CN1375480A - Prepn. of nickel-zirconia cermet - Google Patents

Prepn. of nickel-zirconia cermet Download PDF

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CN1375480A
CN1375480A CN 02115711 CN02115711A CN1375480A CN 1375480 A CN1375480 A CN 1375480A CN 02115711 CN02115711 CN 02115711 CN 02115711 A CN02115711 A CN 02115711A CN 1375480 A CN1375480 A CN 1375480A
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nickel
zirconium white
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composite powder
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CN1160276C (en
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邵刚勤
谢济仁
段兴龙
蔡虎
余晓华
袁润章
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Wuhan University of Science and Engineering WUSE
Wuhan University of Technology WUT
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Abstract

The nickel salt, zirconium salt, stabilizing agent and solvent are mixed into mixed solution, then the mixed solution, additive and complexone are mixed according to a certain ratio into collosol which is then dried into gel, the gel is precombusted to obtain nickel oxide-zirconium oxide nano composite powder which can be used for preparing metal ceramics in two ways: a. said oxide powder is formed and atmospheric fired to obtain nickel oxide-zirconium oxide double-phase ceramics which then is reduced to obtain said nickel-zirconium oxide metal ceramics; and b. the oxide powder is reduced to obtain nickel-zirconium oxide composite powder, then is formed and fired under the condition of vacuum and reduction atmosphere or inert-gas to obtain said product.

Description

The preparation method of nickel-zirconia cermet
Technical field
The present invention relates to a kind of preparation method of nickel-zirconia cermet.
Background technology
Nickel-zirconium white (Ni-ZrO 2) sintering metal is widely used in solid fuel cell (SOFC) anode material, Functionally Graded Materials, ceramic membrane and the oxygen sensor.The general method of general milling or high-energy ball milling (mechanical alloying) that adopts prepares this material, is about to nickel oxide (NiO) powder, zirconium white (ZrO 2) powder and stablizer such as yttrium oxide (Y 2O 3), cerium oxide (CeO 2), behind calcium oxide (CaO) powder technique with hydrogen (H 2), rare gas element-hydrogen mixed gas, carbon monoxide gas (CO), carbon monoxide-carbonic acid gas (CO/CO 2) gas mixture reduction or directly metallic nickel (Ni) powder, Zirconium oxide powder and stablizer powder technique are formed (D.W.Dees et al., Conductivity of PorousNi/ZrO 2-Y 2O 3Cermets, J Electrochemical Soc, 1987,134 (9): 2141-2146; Composite cermet articles and manufacture method thereof, Chinese invention patent ZL 95 1 97006.6, October 30 nineteen ninety-five; Sintering metal and preparation method thereof, Chinese invention patent ZL on March 10th, 94 1 02287.6,1994).
Because Ni and ZrO 2Not exclusively wetting (118 °, 1500 ℃, vacuum) do not dissolve fully, thermal expansivity (Ni:20 * 10 that differ greatly -6/ ℃; ZrO 2: 550 * 10 -6/ ℃), so it is at present also there are many defectives in prepared this ceramic-metallic performance, low as intensity, fragility big, thermoelectricity capability can not effectively mate by metal and ceramic components.
Trace it to its cause, adopt ball milling method to be difficult to reach molecular level or nano level evenly compound, promptly use high-energy ball milling also can only obtain the mixture of nanoparticle and subparticle, it is very difficult to obtain uniform nano particle, and mixing process is easy to cause skewness, the doping of component and granularity.
Therefore, the compound particularly liquid phase of humble level compounding technology is only the only way of preparation desired metallic pottery, along with the development of nanometer composite technology, high-performance Ni-ZrO 2Ceramic-metallic preparation becomes possibility.
