CN1259488A - Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder - Google Patents
Prepn. method of surface doped and weakly agglomerated nanometer zirconium oxide powder Download PDFInfo
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- CN1259488A CN1259488A CN 99100053 CN99100053A CN1259488A CN 1259488 A CN1259488 A CN 1259488A CN 99100053 CN99100053 CN 99100053 CN 99100053 A CN99100053 A CN 99100053A CN 1259488 A CN1259488 A CN 1259488A
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Abstract
The present invention relates to the prepn. method of surface-adulterated, weak-agglomerated nanometer zirconium oxide powder. Zirconium tetrachloride vapour is carried by carrier gas into reactor, mixed with high temp. steam to produce gaseous phase hydrolysis, then fine particle size, regular shape, uneasy to agglomerate nanometer zirconium oxide powder is obtd.. The obtd. nanometer zirconium oxide powder is impregnated in stabilizer metallic salt solution, roasted to obtain nanometer zirconium oxide powder whose surface is adulterated with other oxides.
Description
The present invention relates to the preparation method of the weakly agglomerated nano zirconium oxide powder of surface doping.Be that gas phase hydrolysis method prepares nano zirconium oxide powder, it with other metal salt solution dippings, subsequently again with it thermolysis, is made the weakly agglomerated nano zirconium oxide powder of surface doping.
That zirconium white has is heat-resisting, wear-resisting, and good advantages such as chemical stability, thereby at aspects such as structural ceramics, oxygen sensor and catalytic materials important application is arranged.For example, research work in recent years shows that the compact grained zirconia ceramics has fracture toughness property and superplasticity, is one of the research focus in present material field.Granularity is tiny and even, purity is high, the weak powder of reuniting is the prerequisite that obtains the high-performance zirconia goods.
Zirconium white has three kinds of phases, promptly monocline phase, four directions mutually with cube mutually, they have different crystalline phase density and Thermodynamically stable warm area separately.Generally, ZrO
2In room temperature to 1170 ℃ is the monocline phase, and 1170-2370 ℃ is cubic phase, and 2370-2680 ℃ is a cube phase.The density of monocline phase than the four directions mutually with cube all little mutually.Pure ZrO
2Behind powder high temperature (usually＞1200 ℃) sintering in being cooled to the process of room temperature, because the mutually transformation of high temperature phase (four directions phase or cube phase) to low temperature phase (monocline phase) can take place, volumetric expansion 3-5% or makes goods cracking, fragmentation more, can not get the high strength goods.Therefore in the zirconia ceramics powder, add stablizer, as MgO, CaO, Y
2O
3Deng, form composite oxide power, will be Zirconia-stabilized in the four directions mutually or cube phase so that sintered body unlikely cracking fragmentation in process of cooling.In addition, in zirconia catalyst, for the thermostability that improves Zirconia carrier and at high temperature keep its specific surface area, also achieve the goal by adding the hotchpotch stablizer.
The production method of nano level Zirconium oxide powder is mainly used liquid phase method at present.For example business-like coprecipitation method is to add the alkali lye co-precipitation in the solution that contains zirconates and other metal-salts, obtains precipitation of hydroxide, then after filtration, washing, dry, roasting obtain solid solution build doped zirconia powder.This method is relatively simple, can make that granularity is little, the more manageable multicomponent nanocomposite powder of composition, and JP96000698 has the report of this respect.The shortcoming of this method is many, the long flow path of preparation process step, and the powder agglomeration degree that makes is big, makes that follow-up sintering process needs to carry out under higher temperature, and not only energy consumption height but also grain growth are remarkable, there are crackle or cavity in the goods, influenced ceramic mechanical property.In order to control the reunion of powder, liquid phase method usually adopts organic solvent washing, spraying drying, lyophilize, supercritical drying, component distillation, adding to show means such as promoting agent or superpolymer in preparation powder process.These methods have not only increased the complicacy and the cost of process, and effect still difficulty be entirely satisfactory.
