CN106977201A - High-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof - Google Patents

High-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof Download PDF

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CN106977201A
CN106977201A CN201710201806.0A CN201710201806A CN106977201A CN 106977201 A CN106977201 A CN 106977201A CN 201710201806 A CN201710201806 A CN 201710201806A CN 106977201 A CN106977201 A CN 106977201A
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oxide
purity
thin plate
ductility
ultra thin
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不公告发明人
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Nanjing Jinli New Material Co.,Ltd.
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Nanjing Cloud Qijin Rui New Material Co Ltd
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Abstract

The invention provides a kind of ductile strength is adjustable, there is provided high-purity zirconia and hafnium oxide for cheap zirconia composite ceramics ultra thin plate, yittrium oxide, cerium oxide, calcium oxide, magnesia, aluminum oxide, titanium oxide, silica, cobalt oxide, iron oxide, scandium oxide, vanadium oxide, manganese oxide, nickel oxide, cupric oxide, zinc oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, barium monoxide, tantalum oxide, tungsten oxide, lanthana, praseodymium oxide, neodymia, tellurium oxide, terbium oxide, europium oxide, compound high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate of at least one of erbium oxide and preparation method thereof, using the high-purity combined oxidation zirconium powder of nanoscale and noresidue binding agent, noresidue surfactant, noresidue lubricant, noresidue plasticizer carries out refining glue, refining glue is cast after finishing, three stages homogenization is carried out to curtain coating body and strikes off technique, ensure that processing is dried under specific temperature and damp condition obtains thin plate blank, dumping sintering processes are finally carried out, that is, obtain high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate.

Description

High-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof
Technical field
The invention belongs to material preparation process technical field, and in particular to a kind of high-purity high-strength high-ductility zirconia composite ceramics Ultra thin plate and preparation method thereof.
Background technology
Zirconia ceramics is used widely with its excellent high-temperature physics and mechanical property, especially be used for harsh bar The critical component used under part.Due to ZrO2Heat conductivility is low, thermal coefficient of expansion big, therefore ZrO2The heat endurance of product compared with Difference.But use partially stabilized ZrO2The ZrO that product crystal formation made from raw material is constituted2The heat endurance of ceramic made from raw material It is best.Therefore ZrO is manufactured2Structural ceramics often uses partially stabilized ZrO2Raw material rather than entirely stable ZrO2Raw material.Produce ZrO2 Structural ceramics typically uses 3mo1%Y2O3Stable ZrO2Superfine powder. ZrO2The forming method of structural ceramics has：Hot die-casting molding, Dry-pressing formed and isostatic pressing, injection forming, flow casting molding etc..
Flow casting molding is that ceramic powder and substantial amounts of organic binder bond, plasticizer, dispersant etc. are sufficiently mixed, and obtaining can With the viscous paste of flowing, slurry is added the hopper of casting machine, controls thickness with scraper, flowed out through charging nozzle to conveyer belt, Film base is obtained after drying.This technique is adapted to prepare thin-film material, and substantial amounts of organic matter is added in order to obtain preferable pliability, It is required that strict control technological parameter, peeling, striped, film strength are otherwise easily caused low or the defect such as be not easily stripped.
Chinese patent 03114097.1 provides the method by preparing zirconium oxide ceramic by curtain coating, and (1) gives birth to wet chemistry method The zirconium oxide micro mist of the partially stabilized tetragonal phase of production is calcined 1-3 hours at 600-800 DEG C to be pre-processed, and (2) are located in advance Zirconium oxide micro mist after reason adds ball mill, then calculates to add by weight percentage based on zirconia powder body weight and divides A slurry is made for 10 hours in powder 1-3%, solvent 50-60%, levelling agent 0.5-3%, ball milling.Again in an above-mentioned slurry In be separately added into secondary ball milling after plasticizer 2-8%, bonding agent 3-10% curtain coating slurry be made within 10 hours, above-mentioned dispersant is Castor oil or phosphate, bonding agent are polyvinyl butyral resin, and plasticizer is dibutyl phthalate and phthalic acid The mixture of dioctyl ester, weight is than 1: 1, and solvent is absolute ethyl alcohol, and levelling agent is the casting slurry warp after cyclohexanone, (3) ball milling Cross vacuum stirring de-bubble 10-30 minutes, control slurry viscosity 10000-30000mPa.s, then carried out on large-scale casting machine Curtain coating, while being dried 2-3 hours at 60 DEG C -100 DEG C, is prepared into the green compact after zirconia ceramics green compact, curtain coating and is placed on and hold 600 DEG C are raised to from room temperature with 0.5-1.5 DEG C/min heating rate on burning plate, 4 hours dumpings are incubated, then less than 1540 Sintered 2-4 hours at DEG C.
