CN1528706A

CN1528706A - Y2O3 stable tetragonal phase ZrO2 monodisperse nano posder hydrothermal preparation method

Info

Publication number: CN1528706A
Application number: CNA2003101112256A
Authority: CN
Inventors: 徐华蕊
Original assignee: Individual
Current assignee: Individual
Priority date: 2003-10-10
Filing date: 2003-10-10
Publication date: 2004-09-15

Abstract

The invention relates to a hydrothermal preparing method of Y2O3 stable square-phase ZrO2 monodisperse nano powder, preparing a certain concentration solution by zirconium oxychloride, directly placing in high pressure anticorrosive reacting kettle, reacting at the hydrothermal temperature of 150-260 deg.C for 4-24 h, uniformly stirring the resultant to add in yttrium chloride solution, successively dropping in ammonia, filtering, washing, and sintering to obtain it. The obtained Y2O3-ZrO2 compound powder's average particle size is not greater than 100nm under the observation of scanning electron microscope, its maximum particle size measured by laser particle size measurer is less than 2.0mum when it is dispersed by pure water and ultrasonic wave without dispersing agent, and it is a single square phase and has no other mixed phases analyzed by X-diffraction meter.

Description

Y 2O 3Stablize Tetragonal ZrO 2The hydrothermal preparing process of dispersed nano powder

Technical field

The present invention relates to the preparation method of Zirconium oxide powder, particularly have Y ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder.

Background technology

Zirconium white is a kind of important stupalith.Use Y ₂O ₃Stable Tetragonal ZrO ₂(Y-TZP) pottery has high room temperature strength and fracture toughness.Experiment shows that the highest room temperature fracture toughness property of Y-TZP material can reach 12MPam ^1/2, bending strength can reach 2500MPa, also has fabulous high temperature superplastic ability.Obtained 1038% stretching variable at present, made in all stupaliths superplasticity best.It is found that, when the crystal grain of Y-TZP material is controlled at 100nm when following, the sudden change that may bring material property.The one, intensity might and then reach high value; The 2nd, be difficult for causing transgranular fracture, help improving the fracture toughness property of material; The 3rd, might realize superplasticity under the normal temperature.And in order to obtain the zirconia ceramics of very-high performance like this, one of most important condition need to make the particle diameter of Zirconium powder little exactly, the single dispersion, and it is low also should to possess simultaneously cost, is easy to suitability for industrialized production.