Vapor phase process is produced oxide powder at present, successfully makes high-quality SiO
2, TiO
2, Al
2O
3, nanometer powder such as carbon black, products obtained therefrom purity height, good dispersity, operation are continuous.But it is very few that vapor phase process is produced Zirconium oxide powder and is doped with the zirconic report of other metal oxide.Its major cause is that the present vapor phase process composite oxides that prepare multicomponent mixture are convenient not as liquid phase method generally, and the controllability of component is also relatively poor relatively, has limited by vapor phase process and has directly made multi-component Zirconium oxide powder.At present vapor phase process prepares having of Zirconium oxide powder: the oxidation of zirconium halide, as Suyama etc. at Ceramurgia Intern., 3 (4): 141,1977 articles of delivering, and the method announced of German patent DE 4214724.This method preparation temperature is very high, and has the tangible problem of grain growth.The for example vapour-phase pyrolysis of organic zirconium or hydrolysis discloses clear 61-201604 as Japanese Patent again, and the product that obtains is the vesicular structure of unformed shape, and contains carbon residue.The patent that for example has again relates to the atomizing pyrolysis of zirconates in aerosol reactor, and for example the open CN1040932 of Chinese patent prepares adulterated ZrO
2Powder.The patent that also has as the flat 5-53722 of Japanese patent laid-open publication gazette, sprays into the metal zirconium powder that evaporation, oxidation prepare ZrO in the high temperature oxygen air-flow (＞2000 ℃)
2Powder.
Be the crystalline phase of controlled oxidation zirconium, some patents coat stablizer oxyhydroxide or oxide compound generating the surface cladding type composite oxides at zirconium white or zirconium hydroxide powder surface, its patent quantity far beyond preparation solid solution build powder for few.Its method mainly is to utilize precipitin reaction to have certain thickness stablizer precipitation of hydroxide at zirconium white or zirconium hydroxide surface coating one deck in solution, and as US 5336521, EP 251538.This method can make stablizer wayward in the homogeneity of zirconium white or the distribution of zirconium hydroxide particle surface, and makes powder agglomeration state variation.
The present invention is directed to above-mentioned defective, is raw material with the zirconium tetrachloride at first, with its evaporation, brings reactor into and mixes with water vapour with carrier gas, at 300-700 ℃ hydrolysis reaction takes place, and generates nano zirconium oxide powder rapidly.Because hydrolysis reaction is to carry out in gas phase, and temperature enough makes Zr (OH)
4Dehydration, thereby the ZrO that obtains
2Powder size is little, is evenly distributed and seldom reunion.This nano zirconium oxide powder with behind the metal salt solution dipping, is made the nano zirconium oxide powder that surface doping has other oxide compound through roasting, and through the X-ray diffraction experiment confirm.Be generally called the nano zirconium oxide powder of surface doping in the present invention or claim the nano zircite composite powder.
The hydrolysis reaction of zirconium tetrachloride has very big reaction equilibrium constant and speed of response, and therefore the preparation to nano zirconium oxide powder all is favourable on thermodynamics of reactions and kinetics.Experimental result shows, can easily make little ZrO to several nanometers with gas phase hydrolysis method
2Particle, the tap density of powder is very little, and its volume density can be hanged down and be reached about 1% of tetragonal phase zirconium oxide theoretical density, thereby it is few to reunite.For the crystalline phase of stable and controlled oxidation zirconium, the present invention selects the proper metal salts solution for use, and the nano zirconium oxide powder of dipping gained makes the nano zircite composite powder through thermolysis again.
The nano zircite that the said hydrolyzed reaction generates is scattered in and forms aerosol in the gas.For reducing the product loss and preventing the pollution of the environment, must collect with appropriate means.For example, collect with fiber or ceramic filter layer, also available high voltage electrostatic dust precipitator is collected.In addition, can also utilize the principle of wet dedusting and method to finish the collection of powder and the processing of tail gas simultaneously.This several method principle difference is installed differently, respectively possesses some good points.Usually, can add whirlwind separator or cyclone agglomerator, to improve collection effciency and the burden that alleviates subsequent processes in the front of these devices.After the powder collection, but tail gas is through suitably handling emptying.
The preparation method of the nano zirconium oxide powder of surface doping of the present invention comprises:
(1) is raw material with the zirconium tetrachloride,, carries by dry inert carrier gas and to enter hydrolysis reactor that with the water vapour uniform mixing under 300-700 ℃ temperature through preheating, wherein, the gaseous phase volume concentration of zirconium chloride is 0.1-30% with its gasification.After hydrolysis reaction takes place, obtain containing the aerosol of nano zircite.It is the 3-30 nanometer that this aerosol obtains mean particle size through collection, and outward appearance is bulk, pure white, the nano zirconium oxide powder of hard aggregation-free body.The thing of this powder changes according to the variation of reaction conditions, can make the four directions and be the Zirconium oxide powder of principal crystalline phase mutually.Above-mentioned inert carrier gas is selected from Ar, N
2, He, O
2, air, CO
2, and their mixed gas; Described water vapor can be obtained by the water evaporation, also can use combustible gas, comprising: hydrogen, natural gas, liquefied gas, coal gas or hydro carbons, the steam-laden high-temperature gas that burning obtains.