The characteristic length (as mean free path) of the hot carrier (phonon-electronics) of nano composite pottery can be compared because of nanometer has become, at this moment the physical parameter that reflects the material mechanical property is (as hardness, Young's modulus, intensity), the physical parameter of reflection energy transport rule is (as thermal conductivity, specific heat capacity), the physical parameter of reflection material electromagnetic property is (as specific conductivity, magnetic permeability) etc. all can embody distinct yardstick dependency, nano ceramics has insulation mutually, insulative properties, and having high electricity, nanometer gold symbolic animal of the birth year leads, high thermal conductance characteristic, its performance in function-configuration aspects will be significantly different with micron or submicron material.So correlative study of the present invention has become the focus of current domestic and international investigation of materials.
At present, the liquid phase preparation process of nickel-zirconia cermet is as described below:
I. coprecipitation method: select suitable precipitation agent, make all metal ions in the solution satisfy deposition condition simultaneously, the method for coprecipitation (
Figure A0211571100041
M et al.Preparation of Ni-YSZ composite materials for solid oxidefuel cell anodes by the gel-precipitation method, J Power Sources 2000; 86,383-389; TPLockhalt et al.US Patent No.5261944,16 Nov.1993).This method can prepare be evenly distributed, powder that particle is tiny, but it is still precipitation respectively in essence, so deviation takes place in stoichiometry easily, sedimentary uniform distribution can only reach on the particle diameter level of throw out particulate (the sedimentary particle diameter of gained no matter be principal constituent or trace ingredients much at one), and often be difficult to find suitable precipitation agent, can think or the solid phase mixing method.Other has the investigator to propose some improved precipitator method, and as sluggish precipitation, buffered soln method etc., but the problems referred to above do not solve at all.
II. solution combustion synthesis method: the oxide powder presoma is synthetic with the auto-combustion method of solution, can not need directly prepare final powder through pilot process, but raw material sources harshness, reaction process are difficult to control, be difficult to obtain accurate stoichiometric product (Kim S J et al.Preparation of nanocrystalline nickel oxide-yttria-stabilized zirconiacomposite powder by solution combustion with ignition of glycine fuel, J Mater Res 2001; 16 (12): 3621-3627).
III. sol-gel method:, obtain nano combined NiO-ZrO by hydrolysis and polycondensation with the soluble metal alkoxides of nickel, zirconium, yttrium 2And Ni-ZrO 2Material.This method was just controlled at the preparation material initial stage, made homogeneity can reach submicron, nano level even molecular level level.But the relevant alkoxide that obtains all compound conditions very difficulty even may, even there is its price also will be very expensive.
For this reason, the inventor has proposed the sol-gel method of present this modification, has both inherited the advantage of above-mentioned sol-gel method, has again that temperature of reaction is low, powder diameter is little, narrowly distributing, raw materials cost be low, do not need unconventional preparation condition.
Summary of the invention
The objective of the invention is to propose a kind of method for preparing nickel-zirconia cermet.
The objective of the invention is to realize as follows:
Accompanying drawing is preparation method's sketch of nickel-zirconia cermet, and the present invention will be described below in conjunction with sketch.
Nickel salt (1), zirconates (2), stablizer (3) are selected inorganic salt, acetate, oxalate, the metal alkoxide of its solubility for use, and volumetric molar concentration is 0.5～4.0M, pH=1～6.Wherein stablizer is one or more in the salt of yttrium salt, cerium salt, calcium salt, magnesium salts or other rare earth element, and the kind of stablizer and volume are selected (Chinese invention patent, ZL 94 1 20137.6, on December 29th, 1994) by the requirement of zirconium white series material.
Solvent (4) is a kind of in water, ammoniacal liquor-ammonium salt solution, pure water, ketone water, organic amine, the organic acid, and volumetric molar concentration is not more than 3.0M, pH=1～8.Solvent provides the place of complex reaction, and makes its stable dispersion by the affinity that changes the colloidal sol group.
