, embodiment 6, embodiment 4, embodiment 1 corresponding curve a, b, c, d respectively.
Embodiment
embodiment 1
By raw material Er 2o 3, SrCO 3, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.7 ︰ 0.3 ︰ 1 according to atomic molar, mixed, ground 0.5h left and right, then add dehydrated alcohol (in order to make grinding more full and uniform) to continue to grind 1h left and right, then at 80 ℃, dry 30min, continue to grind several minutes raw material is mixed.Under pressure with single shaft direction tabletting machine 200MPa, be pressed into diameter 10mm, the cylindrical idiosome (determining according to mold shape) of high 5mm left and right.High temperature process furnances is set and makes it be warming up to 900 ℃, sintering 2h, then continues to rise to 1350 ℃ of sintering 10h, cooling naturally in stove.
The XRD figure spectrum material phase analysis that product is corresponding is shown in Fig. 1, knows that by analysis resultant is mainly NiO phase (being for No. PDF 00-004-0835), SrEr mutually 2o 4phase (being for No. PDF 00-046-0132) and No. SrO(PDF are 00-048-1477).
embodiment 2
By raw material Er 2o 3, SrO, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.3 ︰ 0.7 ︰ 1 according to atomic molar, all the other steps are with embodiment 1, and first sintering temperature is 900 ℃, sintering 2h, 1200 ℃ of sintering temperatures for the second time, sintering time 6h.
X-ray diffraction (XRD) the spectrum material phase analysis of the product of preparation is as Fig. 2.Analysis is known, mainly contains NiO phase, SrEr in resultant 2o 4phase and SrO.
embodiment 3
By raw material Er 2o 3, Sr (NO 3) 2, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.3 ︰ 0.7 ︰ 1 according to atomic molar, all the other steps are with embodiment 1, and first sintering temperature is 1000 ℃, sintering 4h, 1300 ℃ of sintering temperatures for the second time, sintering time 6h.
X-ray diffraction (XRD) collection of illustrative plates of the product of preparation is as Fig. 3.In resultant, mainly contain NiO phase, SrEr 2o 4phase and SrO.
As shown in Figure 8, wherein (a) and (b), (c) magnification are respectively 1000,5000,20000 times to scanning electron microscope (SEM) picture of prepared product.
Heat analysis-the thermogravimetric curve (DSC-TG) of prepared product is tested as shown in Figure 9, as can be seen from Figure 9, in the temperature range occurring, has a larger endotherm(ic)peak, and is attended by weightlessness in negative expansion.
embodiment 4
By raw material Er 2o 3, SrCO 3/ SrO/Sr (NO 3) 2, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.3 ︰ 0.7 ︰ 1 according to atomic molar, all the other steps are with embodiment 1, and first sintering temperature is 900 ℃, sintering 4h, 1350 ℃ of sintering temperatures for the second time, sintering time 8h.
X-ray diffraction (XRD) collection of illustrative plates of the product of preparation is as Fig. 4.In resultant, mainly contain NiO phase, SrEr 2o 4phase and SrO.
embodiment 5
By raw material Er 2o 3, SrCO 3/ SrO/Sr (NO 3) 2, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.3 ︰ 0.7 ︰ 1 according to atomic molar, all the other steps are with embodiment 1, and first sintering temperature is 1000 ℃, sintering 4h, 1400 ℃ of sintering temperatures for the second time, sintering time 10h.
X-ray diffraction (XRD) collection of illustrative plates of the product of preparation is as Fig. 5.In resultant, mainly contain NiO phase, SrEr 2o 4phase and SrO.
embodiment 6
By raw material Er 2o 3, SrCO 3/ SrO/Sr (NO 3) 2, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.2 ︰ 0.8 ︰ 1 according to atomic molar, all the other steps are with embodiment 1, and first sintering temperature is 900 ℃, sintering 2h, and sintering temperature is 1350 ℃ for the second time, sintering 8h.
X-ray diffraction (XRD) collection of illustrative plates of the product of preparation is as Fig. 6.Analysis knows, mainly contains and in resultant, mainly contain NiO phase, SrEr in resultant 2o 4phase and SrO.
embodiment 7
By raw material Er 2o 3, SrCO 3/ SrO/Sr (NO 3) 2, Ni 2o 3take respectively than Er ︰ Sr ︰ Ni=0.1 ︰ 0.9 ︰ 1 according to atomic molar, all the other steps are with embodiment 1, and first sintering temperature is 900 ℃, sintering 2 h, and sintering temperature is 1350 ℃ for the second time, sintering 8h.
X-ray diffraction (XRD) collection of illustrative plates of the product of preparation is as Fig. 7.Analysis knows, mainly contains and in resultant, mainly contain NiO phase, SrEr in resultant 2o 4phase and SrO.
The relative length of the prepared novel negative thermal expansion material of embodiment 2, embodiment 3, embodiment 4, embodiment 5 is varied with temperature to curve and contrast mapping as shown in figure 10, a, b, c, d corresponding embodiment 2, embodiment 3, embodiment 4, embodiment 5 respectively in figure.Probe temperature is from room temperature to 800 ℃.As can be seen from the figure.Prepared novel negative thermal expansion material SrEr 2o 4-NiO-SrO is due to sintering temperature difference, and negative expansion performance shows certain difference, as, embodiment 2 negative expansion warm areas are at 420～470 ℃, and negative expansion coefficient is-53 × 10 -6/ ℃ (430～450 ℃), embodiment 4 negative expansion warm areas are about 400～500 ℃, and linear expansivity is-60 × 10 -6/ ℃ (455～485 ℃), embodiment 5 negative expansion warm areas are about 380～507 ℃, and linear expansivity is-67 × 10 -6/ ℃ (435～490 ℃), but simultaneously prepared novel negative thermal expansion material SrEr 2o 4-NiO-SrO between 350～550 ℃, shows again the stability of good negative expansion performance within the scope of larger warm area, and negative expansion coefficient is all-50～-80 × 10 -6/ ℃ between.
The relative length of the prepared novel negative thermal expansion material of embodiment 7, embodiment 6, embodiment 4, embodiment 1 is varied with temperature to curve and contrast mapping as shown in figure 11, a, b, c, d corresponding embodiment 7, embodiment 6, embodiment 4, embodiment 1 respectively in figure.Probe temperature is from room temperature to 800 ℃.As can be seen from the figure.Prepared novel negative thermal expansion material SrEr 2o 4-NiO-SrO is in the time that proportioning raw materials changes, and negative expansion performance has also shown certain difference.
Can draw by Figure 10, Figure 11, in the time of sintering temperature difference, proportioning raw materials difference, prepared novel negative thermal expansion material SrEr 2o 4the negative expansion performance of-NiO-SrO is also different, therefore, can come novel negative thermal expansion material SrEr by the adjustment of temperature and proportioning raw materials 2o 4the negative expansion coefficient of-NiO-SrO regulates and controls.

