CN1891664A - Method for preparing ZrW2O8/Al2O3 nano composite material - Google Patents
Method for preparing ZrW2O8/Al2O3 nano composite material Download PDFInfo
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- CN1891664A CN1891664A CN 200610038710 CN200610038710A CN1891664A CN 1891664 A CN1891664 A CN 1891664A CN 200610038710 CN200610038710 CN 200610038710 CN 200610038710 A CN200610038710 A CN 200610038710A CN 1891664 A CN1891664 A CN 1891664A
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Abstract
This invention relates to a preparing method for nano-composite ZrW2O8/Al2O3 including getting C15H36O5Zr and WOCl4 in accordance with a chemical molar ratio of 1:2 from an airtight container to be mixed into 2-C3H8O then to be solved in the argon atmosphere, putting the container in the water bath, stirring and heating the solution to 60-80deg. C for 4-10 hours till it becomes transparent, and heating is stopped to cool it to room temperature without precipitation. Nano-Al2O3 particles of 0.5~1% of the solution volume is added in the solution in argon atmosphere to stir and heat it to 40-60 deg. C in the waterbath till it becomes gelatinous particles, then to put the colloidal in the moulder, thermo-form it with 60~100Mpa pressure under the temperature of 60-100 deg.C, the blank material is heated to 900 ~ 1000deg.C, then rapid thermal annealing for 1-2 minutes and the composite material is achieved.
Description
Technical field
Patent of the present invention relates to the preparation field of matrix material, refers in particular to a kind of with positive thermal expansivity Al
2O
3With negative expansion coefficient ZrW
2O
8Two phase materials carry out microcosmic compound preparation method.
Background technology
The material coefficient of thermal expansion coefficient just is generally, and promptly adds thermal expansion, meets cold contraction.Equally, also exist the material coefficient of thermal expansion coefficient for negative, promptly heat shrink is met cold expansion.To have negative thermal expansion material and positive expansion coefficient material carries out compound, thereby can realize the material heat expansion performance controlled, even to reach material coefficient of thermal expansion be zero, makes it not changed by outside temperature and cause scantling to change the stress that is produced.One of material with negative expansion performance that research at present is more is ZrW
2O
8It has three relatively more outstanding performances: have the negative expansion temperature range than broad; The negative expansion coefficient of its α phase is bigger; Has isotropy [1～4].ZrW
2O
8Be familiar with the beginning from its negative expansion performance, itself and compound one of the research focus that always becomes of positive thermal expansion, to explore the synthetic matrix material that is not subjected to the outside temperature variable effect with zero thermal expansion coefficient, at present with itself and Cu, Al, cement, ZrO
2Carry out compound [5～9], but the problem that occurs at present fails still to solve in the material recombination process, i.e. infiltration problem between the two-phase, homodisperse problem, not easy-formation problem.Two-phase can not be soaked into mutually, and its interface binding power is not strong, becomes formation of crack easily, reduces the intensity of material; Two phase materials are homodisperse mutually, and reuniting in the part that easily causes forming phase, also easily becomes formation of crack.In addition, because above-mentioned ZrW
2O
8With the other materials compound tense, adopt common pyroceramic sintering, then formability is relatively poor.
Because there is very big interfacial free energy in nanoparticle, the very easily spontaneous reunion of particle, the high interfacial energy that utilizes conventional blend method can not eliminate between inorganic nano-particle and the matrix is poor.Therefore, inorganic nano-particle directly can be scattered in and prepare nano composite material in the organic substrate, open the nanoparticle coacervate by the ultrasonic dispersing technical point free combat of necessity, it is evenly spread in the body material and with body material good affinity.So far, no-trump ZrW still
2O
8With the report of micro-and nano-particles complex method, more do not have the ultrasonic dispersing of employing technology and combine to synthesize ZrW with sol-gel process
2O
8/ Al
2O
3The report of nano composite material.