Admixture solution (5) is with steric dispersion agent (hydroxy propyl cellulose HPC, vinylformic acid-maleic acid, tetrafluoroethylene, polyacrylamide, polystyrene, oleic acid), steric dispersion agent (Witco 1298 Soft Acid DBS, polyoxyethylene glycol PEG, polyacrylic acid PAA, Triton X-100 OP, tween, amino acid, trimethyl-glycine, tetrahydroglyoxaline, alkylol amide, methyl methacrylate), emulsifying agent (nonane diacid diethyl fat, hexanaphthene-polyoxyethylene-4-lauryl ether ICI, hexanaphthene-n-hexyl alcohol-octyl phenol Soxylat A 25-7 Triton) in one or more are dissolved in and form in the water, and weight concentration is 1～5wt.%.Admixture makes colloidal sol stable by space steric effect, micelle surface electrokinetic potential, particle surface vacancy effect, surface modification, surface active, microcell nucleating growth controlling mechanism.
Complexone solution (6) is among edta edta, CDTA DCTA, Diethylenetriaminee (DETA) DETA, triethylenetetramine Trien, tetraethylenepentamine Tetren, pentaethylene hexamine Penten, glycine, nitrilotriacetic acid(NTA) NTA, diethylenetriamine pentaacetic acid DPTA, the teiethylene tetramine-hexacetic acid TTHA one or more to be dissolved in the water form, volumetric molar concentration is 0.1～2.0M, pH=1～6.Complexone provides organic polymer functional group to change the solvability and the reactive behavior of raw material.
With above-mentioned nickel salt (1), zirconates (2), stablizer (3) and solvent (4) are made into mixing solutions by the ceramic-metallic chemical ingredients of required preparation, again with mixing solutions, admixture solution (5) and complexone solution (6) mix by 100: 1: 10 volume ratio, evenly stir (7) at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol is through 105～200 ℃, 12～72 hours drying (8) become gel, gel is through 400～700 ℃, pre-burning (9) in 1～4 hour, obtain nickel oxide-zirconium white nano composite powder, adopt two lines with this powdered preparation sintering metal: a. nickel oxide-zirconium white nano composite powder is through moulding process A, under atmosphere through 1000～1500 ℃, burnt till in 1～4 hour (10), obtain nickel oxide-zirconium white complex phase ceramic, this complex phase ceramic under reducing atmosphere through 800～1200 ℃, 1～4 hour reduction process A (11) makes nickel-zirconia cermet; B. nickel oxide-zirconium white nano composite powder under reducing atmosphere through 600～1000 ℃, 1～4 hour reduction process B (12), obtain nickel-zirconium white nano composite powder, nickel-zirconium white nano composite powder is through moulding process B, under vacuum, reducing atmosphere or inert atmosphere, burnt till (13), make nickel-zirconia cermet through 1000～1500 ℃, 1～4 hour.Wherein reducing atmosphere is a kind of in pure hydrogen, rare gas element-hydrogen (ratio is 5: 95～95: 5), pure carbon monoxide gas, the carbon monoxide-carbon dioxide mix gas (ratio is 5: 95～95: 5).
The invention has the advantages that: (one) admixture makes colloidal sol stable by space steric effect, micelle surface electrokinetic potential, particle surface vacancy effect, surface modification, surface active, microcell nucleating growth controlling mechanism; (2) solvent provides the place of complex reaction, and makes its stable dispersion by the affinity that changes the colloidal sol group; (3) complexone provides organic polymer functional group to change the solvability and the reactive behavior of raw material; (4) reaction makes required nickel-zirconia cermet to the nano composite oxide powder through in-situ reducing.
The present invention has overcome metallographic phase and ceramic phase skewness among other preparation method, the unmanageable shortcoming of technology, and raw material is easy to get, pollution-free, chemical ingredients is with component is easily controlled mutually, technology is simple and direct, cost performance is high.Can be generalized to the material that development has pottery and metal excellent properties concurrently, as novel hi-tech 26S Proteasome Structure and Function materials such as " high hard, high-strength ", " insulation, high thermal conductance ", " high-strength, high electricity is led ", " conversions of heat-electricity ".