Chinese patent 201210445355.2 provides a kind of low temperature co-fired method of chip zirconia sensor, the side Method includes：Low melting point, the glass dust with ionic conductivity are added in yttria-stabilized zirconia, slurry is prepared；By slurry Flow casting molding, cutting, breaks through hole, reference gas passage, gas compartment etc.；The noble metal electrodes such as printing Pt, lamination hot pressing, and Burnt altogether at 1000 DEG C~1200 DEG C 0.5~4 hour.
Chinese patent 201210229317.3 provides a kind of coating preparation method of flaky zirconia ceramics, including following Step：There is provided mass percent be 60-65% zirconia ceramics powder, mass percent be 20-25% organic solvent, quality hundred Divide the increasing that binding agent, mass percent that dispersant, mass percent that ratio is 1.2-1.8% are 4.0-6.0% are 2.5-7.0% Mould agent；The organic solvent uses binary azeotropic mixed organic solvents system, such as butanone and ethanol；The dispersant uses two Kind, such as fish oil and oleic acid；The binding agent is using the molecular chain length two kind different polyvinyl butyral resins short with strand （PVB）；The plasticizer uses polyethylene glycol（PEG）And dibutyl phthalate（DBP）.
Chinese patent 200510063557.0 provides a kind of preparation method of sub-micron zirconium oxide electrolyte film material, Belong to the technical field of electrolyte film material, sub-micron zirconium oxide electrolyte film material can not be prepared in order to solve prior art The problem of material, the preparation method for propose that a kind of technique is simple, sintering in a low temperature of 1200-1300 DEG C, the film material prepared Material has good electrical conductance, and at 1000 DEG C, its electrical conductivity is 0.130-0.150S/cm, and crystallite dimension is 0.1-1 μm, is sub- Micron dimension, so as to improve intensity and thermal shock resistance, meets the synthesis that zirconia solid electrolyte thin-film material prepares device The need for performance.
Chinese patent 201410017105.8 provides a kind of oxygen sensor used in vehicle based on oxide casting slurry, its In, sensitive layer matrix, air duct layer, air duct supporter and zone of heating matrix are made up of casting slurry, casting slurry bag Include the material of following parts by weight：5-7 parts of Zirconium powder, 3-5 parts of organic solvent, 0.5-1.5 parts of auxiliary agent.The oxygen sensor used in vehicle Each layer matrix be made of zirconia material, in sintering process, the sinter bonded degree that each base layer has had, especially sky Gas channel layer, without filling carbon dust, the organic matter such as starch in air duct, it is to avoid because residue is present in air duct and shadow Ring the sensitivity of sensor.
Chinese patent 200910109439.7 provides a kind of chip oxygen sensor, and the chip oxygen sensing includes a heating Device matrix, the heater substrate for a stabilized with yttrium oxide zirconium oxide curtain coating substrate on be sequentially provided with insulating barrier, heating electrode, absolutely Edge layer, the insulating barrier is by Al2O3Slurry coats to be formed, the Al2O3The solid content of slurry is 55wt%~80wt%, slurry Viscosity is 8000~100000mpas, and the bending strength of the chip oxygen sensor is 890~900MPa.