The method for preparing at present nano zirconium oxide powder is a lot, and common have coprecipitation method, alkoxide hydrolysis, basic zirconium chloride hydrolysis method, precipitation---hydrothermal method, colloidal sol---gel method, emulsion method, a microemulsion method etc.As having in the preparation nano zirconium oxide powder of open source literature report: 1, " nanoscale ZrO ₂(Y ₂O ₃)/Al ₂O ₃The preparation of powder and sintering character thereof ", " modern technologies pottery " .1995,16 (1), this paper adopts the chemical coprecipitation gel method to prepare 2mol%Y ₂O ₃-ZrO ₂-20wt%Al ₂O ₃The ceramic powders that nano level superfine is compound has carried out the sintering test under the different temperatures to this powder under normal pressure, the phase composition of powder that utilized XRD analysis; Calculated the powder crystal size with the XRD-BL method, studied the pattern of powder with TEM, size and distribution thereof, measured the bulk density of sintered body with the Archimedes method, with the SEM Observe and measure microstructure of sintered body, the result shows, the powder size narrow distribution range that this legal system is standby, good dispersion, powder sintering is active high; 2, " sol method synthesizes ZrO ₂(Y ₂O ₃) nanocrystalline Ultramicro-powder research "; " Northwestern Polytechnical University's journal " .1995,13 (3). studied the synthetic ZrO of water base sol method ₂(Y ₂O ₃) possibility of nanocrystalline ultrafine powder.The result shows that it is tens of ultrafine powders to several nanometers that this method can be synthesized particle diameter, and the synthetic diameter of particle is evenly distributed good dispersity.By selecting predecessor concentration value in the colloidal sol forming process, can effectively control the particle diameter of synthetic ultrafine powder, concentration increases, and diameter of particle reduces.Synthetic ZrO ₂(Y ₂O ₃) the powder minimum grain size is 6nm, this value is determined by the size of colloidal particle critical nucleus in the colloidal sol; 3, " the alcohol-water solution heating prepares nanometer ZrO ₂The research of powder and correlated process " " Journal of Inorganic Materials " .2000,15 (1). this paper has analyzed the alcohol-water solution heating and has prepared nanometer ZrO ₂(3Y) process of powder and heating-up temperature, time are to the impact of course of reaction and last gained powder.Result of study shows, the standby nanometer ZrO of this legal system ₂Series of chemical has taken place in powder process, and these reactions make Y ₂O ₃The precursor body is at ZrO ₂Evenly distribute Y in the presoma ₂O ₃During powder calcination, be penetrated into gradually ZrO ₂Make it to change into Tetragonal in the particle; 4, " prepare nanometer ZrO with the protection precipitation method ₂(Y ₂O ₃) powder " " investigation of materials journal " .2002,16 (2). proposed to have prepared ZrO with Tween-80 protection coprecipitation ₂(Y ₂O ₃) nano-powder, use differential thermal analysis, thermogravimetric analysis, the technical research institutes such as X-ray diffraction and transmission electron microscope the feature of powder, the result shows: 700 ℃ the burning 0.5h after ZrO ₂(Y ₂O ₃) average grain diameter of powder is 3-9nm, specific surface is 128.5-134.5m ³/ g, ZrO behind 1250 ℃ of calcining 8h ₂(Y ₂O ₃) powder has been completed into the ZrO of Emission in Cubic ₂Big solution, and extraordinary sintering character is arranged.5, " pipe reaction prepares the research of zirconium oxide nano crystal micro mist " " silicate circular " .1998,17 (5). this paper adopts tubular type SK-10/20 type statement mixing reactor to ZrOCl ₂8H ₂OYCl ₃With NHH ₂O carries out the liquid phase coprecipitation reaction with preparation ZrO ₂(Y2O3) nanocrystalline micro mist.Studied the relation that flow velocity, mixed characteristic and reaction density in the statement blender course of reaction distribute to diameter of particle and particle diameter, and carried out analyzing and inquired into.6, effect " Zhongnan Polytechnic Univ journal " .1999 of ethylene glycol in the complex compound sol-gel method, 30 (2)., adopt EDTA (ethylenediamine tetraacetic acid (EDTA)) sol-gel method to prepare ZrO ₂-8%Y2O3 (molar fraction) nanometer powder has been studied the influence mechanism of ethylene glycol to powder median size and coacervate intensity, and the result shows; In solution, add ethylene glycol, can replace hydrogen bond and participate in polyreaction between the EDTA complex molecules, improved gel stability, thereby made the gel of homogeneous transparent, and reduced hard aggregation to a certain extent; Earlier after 400 ℃, 2h and 700 ℃, the 2h calcining, specific surface area respectively is 35m ²/ g, the about 28nm of median size; 7, " a kind of novel method for preparing the ZrO2 nanometer powder " " China YouSe Acta Metallurgica Sinica " .1998,8 (4). adopt EDTA complex compound type sol-gel method to prepare the ZrO that median size is 10mm first ₂-8% (molar fraction), the Y2O3 nanometer powder.Use DTA/TG, XRD, BET, methods such as TEM characterize powder.Studied the pH value, the factors such as reactant concentration and EDTA addition are to the impact of Specific Surface Area Measurement.8, " cladded type all disperses the preparation of nanoparticle Y2O3/ZrO2 " " Qingtao Chemical Engineering College's journal " .1998,19 (1) articles are precursor with the zirconium sulfate, urea is as precipitation agent, made by sol-gel method and all to have disperseed the nanoparticle zirconyl carbonate, gained nanoparticle Zr-HBC is suspended in the dilute phosphoric acid yttrium solution, with urea is that precipitation has made basic carbonate yttrium coating Zr-HBC composite particles, examen all multifactor to forming the influence of above two kinds of particles, composite particles Y-HBC/Zr-HBC after calcining Y2O3/ZrO ₃Particle.9, " tetragonal zirconia polycrystal pottery and preparation method that magnesium oxide and yttrium oxide are steady altogether " Chinese patent＜application number〉02111146, relate to a kind of high-strength and high ductility magnesium oxide, tetragonal zirconia polycrystal (Mg that yttrium oxide is steady altogether, Y)-and the technology of TZP pottery and preparation thereof, it is characterized in that: (1) consists of MgO (5-14mol%)-Y2O3 (0.5-2mol%)-ZrO2; (2) be the nanometer (Mg for preparing said components earlier, Y)-the TZP powder, add the amorphous sintering aid of 0.5-10vol%YAS again, through granulating, to obtain grain-size be about 200-400nm to 1250-1400 ℃ of low-temperature sintering after the dry-pressing, bending strength is 384-818MPa, fracture toughness property be 5.2-8.3MPam ↑ [1/2] (Mg, Y)-the TZP pottery.The present invention has that technology is simple, sintering temperature is low, the Y2O3 consumption is few, production cost is low and characteristics such as mechanical property is superior, casted off once and for all tradition (Mg, Y)-high temperature solid solution and the thermal treatment process of PSZ.10, " a kind of method for preparing the controlled nano zircite of particle diameter ", Chinese patent＜application number〉01130825, relate to the method for preparing the nano level Zirconium oxide powder with the reverse micro emulsion that contains nonionogenic tenside.Prepare at first, respectively two parts of microemulsions that contain a kind of non-ionic surface active agent, n-hexyl alcohol, cyclohexane, zirconium salt solution or ammoniacal liquor.Then, under strong agitation, the microemulsion that will contain zirconates mixes with the microemulsion that contains ammoniacal liquor, the reaction that is hydrolyzed, product through centrifugal or filter after, again with the alcohol and water washing several times, make Zirconium oxide powder finally by super-dry and roasting.The characteristics of this method are that to make the median size size of the zirconia products of acquisition by conditions such as the ratio of concentration, water and the tensio-active agent of ammoniacal liquor in the concentration, microemulsion of zirconates in the control microemulsion and temperature of reaction be several to 30nm, and specific surface area is tens to 300m ²/ g.Can be used as specific function pottery, gas sensor, catalyst or catalyst carrier and adsorbent or adsorbing agent carrier etc. with the standby Zirconium oxide powder of this legal system.11, " preparation method of the weakly agglomerated nano zirconium oxide powder of surface doping ", Chinese patent＜application number〉99100053, the invention discloses a kind of preparation method of weakly agglomerated nano zirconium oxide powder of surface doping.Described preparation method comprises: (1). with the zirconium tetrachloride raw material, with it heating and gasifying, carried by the exsiccant inert carrier gas and to enter hydrolysis reactor, the gas mixture of water vapour and carrier gas thereof is at 300-700 ℃ of uniform mixing, wherein, the gaseous phase volume concentration of zirconium chloride is 0.1-30%, after hydrolysis reaction takes place, obtain containing the aerosol of nano zircite, this aerosol is through collecting, obtain even particle size distribution, the nano zirconium oxide powder of hard aggregation-free; (2). the nano zirconium oxide powder that makes more than inciting somebody to action, in metal salt solution, flood with used as stabilizers, filter, oven dry, carry out thermolysis in 300-800 ℃, obtain having the nano zirconium oxide powder of other metal oxide at the Zirconium oxide powder surface doping, this kind powder has four directions phase or cube phase structure, granularity is tiny, shape is regular, is difficult for reuniting, with the nano zirconium oxide powder that makes, dipping, roasting obtain the nano zirconium oxide powder that surface doping has other oxide compounds in as the metal salt solution of stablizer.