Specific embodiments
Example 1:
The nickelous nitrate of 4M, the basic zirconium chloride of 2M, the Yttrium trichloride of 0.5M and the alcohol solution of 3M are pressed the 25Ni-7Y of required preparation 2O 3-ZrO 2Ceramic-metallic chemical ingredients is made into mixing solutions, again the nitrilotriacetic acid(NTA) NTA solution of the hydroxy propyl cellulose solution of mixing solutions, 1wt.% and the 0.1M volume ratio by 100: 1: 10 is mixed, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol obtains gel through 200 ℃, 12 hours dryings, and gel is obtained NiO-ZrO through pre-burning in 400 ℃, 4 hours 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 9.2nm.With behind this powder compacting under atmosphere through being fired into NiO-ZrO in 1000 ℃, 4 hours 2Complex phase ceramic.NiO-ZrO 2Complex phase ceramic is in pure hydrogen, through being reduced into Ni-ZrO in 1200 ℃, 1 hour 2Sintering metal, scanning electron microscope (SEM) analysis revealed, Ni and ZrO 2Distribution mutually very even, X-ray diffraction analysis (XRD) shows, only contains metal Ni in the sintering metal mutually and ZrO 2Ceramic phase, Rockwell hardness HRA=58, the coefficient of thermal expansion in the time of 1000 ℃ are 10.7 * 10 -6K -1, the specific conductivity in the time of 1000 ℃ is 0.03S/cm.
Example 2:
The nickelous oxalate of 0.5M, the zirconium acetate of 2M, the magnesium nitrate of 4M and the citric acid solution of 2M are pressed the 25Ni-20MgO-ZrO of required preparation 2Ceramic-metallic chemical ingredients is made into mixing solutions, again with the triethylenetetramine Trien solution of Diethylenetriaminee (DETA) DETA, the 3M of the polyacrylamide of mixing solutions, 5wt.%, 5wt.% nonane diacid diethyl lipoprotein solution, 3M by 100: 0.5: 0.5: 5: 5 volume ratio mixes, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol obtains gel through 105 ℃, 72 hours dryings, and gel is obtained NiO-ZrO through pre-burning in 700 ℃, 1 hour 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 8.7nm.With behind this powder compacting under atmosphere through burning till NiO-ZrO in 1500 ℃, 1 hour 2Complex phase ceramic.NiO-ZrO 2Complex phase ceramic is in carbon monoxide-carbon dioxide mix gas (ratio is 5: 95), through being reduced into Ni-ZrO in 800 ℃, 4 hours 2Sintering metal, XRD analysis show, only contain metal Ni phase and ZrO in the sintering metal 2Ceramic phase, HRA=60, the coefficient of thermal expansion in the time of 1000 ℃ are 9.8 * 10 -6K -1
Example 3:
The nickelous chloride of 2M, the zirconium chloride of 1M, the calcium chloride of 2M, the magnesium chloride of 2M and the formic acid solution of 1M are pressed the 35Ni-10MgO-10CaO-ZrO of required preparation 2Ceramic-metallic chemical ingredients is made into mixing solutions, again with the pentaethylene hexamine Penten solution of tetraethylenepentamine Tetren, the 3M of the polyoxyethylene glycol PEG solution of mixing solutions, 2.5wt.%, 3M by 100: 1: 5: 5 volume ratio mixes, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol obtains gel through 160 ℃, 48 hours dryings, and gel is obtained NiO-ZrO through pre-burning in 550 ℃, 2.5 hours 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 6.3nm.With behind this powder compacting under atmosphere through burning till NiO-ZrO in 1300 ℃, 2.5 hours 2Complex phase ceramic.NiO-ZrO 2Complex phase ceramic is in carbon monoxide-carbon dioxide mix gas (ratio is 95: 5), through being reduced into Ni-ZrO in 1100 ℃, 2.5 hours 2Sintering metal, scanning electron microscope (SEM) analysis revealed, Ni and ZrO 2Distribution mutually very even, XRD analysis shows, only contains metal Ni in the sintering metal mutually and ZrO 2Ceramic phase, HRA=54, the coefficient of thermal expansion in the time of 1000 ℃ are 10.9 * 10 -6K -1
Example 4:
The nickelous oxalate of 0.5M, the oxalic acid zirconium of 2M, the cerous nitrate of 4M and the alcohol solution of 4M are pressed the 17Ni-34CeO of required preparation 2-ZrO 2Ceramic-metallic chemical ingredients is made into mixing solutions, again with the CDTA DCTA solution of tween, 2.5wt.% polystyrene solution and the 1.5M of mixing solutions, 2.5wt.% by 100: 0.5: 0.5: 10 volume ratio mixes, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol obtains gel through 105 ℃, 72 hours dryings, and gel is obtained NiO-ZrO through pre-burning in 700 ℃, 1 hour 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 5.5nm.With this powder in carbon monoxide-carbon dioxide mix gas (ratio is 5: 95), through being reduced into Ni-ZrO in 600 ℃, 4 hours 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 26.2nm, XRD analysis shows, only contains metal Ni phase and ZrO in the powder 2Ceramic phase.With Ni-ZrO 2Be placed on after the nano composite powder moulding in the hot pressing furnace of argon shield and carry out sintering, through burning till Ni-ZrO in 1500 ℃, 1 hour 2Sintering metal, sem analysis show, Ni and ZrO 2Distribution mutually very even, XRD analysis shows, only contains metal Ni in the sintering metal mutually and ZrO 2Ceramic phase.HRA＝61。
Example 5:
With the nickelous nitrate of 4M, the ethanol zirconium of 0.5M, the Yttrium trichloride of 1M, the Cerium II Chloride of 1M and the urea CO (NH of 1M 2) 2Solution is by the 25Ni-3.5Y of required preparation 2O 3-29CeO 2-ZrO 2Ceramic-metallic chemical ingredients is made into mixing solutions, vinylformic acid-maleic acid of mixing solutions, 5wt.%, the Witco 1298 Soft Acid DBS solution of 5wt.%, the diethylenetriamine pentaacetic acid DPTA solution of 0.1M were pressed 100: 0.5: 0.5: 10 volume ratio mixes again, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol obtains gel through 200 ℃, 12 hours dryings, and gel is obtained NiO-ZrO through pre-burning in 400 ℃, 4 hours 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 7.1nm.With this powder in carbon monoxide-carbon dioxide mix gas (ratio is 95: 5), through being reduced into Ni-ZrO in 1000 ℃, 1 hour 2Nano composite powder, with X-ray diffraction line width method analysis revealed, powder average crystal grain particle diameter is 28.3nm, XRD analysis shows, only contains metal Ni phase and ZrO in the powder 2Ceramic phase.With Ni-ZrO 2Be placed on after the nano composite powder moulding and carry out sintering in the vacuum oven, through burning till Ni-ZrO in 1000 ℃, 4 hours 2Sintering metal, XRD analysis show, only contain metal Ni phase and ZrO in the sintering metal 2Ceramic phase.HRA＝62。
Example 6:
The nickelous nitrate of 2.5M, the basic zirconium chloride of 4M, Yttrium trinitrate and the distilled water of 0.5M are pressed the ceramic-metallic chemical ingredients 40Ni-6Y of required preparation 2O 3-ZrO 2Be made into mixing solutions, again the edta edta solution of the amino acid solution of mixing solutions, 1wt.% and the 1.5M volume ratio by 100: 1: 10 is mixed, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol obtains gel through 150 ℃, 50 hours dryings, and gel is obtained NiO-ZrO through pre-burning in 550 ℃, 2.5 hours 2Nano composite powder, high-resolution-ration transmission electric-lens (HRTEM) analysis revealed, powder diameter is in the 5-15nm scope.With this powder in hydrogen, through being reduced into Ni-ZrO in 800 ℃, 2.5 hours 2Nano composite powder, high-resolution-ration transmission electric-lens (HRTEM) analysis revealed, powder diameter shows with power spectrum and in conjunction with morphology analysis in the 25-35nm scope, Ni and ZrO 2Formed nano level compoundly, X-ray diffraction analysis (XRD) shows, only contains metal Ni in the powder mutually and ZrO 2Ceramic phase.With Ni-ZrO 2Be placed on after the nano composite powder moulding in the hot pressing furnace of argon shield and carry out sintering, through burning till Ni-ZrO in 1300 ℃, 2.5 hours 2Sintering metal, its Rockwell hardness HRA=47, XRD analysis shows, only contains metal Ni phase and ZrO in the sintering metal 2Ceramic phase, the coefficient of thermal expansion in the time of 1000 ℃ are 12.8 * 10 -6K -1, specific conductivity is 0.4S/cm.

