CN102432292A - Sintering synthesis method for nanometer negative expansion ceramic Zr2(WO4)(PO4)2 - Google Patents

Sintering synthesis method for nanometer negative expansion ceramic Zr2(WO4)(PO4)2 Download PDF

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CN102432292A
CN102432292A CN2011102837248A CN201110283724A CN102432292A CN 102432292 A CN102432292 A CN 102432292A CN 2011102837248 A CN2011102837248 A CN 2011102837248A CN 201110283724 A CN201110283724 A CN 201110283724A CN 102432292 A CN102432292 A CN 102432292A
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sintering
mgo
temperature
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梁二军
刘献省
商瑞
晁明举
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Zhengzhou University
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Abstract

The invention discloses a sintering synthesis method for nanometer negative expansion ceramic Zr2(WO4)(PO4)2, which belongs to the field of inorganic non-metallic materials. According to the invention, ZrO2, WO3 and P2O5 are used as raw materials; the raw materials are weighed according to a stoichiometric ratio of Zr to W to P in the target product Zr2(WO4)(PO4)2 of 2: 1: 2; MgO which accounts for 0.5 to 1.5% of the total weight of the raw materials of ZrO2, WO3 and P2O5 is added, MgO and the raw materials are ground and uniformly mixed, then are dried, and then are ground and uniformly mixed again, and an obtained mixture is subjected to direct one-step sintering synthesis or to one-step sintering synthesis after performing, and a product obtained after sintering synthesis is quenched in the air so as to obtain the target product; wherein, sintering parameters are: temperature 1350 to 1450 DEG C, time 2 to 20 min. The invention has the advantages of a simple process, no pollution, a fast sintering speed and suitability for large scale production; Zr2(WO4)(PO4)2 has an average particle size in order of magnitude of hundreds of nanometers.