(2) nano zirconium oxide powder that will make above floods, filters, dries with metal salt solution and in 300-800 ℃ of thermolysis, obtains the Zirconium oxide powder that surface doping has the stabilizer metals oxide compound.This powder has that granularity is little, weak characteristics are evenly distributed, reunite.Described metal-salt is selected from: the acetate of Ca, Mg, Sc, Y, Ti, Fe, Zn, Al, La, Ce, nitrate or muriate, or the mixture of above-mentioned metal-salt.
The advantage of the inventive method is:
(1) is raw material with the zirconium tetrachloride, makes its gas in the rapid hydrolysis of proper temperature and taken out of reaction zone fast, prevented growing up and reuniting of zirconium white crystal grain.Powder size is evenly distributed, the regular and good dispersity of shape.
(2) the doping process is independent of the vapor phase production process, can makes the distribution of stablizer and doping all be easy to control.
(3) the preparation raw material is cheap zirconium tetrachloride and water; Zirconic preparation process is continuous, directly makes the oxide compound of zirconium, has avoided the roasting process of oxyhydroxide, and the formation of the hard agglomeration that brings thus, can obtain the high-performance zirconia goods.
(4) zirconium white that makes has big specific surface area, and in the doping process, stablizer is uniformly distributed in the Zirconia particles surface with the individual layer dispersion state, is evenly distributed, and enters zirconium white body phase after the roasting easily, thereby plays the effect of stablizing crystalline phase.
(5) stabilizer oxide that is scattered in zirconium surface can improve zirconic anti-caking power effectively, suppresses grain growth and specific surface area and descends.
The Zirconium oxide powder particle that makes in order to the top method can be as small as several nanometer to tens nanometers, reunite few and hard aggregation-free body, make sintering process can be at a lower temperature evenly, carry out apace, can obtain the density height, grain-size is little, the high quality zircite product of uniform microstructure.
Zircite product by the preparation of this patent disclosed method has good character, thereby important application is arranged in many aspects.For example, utilize its high strength and toughness, be used to make cutters such as ceramic scissors, be used for aspects such as industry and medical treatment.Utilize its wear resistance, can make bearing, nozzle, valve, abrasive material.Utilize its high temperature resistant and thermal insulation, expect it as diesel motor parts and high-temperature fuel gas turbine material, and high-temperature furnace body, heating element etc.Because the compact grained zirconia ceramics shows superplasticity, important application is arranged in the expectation of the aspects such as workability of ceramic.
In order to be illustrated more clearly in the present invention, enumerate following examples, but it there is not any restriction to the present invention.
The used reactor of embodiment is that two concentric pipes constitute, and outer tube diameter is 25mm, and inner tube diameter is 5.2mm.ZrCl
4Steam exports (nozzle) by interior pipe and imports reactor; Water vapour enters reactor by the inner and outer pipe gap.The later reactor section of nozzle is divided into conversion zone.Two strands of gases begin in interior pipe exit to mix and reaction, generate ZrO
2Aerosol.The outer wall of conversion zone is incubated with resistance furnace, and reactor pressure is a normal pressure.After the zirconium white aerosol flowed out reactor, the overwhelming majority was filtered film and collects.Tail gas is emptying after washing.
Embodiment 1
Zirconium tetrachloride is carried by drying nitrogen, and its dividing potential drop is 17kPa, enters conversion zone by interior pipe nozzle.Water vapour from water evaporimeter is carried by nitrogen, and its dividing potential drop is 97kPa, is entered reactor by the gap of inner and outer pipe after the resistance furnace preheating.Reaction zone temperature is set at 375 ℃, and gas space velocity is 2300/h.Wherein, the ratio of the volumetric flow of gas in the inner and outer pipes is 9: 16.Reaction product is the powder of white, undefined structure, and specific surface area (BET) is 84m
2/ g.Observe under Electronic Speculum, its mean particle size is 12nm, and particle is spherical.
Embodiment 2
Water vapour among the embodiment 1 changed by interior pipe nozzle enter reactor, and zirconium tetrachloride steam is imported by the inner and outer pipes gap, the gas flow ratio in the inner and outer pipes is 16: 9.Other condition is with embodiment 1.The product that obtains is the unformed powder of white loose.Observe under transmission electron microscope, the granularity of most of particle is about 12nm, and having on a small quantity, the particle of big (about 20nm) occurs.