Can recognize that from above-mentioned these documents that retrieve these methods respectively have its characteristics, but the part that also comes with some shortcomings, as the coprecipitation method preparation yttrium oxide---often there is considerable coacervate in Zirconium powder; Alkoxide hydrolysis raw material sources difficulty, price is higher; Basic zirconium chloride hydrolysis method long reaction time, productive rate is low excessively; Precipitation---component skewness in the hydrothermal method product; Microemulsion method output is low excessively, can't realize industry law etc.

Technology contents

The inventor is through arduous research and test, found that a kind of technology is simple, constant product quality, cost be lower, and the method for the stabilized with yttrium oxide tetragonal phase zirconium oxide nano powder of can be mass-produced single dispersion, uniform component distribution.

Method of the present invention is achieved in that a kind of Y ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder, be after basic zirconium chloride is made into the solution that concentration is 0.2～3.0mol/L, directly insert high pressure corrosion resistant erosion reactor and carry out hydro-thermal reaction that high pressure corrosion resistant erosion reactor is withstand voltage greater than 8Mpa, described hydrothermal temperature is 150～260 ℃, the hydro-thermal reaction time is 4～24h, adds yttrium chloride solution by Y/Zr chemical reaction metered proportions after product is stirred, and slow dropping ammonia more after filtration subsequently, washing, drying after the calcining, is prepared Y ₂O ₃Stablize Tetragonal ZrO ₂The dispersed nano powder.