Description

A kind of nanometer negative expansion pottery Zr 2(WO 4) (PO 4) 2Sintering and synthesizing method
Technical field
The invention belongs to field of inorganic nonmetallic material, particularly a kind of nanometer negative expansion pottery Zr 2(WO 4) (PO 4) 2Sintering and synthesizing method.
Background technology
In engineering materials; Must use differing materials could satisfy the multifunction requirement; But when temperature variation since the thermal stresses that thermal expansion coefficient difference produces usually can cause material or device degradation, provisional or permanent inefficacy, come off and a series of problems such as fracture, as Fiber Bragg Grating FBG centre wavelength with the systematic error of temperature drift, thermal dilatometer, space telescope focal length with temperature variation cause that image quality descends, Copper Foil on the printed substrate since the disengaging of being heated, laser apparatus because of the dispersing of thermal lensing effect outgoing beam, the spacecraft thermofin comes off etc.In order to reduce the thermal stresses of differing materials, must explore thermal expansivity can matched materials.
At occurring in nature, most materials have the characteristic of expanding with heat and contract with cold, yet, also there are some materials in certain temperature range, to show the character of pyrocondensation cold expanding, negative expansion just is such as ZrW 2O 8, ZrV 2O 7, Y 2M 3O 12(M--W, Mo) and Zr 2(WO 4) (PO 4) 2Or the like.Negative thermal expansion material can with the positive thermal expansion material compound preparation controlled thermal coefficient of expansion or Zero-expansion material, the thermal stresses of material when reducing high temperature to greatest extent increases the heat shock resistance intensity of material.At present, the negative expansion material causes everybody attention gradually, yet; The research of this type material also is in the test exploratory stage; So far also do not obtain large-scale application, also have a lot of problems anxious to be solved, choose as raw-material; The phase transformation of product, suction etc. cause the variation of mechanical property and negative expansion performance, complex manufacturing etc.
For Zr 2(WO 4) (PO 4) 2, in large-temperature range very (from room temperature to 800 ℃), be stable quadrature phase, show tangible negative expansion characteristic, prepare more employing solid sintering technology [Gregory A.Merkel et al. United States, US6377729B2 at present; Mehmet Cetinkol et al. Phys. Rev. B 79 (2009) 224118].Use ZrO 2, WO 3And NH 4H 2PO 4Or (NH 4) 2HPO 4Preparation negative thermal expansion ceramic Zr 2(WO 4) (PO 4) 2, but the NH that in 900 ℃ of presintering processes, discharges 3Can bring pollution to environment, and grow (8 h) at the sintering time of 1250 ℃ of high temperature, the finished product density is lower.Because the high temperature sintering time is long, the crystal growth particle is bigger, and pore is more, causes product density also lower, has a strong impact on Zr 2(WO 4) (PO 4) 2Practical application.
Therefore, research and develop a kind of pollution-free, preparation more fast, low-cost, be fit to large-scale production nano-scale particle, negative expansion pottery Zr that density is big 2(WO 4) (PO 4) 2The preparation method significant.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, pollution-free, sintering velocity is fast and the nanometer negative expansion pottery Zr of suitable large-scale production 2(WO 4) (PO 4) 2Sintering and synthesizing method.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is following:
A kind of nanometer negative expansion pottery Zr 2(WO 4) (PO 4) 2Sintering and synthesizing method: with ZrO 2, WO 3And P 2O 5Be raw material, according to target product Zr 2(WO 4) (PO 4) 2Middle stoichiometric ratio (mol ratio) Zr:W:P=2:1:2 takes by weighing raw material, adds accounting for raw material ZrO 2, WO 3And P 2O 5The MgO of gross weight 0.5 ~ 1.5%, ground and mixed is even, oven dry, ground and mixed is even again, directly or behind the compressing tablet (compressing tablet helps improving the density of product) once sintered synthetic, take out that quenching gets title product in air; Wherein, the sintering parameter is: 1350 ~ 1450 ℃ of temperature, times 3 ~ 20 min.
Preferably, bake out temperature is 150 ~ 153 ℃, and the time is 6 ~ 10 h.
Beneficial effect of the present invention is:
1, technology is simple, pollution-free, sintering velocity fast and suitable large-scale production;
2, sintering and synthesizing method of the present invention avoids under lower temperature, generating ZrP 2O 7, sintering time obviously shortens.Because ZrP 2O 7Need long period and WO 3Reaction generates Zr 2(WO 4) (PO 4) 2Simultaneously, the sintering time short-range missile causes Zr 2(WO 4) (PO 4) 2The grain growing time is shorter, and average particle size particle size is in the hundreds of nanometer scale, be several microns of long-time sintered particles about 1/10th;
3, additive MgO and Zr 2(WO 4) (PO 4) 2Form sosoloid, do not form the MgO phase separately, improved ceramic density effectively.On the one hand, MgO is distributed in Zr 2(WO 4) (PO 4) 2As weighting agent, reduce the pore between the particle between the particle; On the other hand, MgO hinders Zr 2(WO 4) (PO 4) 2Hard group of particle bunch and macrobead growth.This two aspect all can obviously improve Zr 2(WO 4) (PO 4) 2The density of pottery.
Description of drawings
Fig. 1 is the mix Zr of 0.5 wt.% MgO of embodiment 1 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 2 is the mix Zr of 1 wt.% MgO of embodiment 2 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 3 is the mix Zr of 1 wt.% MgO of embodiment 3 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 4 is the mix Zr of 1 wt.% MgO of embodiment 4 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 5 is the mix Zr of 1 wt.% MgO of embodiment 5 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 6 is the mix Zr of 1 wt.% MgO of embodiment 6 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 7 is the Zr of embodiment 7 synthetic doping 1.5wt.%MgO 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 8 is the not Zr of doped with Mg O of embodiment 8 synthetic 2(WO 4) (PO 4) 2XRD figure spectrum;
Fig. 9 is that (a) embodiment 8 does not mix and (b) embodiment 2 doping 1wt.%MgO synthetic Zr 2(WO 4) (PO 4) 2Stereoscan photograph;