Embodiment 3
Zirconium tetrachloride is that reactor is brought in carrier gas into the dry air, and its dividing potential drop is 5.4kPa.Obtain after the water vapor that another strand reaction gas is come with being evaporated by water evaporimeter by the natural gas burning product mixes, its temperature is 680 ℃.Wherein, steam partial pressure is 90kPa.In addition, it also contains the carbonic acid gas of 3.9kPa and the oxygen of 1.9kPa, and remaining is nitrogen.Two strands of reactant gasess enter 650 ℃ of reactors and react, and gas space velocity is 7560/h.Reaction product is white, bulk Zirconium oxide powder, and crystal grain diameter is 5.4nm, and crystalline phase is the cubic mixed phase that reaches the monocline phase mutually, and wherein cubic phase content is 85%.Even particle size distribution, grain type almost spherical.
Embodiment 4
High pure nitrogen and carbon dioxide gas with 2: 1 mixed after, enter the zirconium tetrachloride vaporizer, the steam that carries 4kPa enters reactor.The water vapour that another road air carries 27kPa enters reactor.Reactant gases flows into 520 ℃ of reactors after preheating, the air speed of gas is 4300/h.The Zirconium oxide powder specific surface area that obtains behind the hydrolysis reaction is 150m
2/ g, its grain size is 6.1nm, and crystalline phase is the cubic mixed phase that reaches the monocline phase mutually, and wherein the four directions is 78% mutually.The volume density of powder is about 0.06g/cm
3
Embodiment 5
The powder that embodiment 3 is obtained is scattered in Mg (NO
3)
2In the solution, the heating evaporation solvent.Behind the solvent evaporate to dryness, put into 110 ℃ of oven drying 20h.Obtain MgO-ZrO in 500-700 ℃ of processing then
2Composite powder.The dosage of MgO is 10mol%MgO-ZrO
2After the powder dry-pressing,, obtain the garden sheet sample of diameter 20mm * 2mm in the 250MPa cold isostatic compaction.Sample is placed non-pressure sintering furnace,, be cooled to room temperature then in 1500 ℃ of sintering two hours.Be determined as cubic zirconia through X-ray diffraction, its density is measured as 96% of theoretical density by the Archimedes method.
Embodiment 6
The powder that embodiment 4 is obtained is dispersed in Y (NO then in 570 ℃ of thermal treatment 1h
3)
3Solution in, Y (NO
3)
3Add-on with Y
2O
3Meter, its content is 3mol%ZrO
2Heating evaporation solvent while stirring then.After treating the solvent evaporate to dryness, put into 110 ℃ of oven drying 10h.Obtain 3mol%Y in 400-500 ℃ of thermal treatment then
2O
3-ZrO
2Composite powder.With the powder dry-pressing, isostatic cool pressing 240MPa moulding obtains 5.8 * 7.1 * 11mm then
3Formed body.Then place non-pressure sintering furnace, be warming up to 1300 ℃ of insulations two hours, be cooled to room temperature then.Ceramic density after the polishing is measured as 99% of cubic phase theoretical density.
Claims (7)
1. the preparation method of a nano zirconium oxide powder is characterized in that, described preparation method comprises:
(1). with the zirconium tetrachloride is 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 at the Zirconium oxide powder surface doping nano zirconium oxide powder of other metal oxide, this kind powder has four directions phase or cube phase structure;
2. in accordance with the method for claim 1, it is characterized in that the inert support in the described method is selected from: Ar, N
2, He, O
2, CO
2Or air or their mixture;
3. in accordance with the method for claim 1, it is characterized in that the hydrolysis temperature in the described method is 350-650 ℃;
4. in accordance with the method for claim 1, it is characterized in that the volumetric concentration of the zirconium chloride in the described method in the mixture of reactant gases is 0.2-20%;
5. in accordance with the method for claim 1, it is characterized in that the water vapour in the described method is produced by the water direct gasification or selects fuel gas for use, comprising: the steam-laden high-temperature gas that hydrogen, natural gas, liquefied gas, coal gas or hydrocarbon fuel obtain;
6. in accordance with the method for claim 1, it is characterized in that, the Zirconium oxide powder that hydrolysis obtains in the described method, its median size is 3-30nm, the powder bulk density, promptly volume density is 0.05-0.08g/cm
3
7. in accordance with the method for claim 1, it is characterized in that used metal-salt in the described method is selected from: the acetic acid of Ca, Mg, Sc, Y, Ti, Fe, Zn, Al, La, Ce, nitric acid or muriate or their mixture.