The material of above-described high pressure protection against corrosion reactor is pure zirconium or zirconium alloy, titanium alloy, pure nickel, nickelalloy etc.Described high pressure protection against corrosion reactor is withstand voltage greater than 8MPa.Described hydrothermal temperature is 150～260 ℃, and the hydro-thermal reaction time is 4～24h.PH value of solution=5～9 after described ammoniacal liquor drips.Described calcining is to carry out under 400～1000 ℃, and the time is 1～2h.The described Y for preparing ₂O ₃-ZrO ₂Composite granule is observed the average grain diameter≤100nm of powder under ESEM, disperse with pure water and ultrasonic wave, does not add under the condition of dispersant the maximum particle diameter of employing laser particle analyzer test≤2.0 μ m, resulting Y ₂O ₃-ZrO ₂It is single Tetragonal that composite granule adopts the analysis of X diffractometer, does not contain other dephasigns.

Compared with prior art, outstanding substantive distinguishing features of the present invention and obvious improvement are:

Y of the present invention ₂O ₃-ZrO ₂It is the characteristics of Tetragonal that composite granule has purity height, monodispersity, uniform component distribution, crystal formation, at electronic information material, optoelectronic areas important using value is arranged.In addition, hydrothermal synthesis method operation of the present invention is simple, easy handling, and the cost of producing is also lower, is suitable for suitability for industrialized production.

Further specify outstanding feature of the present invention below by example, only never limit the present invention in explanation the present invention, outstanding feature of the present invention and marked improvement never are limited to following example.

Embodiment

Embodiment 1, take by weighing 323 gram basic zirconium chloride (ZrOCl ₂8H ₂O) be dissolved in the 1000ml deionized water after, directly insert in the pure zirconium reactor of high pressure, reactor is warming up to 150 ℃ and constant temperature keeps 24h.After the question response still cooling, with the stir yttrium chloride solution 10ml of rear adding 0.2mol/l of product, subsequently slowly dropping ammonia to pH value of solution=9, after filtration, washing, drying, and behind 900 ℃ of lower calcining 1h, namely prepare and contain 3%Y ₂O ₃ZrO ₂Powder.Resulting Y ₂O ₃-ZrO ₂Composite granule is observed the average grain diameter≤80nm of powder, resulting Y under ESEM ₂O ₃-ZrO ₂Composite granule disperses with pure water and ultrasonic wave, does not add under the condition of dispersant the maximum particle diameter of employing laser particle analyzer test≤1.5 μ m, resulting Y ₂O ₃-ZrO ₂It is single Tetragonal that composite granule adopts the analysis of X diffractometer, does not contain other dephasigns, resulting Y ₂O ₃-ZrO ₂Composite granule adopts the X-fluorescence quantitative analysis to contain 3%Y ₂O ₃

Embodiment 2, take by weighing 323 gram basic zirconium chloride (ZrOCl ₂8H ₂O) be dissolved in the 1000ml deionized water after, directly insert in the pure zirconium reactor of high pressure, reactor is warming up to 260 ℃ and constant temperature keeps 8h.After the question response still cooling, with the stir yttrium chloride solution 10ml of rear adding 3mol/l of product, subsequently slowly dropping ammonia to pH value of solution=9, after filtration, washing, drying, and behind 900 ℃ of lower calcining 1h, namely prepare and contain 3%Y ₂O ₃ZrO ₂Powder.Resulting Y ₂O ₃-ZrO ₂Composite granule is observed the average grain diameter≤80nm of powder, resulting Y under ESEM ₂O ₃-ZrO ₂Composite granule disperses with pure water and ultrasonic wave, does not add under the condition of dispersant the maximum particle diameter of employing laser particle analyzer test≤1.5 μ m, resulting Y ₂O ₃-ZrO ₂It is single Tetragonal that composite granule adopts the analysis of X diffractometer, does not contain other dephasigns, resulting Y ₂O ₃-ZrO ₂Composite granule adopts the X-fluorescence quantitative analysis to contain 3%Y ₂O ₃