Reference:
1.T.A.Mary，J.S.O.Evans，T.Vogt，A.W.Sleight，Negative?Thermal?Expansion?from?0.3?to?1050?Kelvin?inZrW
2O
8，Science，1996，Vol?272，90～92
2.J.S.O.Evans，Z.Hu，J.D.Jorgensen，D.N.Argyriou，S.Short，A.W.Sleight，Compressibility，Phase?Transition，and?Oxygen?Migration?in?Zirconium?Tungstate，ZrW
2O
8，Science，1997，Vol?275，61～65
3.C.A.Perottoni，J.A.H.da?Jornada，Pressure-Induced?Amorphization?and?Negative?Thermal?Expansion?inZrW
2O
8，Science，1998，Vol?280，886～889
4.G.Ernst，C.Broholm，G.R.Kowach，A.P.Ramirez，Phonon?density?of?states?and?negative?thermal?expansion?inZrW
2O
8，Nature，1998，Vol?396，147～149
5.C.Verdon，D.C.Dunand，High-temperature?reactivity?in?the?ZrW2O8-Cu?system，Scripta?Materialia，1997，36(9)：1037-1067
6.Eiki?NIWA，Shuhji?WAKAMIKO，Takaaki?ICHIKAWA?et?al，Preparation?of?Dense?ZrO2/ZrW2O8Cosintered?Ceramics?with?Controlled?Thermal?Expansion?Coefficients，Journal?of?the?Ceramic?Society?ofJapan，2004，1305：271-275
7.Klaartje?De?Buysser，Petra?Lommens，C.De.Meyer?et?al，ZrO2-ZrW2O8?composites?with?tailor-madethermal?expansion，Journal?Ceramics-silikaty，2004，48(4)：139-144
8.M.Kofteros，S.Rodriguez，V.Tandon?et?al，Preliminary?study?of?thermal?expansion?compensation?in?cement?byZrW
2O
8?additions，Scripta?Materialia，2001，45：369-374
9.Akihiro?Matsumoto，Keizo?Kobayashi，Toshiyuki?Nishio?et?al，Fabrication?and?Thermal?Expansion?ofAl-ZrW
2O
8?Composites?by?Pulse?Current?Sintering?Process，Materials?Science?Forum，2003，426-432：2279-2284
Summary of the invention
In order to overcome not soaking between two phase materials, be difficult for homodisperse shortcoming, realize the formability of matrix material, special proposition patent of the present invention.The present invention is with ZrW
2O
8Sol-gel synthesis technique characteristic combine with ultrasonic technology, can will have the ZrW of negative expansion performance
2O
8Nanometer Al with positive hot expansibility
2O
3It is compound to carry out microcosmic, thus the nano composite material of preparing.
The object of the present invention is achieved like this:
1, colloidal sol process
According to 1: 2 weighing C of chemistry mole metering ratio
15H
36O
5Zr and WOCl
4Place encloses container to take out, under argon gas atmosphere, with C
15H
36O
5Zr, WOCl
4Be dissolved in 2-C
3H
8Form mixing solutions among the O, encloses container is inserted in the water-bath, be heated to 60～80 ℃ and stir and can obtain as clear as crystal solution in 4～10 hours, stop heating, being cooled to room temperature does not have precipitation and separates out.
2, nanometer Al
2O
3The adding of particle
Weighing accounts for the nanometer Al of liquor capacity 0.5～1%
2O
3Particle under argon gas atmosphere, joins in the solution, and heating in water bath is 40～60 ℃ when mixing, and makes solution be the gel particle.
3, the preparation of original embryo material and postheat treatment
Composite gel is inserted in the die cavity, and the pressure that applies 60～100Mpa in 60～100 ℃ temperature range carries out hot-forming; The base material is heated to 900～1000 ℃, carries out short annealing then and just can obtain final matrix material in 1～2 minute.
In the colloidal sol process with WOCl
4Be dissolved in 2-C
3H
8It is 0.08～0.5mol/l that O calculates the volumetric molar concentration of adjusting mixing solutions, at nanometer Al
2O
3In the adition process of particle, adopt ultrasonic unit to carry out dispersing and mixing 1～3 hour.
The inventive method and existing preparation ZrW
2O
8Composite process is compared has following advantage:
(1) chemosynthesis process (sol-gel) and physics dispersion technology (ultrasonic dispersing) are combined, can be to ZrW from the yardstick on the microcosmic
2O
8/ Al
2O
3Nano composite material is synthesized;
(2) composite gel that is obtained, easy-formation;
(3) reduce synthetic ZrW
2O
8Temperature and time (solid phase synthesis ZrW
2O
8Temperature range is 1100～1250 ℃, needs generated time simultaneously: between 24 hours to a week)
Embodiment
Utilize chemosynthesis process and physics dispersion technology to synthesize ZrW
2O
8/ Al
2O
3Nano composite material further specifies below in conjunction with example.