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|---|---|---|---|
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| CN1108195C (en) * | 2000-09-01 | 2003-05-14 | 清华大学 | Nm-class crystal oxide carried nickel catalyst and its preparing process |
| CN1321066C (en) * | 2005-08-12 | 2007-06-13 | 安泰科技股份有限公司 | Zirconium dioxide nano powder material preparation method |
| CN1326778C (en) * | 2005-11-09 | 2007-07-18 | 山西大学 | Process for preparing single tetragonal crystal structure ZrO2 |
| CN103120933A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of nanometer TiO2/ZrO2 composite material |
| CN103739014A (en) * | 2013-12-04 | 2014-04-23 | 首都师范大学 | Vapor phase method for controllable synthesis of biocompatible zirconium dioxide nano powder |
| CN106698509A (en) * | 2015-11-17 | 2017-05-24 | 林莉 | Composite nano zirconium oxide with uniform particle size distribution, and continuous preparation method and equipment thereof |
| US9750828B2 (en) | 2012-03-29 | 2017-09-05 | Basf Corporation | Amorphous carbon supported nanoparticles comprising oxides of lanthanides and method for preparing them |
| CN108190950A (en) * | 2018-02-06 | 2018-06-22 | 新疆晶硕新材料有限公司 | The preparation method and device of zirconium dioxide |
| CN113371756A (en) * | 2021-07-13 | 2021-09-10 | 河南工业大学 | La-Sc-ZrO2 nano-crystal material and preparation method thereof |
| CN115041699A (en) * | 2022-07-22 | 2022-09-13 | 华材(山东)新材料有限公司 | Production method of spherical zirconium powder for 3D printing |
| CN115432735A (en) * | 2022-07-27 | 2022-12-06 | 南通江山新能科技有限公司 | Preparation process and application of gas-phase-method nano-zirconia |
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| CN101164896B (en) * | 2006-10-20 | 2010-12-01 | 中国科学院大连化学物理研究所 | Method for stabilizing anatase phase nano titanium oxide and cubic phase nano zirconium oxide |
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|---|---|---|---|---|
| CN1108195C (en) * | 2000-09-01 | 2003-05-14 | 清华大学 | Nm-class crystal oxide carried nickel catalyst and its preparing process |
| CN1321066C (en) * | 2005-08-12 | 2007-06-13 | 安泰科技股份有限公司 | Zirconium dioxide nano powder material preparation method |
| CN1326778C (en) * | 2005-11-09 | 2007-07-18 | 山西大学 | Process for preparing single tetragonal crystal structure ZrO2 |
| CN103120933A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of nanometer TiO2/ZrO2 composite material |
| US9750828B2 (en) | 2012-03-29 | 2017-09-05 | Basf Corporation | Amorphous carbon supported nanoparticles comprising oxides of lanthanides and method for preparing them |
| US10046069B2 (en) | 2012-03-29 | 2018-08-14 | Basf Corporation | Amorphous carbon supported nanoparticles comprising oxides of lanthanides and method for preparing them |
| CN103739014A (en) * | 2013-12-04 | 2014-04-23 | 首都师范大学 | Vapor phase method for controllable synthesis of biocompatible zirconium dioxide nano powder |
| CN106698509A (en) * | 2015-11-17 | 2017-05-24 | 林莉 | Composite nano zirconium oxide with uniform particle size distribution, and continuous preparation method and equipment thereof |
| CN106698509B (en) * | 2015-11-17 | 2019-06-11 | 林莉 | Composite Nano zirconium oxide, continuous preparation method and its equipment of even particle size distribution |
| CN108190950A (en) * | 2018-02-06 | 2018-06-22 | 新疆晶硕新材料有限公司 | The preparation method and device of zirconium dioxide |
| CN113371756A (en) * | 2021-07-13 | 2021-09-10 | 河南工业大学 | La-Sc-ZrO2 nano-crystal material and preparation method thereof |
| CN115041699A (en) * | 2022-07-22 | 2022-09-13 | 华材(山东)新材料有限公司 | Production method of spherical zirconium powder for 3D printing |
| CN115432735A (en) * | 2022-07-27 | 2022-12-06 | 南通江山新能科技有限公司 | Preparation process and application of gas-phase-method nano-zirconia |
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