Figure 10 is (a) embodiment 2, (b) embodiment 1, (c) embodiment 6 doped with Mg O and (d) embodiment 8 doped with Mg O synthetic Zr not 2(WO 4) (PO 4) 2The relative length of pottery and the variation relation of probe temperature.
Embodiment
Embodiment 1
With raw material ZrO 2, WO 3And P 2O 5Zr:W:P=2:1:2 takes by weighing by stoichiometric ratio (mol ratio), grinds about 0.5 h to evenly, adds to account for raw material ZrO again 2, WO 3And P 2O 5The MgO of total amount 0.5 wt.% continues to grind 1.5 h to evenly, then 150 oC is oven dry 6 h down.Several minutes is ground in the oven dry back makes raw materials mix even, presses down with regard to the pressure with single shaft direction tabletting machine 300 MPa and processes diameter 10 mm, the right cylinder of high 10 mm.High temperature process furnances is set makes it be warming up to 1350 ℃ of sintering temperatures, the corundum crucible that sample is housed is put into tube furnace under sintering temperature, sintering 10 min in the atmospheric air take out quenching in air.X-ray diffraction (XRD) the collection of illustrative plates material phase analysis that product is corresponding is seen Fig. 1, and the XRD diffraction peak explains that corresponding to PDF# 01-085-2239 the short period of time sample of preparation is the Zr of pure phase 2(WO 4) (PO 4) 2(peak that does not have impurity phase and raw material among the XRD).
Embodiment 2
Be with the difference of embodiment 1: sintering temperature is 1400 oC, sintering time are 3 min.The XRD figure spectrum material phase analysis that product is corresponding is seen Fig. 2, and the XRD diffraction peak explains that corresponding to PDF# 01-085-2239 the short period of time sample of preparation is the Zr of pure phase 2(WO 4) (PO 4) 2
Embodiment 3
Be with the difference of embodiment 2: sintering time is 5 min, synthetic Zr 2(WO 4) (PO 4) 2Corresponding XRD material phase analysis is seen Fig. 3, and XRD result shows and formed pure Zr 2(WO 4) (PO 4) 2Phase.
Embodiment 4
Be with the difference of embodiment 2: sintering time is 10 min, the Zr of formation 2(WO 4) (PO 4) 2Corresponding XRD material phase analysis is seen Fig. 3, and XRD result shows and formed pure Zr 2(WO 4) (PO 4) 2Phase.
Embodiment 5
Be with the difference of embodiment 2: sintering time is 15 min, the Zr of formation 2(WO 4) (PO 4) 2Corresponding XRD material phase analysis is seen Fig. 5, and XRD result shows and formed pure Zr 2(WO 4) (PO 4) 2Phase.
Embodiment 6
Be with the difference of embodiment 2: sintering time is 20 min, the Zr of formation 2(WO 4) (PO 4) 2Corresponding XRD material phase analysis is seen Fig. 6, and XRD result shows and formed pure Zr 2(WO 4) (PO 4) 2Phase.
Embodiment 7
Be with the difference of embodiment 1: adding accounts for raw material ZrO 2, WO 3And P 2O 5The MgO of total amount 1.5 wt.%, sintering temperature is 1450 oC, sintering time are 3 min, the Zr of formation 2(WO 4) (PO 4) 2Corresponding XRD material phase analysis is seen Fig. 7, and XRD result shows and formed pure Zr 2(WO 4) (PO 4) 2Phase.
Embodiment 8
Be with the difference of embodiment 2: in raw material, do not add additive MgO (in order to contrast with the sample that adds MgO), bake out temperature is 180 oC, the time is that 3 h{ are for the sample that does not add MgO, 150 oC is difficult to oven dry (needing several days time to dry), 180 oSeveral hrs can be dried under the C, and adds the sample of MgO, 150 oC needs only several hrs and just can dry }.The XRD figure spectrum material phase analysis that product is corresponding is seen Fig. 8, and the XRD diffraction peak explains that corresponding to PDF# 01-085-2239 the short period of time sample of preparation is the Zr of single phase 2(WO 4) (PO 4) 2
The performance test experiment
Electronics microcosmic ESEM (SEM) experiment
Fig. 9 a is the prepared Zr of embodiment 8 2(WO 4) (PO 4) 2The SEM photo of pottery.This ceramic particle size is not really even, and mean particle size is about 1 μ m.
Fig. 9 b is the prepared Zr of embodiment 2 2(WO 4) (PO 4) 2The SEM photo of pottery.This ceramic particle size is more even, and mean particle size is about 400 nm, and crystal grain obviously reduces.Other adds the Zr of the embodiment preparation of MgO 2(WO 4) (PO 4) 2SEM photo situation and Fig. 9 b of pottery are basic identical.Explain that MgO is generating Zr 2(WO 4) (PO 4) 2In the process, play prevention Zr 2(WO 4) (PO 4) 2The particulate growth reduces pore, has improved ceramic density.
Coefficient of expansion test
Figure 10 (a) is the prepared Zr of embodiment 2 2P 2WO 12The relative length of pottery is with the variation of temperature curve.This ceramic length is dwindled with the increase of temperature, shows that prepared material is the negative thermal expansion ceramic material.Calculating its thermal expansivity is-2.68 * 10 -6oC -1(20-700 oC).
Figure 10 (b) is the prepared Zr of embodiment 1 2P 2WO 12The relative length of pottery is with the variation of temperature curve.This ceramic length is dwindled with the increase of temperature, shows that prepared material is the negative thermal expansion ceramic material.Calculating its thermal expansivity is-2.03 * 10 -6oC -1(20-900 oC).
Figure 10 (c) is the prepared Zr of embodiment 6 2P 2WO 12The relative length of pottery is with the variation of temperature curve.This ceramic length is dwindled with the increase of temperature, shows that prepared material is the negative thermal expansion ceramic material.Calculating its thermal expansivity is-2.41 * 10 -6oC -1(20-700 oC).
Figure 10 (d) is the prepared Zr of embodiment 8 2P 2WO 12The relative length of pottery is with the variation of temperature curve.This ceramic length is dwindled with the increase of temperature, shows that prepared material is the negative thermal expansion ceramic material.Calculating its thermal expansivity is-1.87 * 10 -6oC -1(20-900 oC).
The specific density test
Adopt the density of Archimedes' principle test ceramic plate sample, the specific density of the sample of embodiment 2,3,4,5 and embodiment 8 preparations is respectively 80.5%, 85.47%, 88.59%, 88.09% and 76.58%.Test result shows: when not adding MgO, sample rate can only reach 73 ~ 76% of its theoretical value, behind the interpolation MgO density is obviously improved.In addition, when sintering time was less than 10min behind the interpolation MgO, density prolonged with sintering time and increases, and reduces on the contrary to 15min density yet surpass 10 min.