Chinese patent 200710051946.0 provides a kind of flat oxygen for being used to control air-fuel ratio in automobile engine The manufacture method of sensor chip, its processing step is that doped yttrium zirconia ceramics powder is made into casting slurry, passes through curtain coating Bright and clean smooth thin slice is made in technique, then is cut into corresponding vane, heating plate and intermediate by noncontact cutting machine, is passing Printed electrode inside and outside sense piece, adding thermal resistance is stamped on heating plate, then three are pressed into lamination hot pressing mode flat Lambda sensor is overall, is finally formed through removing organic matter in 1300 DEG C~1500 DEG C sintering.
Chinese patent 200510121311.4 provides a kind of preparation side of solid oxide fuel battery electrolyte diaphram Method, is realized according to the following steps：(1) using the zirconium oxide added with stabilizer as electrolyte, ball milling is put into after adding shaping assistant Disperse in machine, add PVB solution continuation mix grinding and obtain slurry；(2) slurry is subjected to vacuum defoamation and old processing；(3) Carry out curtain coating and be made filming band, then through die for cutting into filming piece；(4) filming piece is pressed into required thickness lamination, Ran Houfang Blank is pressed into hydraulic press in meditation, and makees surface coarsening processing, then punching molding simultaneously；(5) the blank loading of kiln of shaping is burnt Knot.
Chinese patent 201310049370.X provides a kind of borosilicate glass and ball-aluminium oxide LTCC Green band and preparation method thereof, the green band is made up of glassceramic composites and casting medium, and wherein glass-ceramic is answered Condensation material is made up of borosilicate glass, ball-aluminium oxide；Casting medium is by mixed solvent, monomeric binder, plastic agent With dispersant composition.It is LTCC green tape surfacing prepared by the present invention, smooth, green tape solid content up to 88 ~ 92wt%, percent of firing shrinkage is 9 ~ 11%, and all directions sintering shrinkage difference is small, can be in the low melting point such as 850 DEG C of realizations and Au, Ag Metal line burns altogether.The raw material band sintering porcelain body that the present invention is provided has excellent dielectric properties：Under 10GHz, dielectric constant（ε r）For 7 ~ 8, dielectric loss（tanδ）Less than 2 × 10-3, and it is each to different with sintering shrinkage to efficiently solve traditional LTCC greens Sex chromosome mosaicism.
Chinese patent 201110363370.8 provides a kind of preparation method of nano porous high-efficiency heat insulation board, belongs to nanometer Porous heat insulation material field.Technique is：The method that nano-powder is combined using mechanical dispersion and chemical dispersion and fiber, combination Agent, opacifier, plasticizer, drying control agent, the reagent of dispersant and appropriate regulation dry and wet degree are uniformly mixed；Using dry The method such as molded, flow casting molding or extrusion forming is molded it；Drying condition is controlled, molded samples are dried, then It is covered with the reflecting layer of certain thickness and material, you can obtain nano porous high-efficiency heat insulation board.
Prior art is studied only for low-purity zirconium oxide flow casting molding technology, not low for high-purity fine grain Temperature sintering ultra-toughness technology is studied, so that the application surface of product is narrower, without the property of toughness for really playing zirconia material.
The content of the invention
Make to solve prior art in high-end precision equipment high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate The situation of requirement can not be met in, the invention provides a kind of brand-new high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate And preparation method thereof.It is an object of the invention to overcome the shortcoming of prior art, and provide that a kind of ductile strength is adjustable, price is low Honest and clean zirconia composite ceramics ultra thin plate there is provided high-purity zirconia and hafnium oxide, yittrium oxide, cerium oxide, calcium oxide, magnesia, Aluminum oxide, titanium oxide, silica, cobalt oxide, iron oxide, scandium oxide, vanadium oxide, manganese oxide, nickel oxide, cupric oxide, zinc oxide, Niobium oxide, molybdenum oxide, indium oxide, tin oxide, barium monoxide, tantalum oxide, tungsten oxide, lanthana, praseodymium oxide, neodymia, tellurium oxide, The compound high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate of at least one of terbium oxide, europium oxide, erbium oxide and its system Preparation Method, using the high-purity combined oxidation zirconium powder of nanoscale and noresidue binding agent, noresidue surfactant, noresidue lubrication Agent, noresidue plasticizer carries out refining glue, and refining glue is cast after finishing, and carrying out three stages homogenization to curtain coating body strikes off technique, Ensure that processing is dried under specific temperature and damp condition obtains thin plate blank, finally carries out dumping sintering processes, that is, obtains Obtain high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate.The present invention has the advantages that high-purity high-strength High-tenacity high-strength degree, the present invention Not only technique and equipment are simple, and cost is low, and high income, energy consumption is low, and production efficiency is high, are adapted to industrialized production, and can obtain Steady quality, the tiny controllable zirconia composite ceramics ultra thin plate of crystal grain are obtained, process of the present invention, without Environment pollution, is a kind of new Low cost, the preparation method of the high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate of steady quality.