Example one
1, gelation process
In vacuum chamber, measure than 1: 2 weighing C according to the chemistry mole
15H
36O
5Zr and WOCl
4Place encloses container to take out; With WOCl
4Be dissolved in 2-C
3H
8It is 0.08M that O calculates volumetric molar concentration, and then under argon gas atmosphere, the limit is stirred the limit and splashed into required 2-C
3H
8O; Encloses container is inserted in the water-bath, be heated to 60 ℃ and stir and can obtain as clear as crystal solution in 4 hours, stop heating, being cooled to fusion-room temperature long placing does not have precipitation and separates out.
2, nanometer Al
2O
3The adding of particle
Weighing accounts for the nanometer Al of liquor capacity 0.5%
2O
3Particle after the adding, under argon gas atmosphere, is used ultrasonic unit instead and was disperseed 1 hour equally, and mixing simultaneously, heating in water bath is the gel particle for 40 ℃.
3, the preparation of original embryo material and postheat treatment
Composite gel is inserted in the die cavity, and 60 ℃ of pressure that apply 60Mpa are hot-forming; The base material is put into quick quenching furnace be heated to 900 ℃, carried out short annealing then 1 minute, just can obtain final matrix material.
Example two
1, gelation process
In vacuum chamber, measure than 1: 2 weighing C according to the chemistry mole
15H
36O
5Zr and WOCl
4Place encloses container to take out; With WOCl
4Be dissolved in 2-C
3H
8It is 0.25M that O calculates volumetric molar concentration, and then under argon gas atmosphere, the limit is stirred the limit and splashed into required 2-C
3H
8O; Encloses container is inserted in the water-bath, be heated to 70 ℃ and stir and can obtain as clear as crystal solution in 7 hours, stop heating, being cooled to fusion-room temperature long placing does not have precipitation and separates out.
2, nanometer Al
2O
3The adding of particle
Weighing accounts for the nanometer Al of liquor capacity 0.8%
2O
3Particle after the adding, under argon gas atmosphere, is used ultrasonic unit instead and was disperseed 2 hours equally, and mixing simultaneously, heating in water bath is the gel particle for 50 ℃.
3, the preparation of original embryo material and postheat treatment
Composite gel is inserted in the die cavity, and 80 ℃ of pressure that apply 80Mpa are hot-forming; The base material is put into quick quenching furnace be heated to 950 ℃, carried out short annealing then 1.5 minutes, just can obtain final matrix material.
Example three
1, gelation process
In vacuum chamber, measure than 1: 2 weighing C according to the chemistry mole
15H
36O
5Zr and WOCl
4Place encloses container to take out; With WOCl
4Be dissolved in 2-C
3H
8It is 0.5M that O calculates volumetric molar concentration, and then under argon gas atmosphere, the limit is stirred the limit and splashed into required 2-C
3H
8O; Encloses container is inserted in the water-bath, be heated to 80 ℃ and stir and can obtain as clear as crystal solution in 10 hours, stop heating, being cooled to fusion-room temperature long placing does not have precipitation and separates out.
2, nanometer Al
2O
3The adding of particle
Weighing accounts for the nanometer Al of liquor capacity 1%
2O
3Particle after the adding, under argon gas atmosphere, is used ultrasonic unit instead and was disperseed 3 hours equally, and mixing simultaneously, heating in water bath is the gel particle for 60 ℃.
3, the preparation of original embryo material and postheat treatment
Composite gel is inserted in the die cavity, and 100 ℃ of pressure that apply 100Mpa are hot-forming; The base material is put into quick quenching furnace be heated to 1000 ℃, carried out short annealing then 2 minutes, just can obtain final matrix material.
It is ZrW that above-mentioned three example institute synthetic nano composite materials are analyzed all through XRD (X diffraction X-ray analysis X)
2O
8And Al
2O
3Phase; Observe through SEM (scanning electron microscope), its particle is uniformly dispersed, and with matrix between the interface combine well.