Claims (2)

1. nanometer negative expansion pottery Zr 2(WO 4) (PO 4) 2Sintering and synthesizing method, it is characterized in that: with ZrO 2, WO 3And P 2O 5Be raw material, according to target product Zr 2(WO 4) (PO 4) 2Middle stoichiometric ratio Zr:W:P=2:1:2 takes by weighing raw material, adds accounting for raw material ZrO 2, WO 3And P 2O 5The MgO of gross weight 0.5 ~ 1.5%, ground and mixed is even, and oven dry, ground and mixed is even again, directly or once sintered synthetic behind the compressing tablet, takes out that quenching gets title product in air; Wherein, the sintering parameter is: 1350 ~ 1450 ℃ of temperature, times 3 ~ 20 min.
2. nanometer negative expansion pottery Zr as claimed in claim 1 2(WO 4) (PO 4) 2Sintering and synthesizing method, it is characterized in that: bake out temperature is 150 ~ 153 ℃, the time is 6 ~ 10 h.
CN2011102837248A 2011-09-22 2011-09-22 Sintering synthesis method for nanometer negative expansion ceramic Zr2(WO4)(PO4)2 Pending CN102432292A (en)

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JP6190023B1 (en) * 2015-10-07 2017-08-30 日本化学工業株式会社 Method for producing zirconium tungstate phosphate
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Cited By (12)

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Publication number Priority date Publication date Assignee Title
WO2017061402A1 (en) * 2015-10-07 2017-04-13 日本化学工業株式会社 Production method for zirconium tungsten phosphate
JP6190023B1 (en) * 2015-10-07 2017-08-30 日本化学工業株式会社 Method for producing zirconium tungstate phosphate
JP2018002578A (en) * 2015-10-07 2018-01-11 日本化学工業株式会社 Manufacturing method of zirconium tungstate phosphate
KR20180059784A (en) * 2015-10-07 2018-06-05 니폰 가가쿠 고교 가부시키가이샤 Preparation method of zirconium tungstate phosphate
US10167197B2 (en) 2015-10-07 2019-01-01 Nippon Chemical Industrial Co., Ltd. Method for producing zirconium tungsten phosphate
KR102611412B1 (en) 2015-10-07 2023-12-07 니폰 가가쿠 고교 가부시키가이샤 Method for producing zirconium tungstate phosphate
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

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