Claims (6)

1. a negative thermal expansion material SrEr 2o 4-NiO-SrO, is characterized in that: with Er 2o 3, SrCO 3/ SrO/Sr (NO 3) 2, Ni 2o 3for raw material, according to atomic molar than Er: Sr: Ni=1-x: x: 1 ratio adopts solid phase method sintering synthetic, wherein 0<x<1.
2. negative thermal expansion material SrEr as claimed in claim 1 2o 4-NiO-SrO, is characterized in that: x is 0.7 ~ 0.9.
3. negative thermal expansion material SrEr described in claim 1 2o 4the preparation method of-NiO-SrO, is characterized in that: comprises the steps,
(1) raw material is proportionally ground, it is mixed;
(2) will after the raw material drying mixing, carry out compressing tablet with tabletting machine;
(3) compressing tablet is put into High Temperature Furnaces Heating Apparatus and carried out sintering, first High Temperature Furnaces Heating Apparatus is warming up to 900～1000 ℃ and carries out first sintering, and sintering 2 ~ 4 hours continues to be subsequently warming up to 1200 ~ 1400 ℃ and carries out sintering for the second time, sintering 5 ~ 10 hours;
(4) High Temperature Furnaces Heating Apparatus naturally cooling obtains target product.
4. negative thermal expansion material SrEr as claimed in claim 3 2o 4the preparation method of-NiO-SrO, is characterized in that: in step (1), and Er in raw material: Sr: Ni atomic molar is than being 1-x: x: 1, wherein 0<x<1.
5. negative thermal expansion material SrEr as claimed in claim 3 2o 4the preparation method of-NiO-SrO, is characterized in that: x is 0.7 ~ 0.9.
6. negative thermal expansion material SrEr as claimed in claim 3 2o 4the preparation method of-NiO-SrO, is characterized in that: in step (1), add dehydrated alcohol in raw material.
CN201310238773.9A 2013-06-17 2013-06-17 Novel negative thermal expansion material SrEr2O4-NiO-SrO and preparation method thereof Expired - Fee Related CN103265269B (en)

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Publication number Priority date Publication date Assignee Title
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CN101831602A (en) * 2010-02-09 2010-09-15 江苏大学 Method for preparing thermal expansion matching composite thermal barrier coating

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CN101831602A (en) * 2010-02-09 2010-09-15 江苏大学 Method for preparing thermal expansion matching composite thermal barrier coating

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