Claims (1)

1. the preparation method of nickel-zirconia cermet is characterized in that volumetric molar concentration is 0.5～4.0M, the nickel salt of pH=1～6, zirconates, stablizer and volumetric molar concentration are not more than 3.0M, the solvent of pH=1～8 is made into mixing solutions by the ceramic-metallic chemical ingredients of required preparation, again with mixing solutions, weight concentration is that admixture solution and the volumetric molar concentration of 1～5wt.% is 0.1～2.0M, the complexone solution of pH=1～6 mixes by 100: 1: 10 volume ratio, evenly stir at 5～50 ℃, reacting becomes complex compound colloidal sol, colloidal sol is through 105～200 ℃, drying became gel in 12～72 hours, gel is through 400～700 ℃, pre-burning in 1～4 hour, obtain nickel oxide-zirconium white nano composite powder, adopt two lines with this powdered preparation sintering metal:
A. nickel oxide-zirconium white nano composite powder is through overmolding, burnt till through 1000～1500 ℃, 1～4 hour under atmosphere, obtain nickel oxide-zirconium white complex phase ceramic, this complex phase ceramic through reduction in 800～1200 ℃, 1～4 hour, makes nickel-zirconia cermet under reducing atmosphere;
B. nickel oxide-zirconium white nano composite powder reduced through 600～1000 ℃, 1～4 hour under reducing atmosphere, obtain nickel-zirconium white nano composite powder, nickel-zirconium white nano composite powder is through overmolding, under vacuum, reducing atmosphere or inert atmosphere, burnt till, make nickel-zirconia cermet through 1000～1500 ℃, 1～4 hour;
Wherein: stablizer is one or more in the salt of yttrium salt, cerium salt, calcium salt, magnesium salts or other rare earth element, and the kind of stablizer and volume are selected by the requirement of zirconium white series material; Solvent is a kind of in water, ammoniacal liquor-ammonium salt solution, pure water, ketone water, organic amine, the organic acid; Admixture is a kind of or a few profit in steric dispersion agent, tensio-active agent, the emulsifying agent to be dissolved in the water form; Complexone solution is in the complexone one or more to be dissolved in the water form; Reducing atmosphere is a kind of in pure hydrogen, rare gas element-hydrogen (ratio is 5: 95～95: 5), pure carbon monoxide gas, the carbon monoxide-carbon dioxide mix gas (ratio is 5: 95～95: 5).
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Cited By (3)

* Cited by examiner, † Cited by third party
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CN102199033A (en) * 2010-03-26 2011-09-28 迪亚摩弗股份公司 Functionally graded material shape and method for producing such a shape
CN102896317A (en) * 2012-10-23 2013-01-30 上海大学 Method for preparing Mo-ZrO2 metal ceramic electrode by utilizing sol-gel method
TWI498278B (en) * 2012-08-28 2015-09-01 Advanced Lithium Electrochemistry Co Ltd Preparation method of battery composite material and precursor thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102199033A (en) * 2010-03-26 2011-09-28 迪亚摩弗股份公司 Functionally graded material shape and method for producing such a shape
CN102199033B (en) * 2010-03-26 2014-07-09 迪亚摩弗股份公司 Functionally graded material shape and method for producing such a shape
TWI498278B (en) * 2012-08-28 2015-09-01 Advanced Lithium Electrochemistry Co Ltd Preparation method of battery composite material and precursor thereof
US9932235B2 (en) 2012-08-28 2018-04-03 Advanced Lithium Electrochemistry Co., Ltd. Preparation method of battery composite material and precursor thereof
CN102896317A (en) * 2012-10-23 2013-01-30 上海大学 Method for preparing Mo-ZrO2 metal ceramic electrode by utilizing sol-gel method

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