Embodiment 3, take by weighing 162 gram basic zirconium chloride (ZrOCl ₂8H ₂O) be dissolved in the 1000ml deionized water after, directly insert in the pure zirconium reactor of high pressure, reactor is warming up to 200 ℃ and constant temperature keeps 12h.After the question response still cooling, with the stir yttrium chloride solution 10ml of rear adding 2mol/l of product, subsequently slowly dropping ammonia to pH value of solution=7, after filtration, washing, drying, and behind 600 ℃ of lower calcining 2h, namely prepare and contain 8%Y ₂O ₃ZrO ₂Powder.Resulting Y ₂O ₃-ZrO ₂Composite granule is observed the average grain diameter≤100nm of powder, resulting Y under ESEM ₂O ₃-ZrO ₂Composite granule disperses with pure water and ultrasonic wave, does not add under the condition of dispersant the maximum particle diameter of employing laser particle analyzer test≤1.5 μ m, resulting Y ₂O ₃-ZrO ₂It is single Tetragonal that composite granule adopts the analysis of X diffractometer, does not contain other dephasigns, resulting Y ₂O ₃-ZrO ₂Composite granule adopts the X-fluorescence quantitative analysis to contain 8%Y ₂O ₃

Embodiment 4, take by weighing 162 gram basic zirconium chloride (ZrOCl ₂8H ₂O) be dissolved in the 1000ml deionized water after, directly insert in the pure zirconium reactor of high pressure, reactor is warming up to 220 ℃ and constant temperature keeps 20h.After the question response still cooling, with the stir yttrium chloride solution 10ml of rear adding 5mol/l of product, subsequently slowly dropping ammonia to pH value of solution=7, after filtration, washing, drying, and behind 600 ℃ of lower calcining 2h, namely prepare and contain 8%Y ₂O ₃ZrO ₂Powder.Resulting Y ₂O ₃-ZrO ₂Composite granule is observed the average grain diameter≤100nm of powder, resulting Y under ESEM ₂O ₃-ZrO ₂Composite granule disperses with pure water and ultrasonic wave, does not add under the condition of dispersant the maximum particle diameter of employing laser particle analyzer test≤1.5 μ m, resulting Y ₂O ₃-ZrO ₂It is single Tetragonal that composite granule adopts the analysis of X diffractometer, does not contain other dephasigns, resulting Y ₂O ₃-ZrO ₂Composite granule adopts the X-fluorescence quantitative analysis to contain 8%Y ₂O ₃

Claims

1, a kind of Y ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder, after it is characterized in that basic zirconium chloride is made into the solution that concentration is 0.2～3.0mol/L, directly insert high pressure corrosion resistant erosion reactor and carry out hydro-thermal reaction, high pressure corrosion resistant erosion reactor is withstand voltage greater than 8Mpa, described hydrothermal temperature is 150～260 ℃, the hydro-thermal reaction time is 4～24h, it is rear by Y/Zr chemical reaction metered proportions adding yttrium chloride solution that product is stirred, slow dropping ammonia more after filtration subsequently, washing, drying after the calcining, is prepared Y ₂O ₃Stablize Tetragonal ZrO ₂The dispersed nano powder.

2, Y according to claim 1 ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder, the material that it is characterized in that described high pressure corrosion resistant erosion reactor are pure zirconium or zircaloy, titanium alloy, pure nickel, nickel alloy.

3, Y according to claim 1 ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder is characterized in that described high pressure corrosion resistant erosion reactor is withstand voltage greater than 8MPa.

4, Y according to claim 1 ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder is characterized in that the pH value of solution=5～9 after described ammoniacal liquor drips.

5, Y according to claim 1 ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder is characterized in that described calcining heat is 400～1000 ℃, and the time is 1～2h.

6, a kind of Y as claimed in claim 1 ₂O ₃Stablize Tetragonal ZrO ₂The hydrothermal preparing process of dispersed nano powder is characterized in that the described Y for preparing ₂O ₃-ZrO ₂Composite granule is observed the average grain diameter≤100nm of powder under ESEM, disperse with pure water and ultrasonic wave, does not add under the condition of dispersant the maximum particle diameter of employing laser particle analyzer test≤2.0 μ m, resulting Y ₂O ₃-ZrO ₂It is single Tetragonal that composite granule adopts the analysis of X diffractometer, does not contain other dephasigns.