Claims (3)
1, a kind of ZrW
2O
8/ Al
2O
3The preparation method of nano composite material is characterized in that: adopt following steps to prepare ZrW
2O
8/ Al
2O
3Nano composite material:
(1) colloidal sol process
According to 1: 2 weighing C of chemistry mole metering ratio
15H
36O
5Zr and WOCl
4Place encloses container to take out, under argon gas atmosphere, with C
15H
36O
5Zr, WOCl
4Be dissolved in 2-C
3H
8Form mixing solutions among the O, encloses container is inserted in the water-bath, be heated to 60～80 ℃ and stir and can obtain as clear as crystal solution in 4～10 hours, stop heating, being cooled to room temperature does not have precipitation and separates out;
(2) nanometer Al
2O
3The adding of particle
Weighing accounts for the nanometer Al of liquor capacity 0.5～1%
2O
3Particle under argon gas atmosphere, joins in the solution, and heating in water bath is 40～60 ℃ when mixing, and makes solution be the gel particle;
(3) preparation of original embryo material and postheat treatment
Composite gel is inserted in the die cavity, and the pressure that applies 60～100Mpa in 60～100 ℃ temperature range carries out hot-forming; The base material is heated to 900～1000 ℃, carries out short annealing then and just can obtain final matrix material in 1～2 minute.
2, a kind of ZrW according to claim 1
2O
8/ Al
2O
3The preparation method of nano composite material is characterized in that: in the colloidal sol process with WOCl
4Be dissolved in 2-C
3H
8It is 0.08～0.5mol/l that O calculates the volumetric molar concentration of adjusting mixing solutions.
3, a kind of ZrW according to claim 1
2O
8/ Al
2O
3The preparation method of nano composite material is characterized in that: at nanometer Al
2O
3In the adition process of particle, adopt ultrasonic unit to carry out dispersing and mixing 1～3 hour.
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| CN100455535C CN100455535C (en) | 2009-01-28 |
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Cited By (4)
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| CN103909265A (en) * | 2014-04-14 | 2014-07-09 | 哈尔滨工业大学 | Molybdenum-tungsten acid scandium composite material and preparation method thereof |
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| CN114231784A (en) * | 2021-12-20 | 2022-03-25 | 哈尔滨工业大学 | Preparation method of low-expansion zirconium tungstate/aluminum composite material |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1999064898A2 (en) * | 1998-05-19 | 1999-12-16 | Corning Incorporated | Negative thermal expansion materials including method of preparation and uses therefor |
| CN1100155C (en) * | 2000-01-13 | 2003-01-29 | 上海交通大学 | High-thermal-conductivity low-expansibility compound material and its preparing process |
| CN1091084C (en) * | 2000-03-10 | 2002-09-18 | 上海交通大学 | Low (or negative)-expansibility complex-phase ceramic and its preparing process |
| CN1159258C (en) * | 2002-06-03 | 2004-07-28 | 上海交通大学 | Multi-element negative-expansion tungstate layer coated on microcrystal ceramics and its preparing process |
| CN1238303C (en) * | 2004-07-01 | 2006-01-25 | 上海交通大学 | Negative thermal-expansion coefficient adjustable laminated ceramic matrix composite and preparing method thereof |
| CN1301347C (en) * | 2005-01-25 | 2007-02-21 | 北京科技大学 | Preparation of single-crystal of thermal negative expanding material ZrW2O8 |
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- 2006-03-08 CN CNB2006100387109A patent/CN100455535C/en not_active Expired - Fee Related
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| CN103909265A (en) * | 2014-04-14 | 2014-07-09 | 哈尔滨工业大学 | Molybdenum-tungsten acid scandium composite material and preparation method thereof |
| CN103909265B (en) * | 2014-04-14 | 2017-02-15 | 哈尔滨工业大学 | Molybdenum-tungsten acid scandium composite material and preparation method thereof |
| RU2592923C1 (en) * | 2015-07-02 | 2016-07-27 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский государственный университет" (ТГУ) | Method of producing ceramic composite with zero coefficient of thermal linear expansion |
| CN114231784A (en) * | 2021-12-20 | 2022-03-25 | 哈尔滨工业大学 | Preparation method of low-expansion zirconium tungstate/aluminum composite material |
| CN115594490A (en) * | 2022-08-25 | 2023-01-13 | 山东大学（Cn） | Low-thermal-expansion alumina-based ceramic cutter material and preparation process thereof |
| CN115594490B (en) * | 2022-08-25 | 2023-04-14 | 山东大学 | Low-thermal-expansion alumina-based ceramic cutter material and preparation process thereof |
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| CN100455535C (en) | 2009-01-28 |
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