Zirconia composite ceramics ultra thin plate relative density of the present invention be 90% ~ 99%, host element purity be 99.5% ~ 99.999%, bending strength is 400 ~ 2000MPa, and crystallite dimension is 0.1 ~ 20 micron, and Vickers hardness is HV2000 ~ 20000.
Preferably, the relative density of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 92% ~ 96%.
Preferably, the host element purity of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate be 99.9% ~ 99.999%。
Preferably, the bending strength of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 600 ~ 1800MPa.
Preferably, the crystallite dimension of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 0.2 ~ 2 micron.
Preferably, the Vickers hardness of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate be HV2500 ~ 16000。
The host element of high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate of the present invention be zirconium oxide, hafnium oxide, Yittrium oxide, cerium oxide, calcium oxide, magnesia, aluminum oxide, titanium oxide, silica, cobalt oxide, iron oxide, scandium oxide, vanadium oxide, Manganese oxide, nickel oxide, cupric oxide, zinc oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, barium monoxide, tantalum oxide, tungsten oxide, Lanthana, praseodymium oxide, neodymia, tellurium oxide, terbium oxide, europium oxide, erbium oxide, described host element purity are main element wt With the percentage by weight of gross weight.
In order to reach above-mentioned use requirement, the technical scheme that the present invention is used is high-purity high-strength high-ductility zirconia composite ceramics The preparation method of ultra thin plate, methods described is comprised the following steps that.
（1）Nano level zirconia powder doped zirconia, hafnium oxide, yittrium oxide, cerium oxide, oxygen are chosen by specific proportioning Change calcium, magnesia, aluminum oxide, titanium oxide, silica, cobalt oxide, iron oxide, scandium oxide, vanadium oxide, manganese oxide, nickel oxide, oxygen Change copper, zinc oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, barium monoxide, tantalum oxide, tungsten oxide, lanthana, praseodymium oxide, oxygen Change the nano composite oxides zirconium powder of at least one of neodymium, tellurium oxide, terbium oxide, europium oxide, erbium oxide, nothing is put into nano powder Dispersant, noresidue binding agent are remained, noresidue surfactant, noresidue lubricant, noresidue plasticizer carries out vacuum refining Glue.
（2）By step（1）Middle acquisition refining glue material carries out curtain coating processing, and curtain coating thin plate is carried out striking off processing three times, and Carry out constant temperature and humidity drying.
（3）By step（2）Middle acquisition flow casting molding blank carries out dumping and sintering processes, produces the oxidation of high-purity high-strength high-ductility Zirconium composite ceramics ultra thin plate.
（4）Measuring process（3）The density of middle high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate, purity, crystallite dimension, Bending strength and hardness.
The present invention is high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof, in order to allow the present invention to have Effect to above-mentioned steps, it is necessary to refine, and specific thinning parameter is as follows.
Step（1）In, the percentage by weight of zirconium oxide is 10% ~ 99% in described nano composite oxides zirconium powder, and surplus is Hafnium oxide, yittrium oxide, cerium oxide, calcium oxide, magnesia, aluminum oxide, titanium oxide, silica, cobalt oxide, iron oxide, scandium oxide, Vanadium oxide, manganese oxide, nickel oxide, cupric oxide, zinc oxide, niobium oxide, molybdenum oxide, indium oxide, tin oxide, barium monoxide, tantalum oxide, At least one of tungsten oxide, lanthana, praseodymium oxide, neodymia, tellurium oxide, terbium oxide, europium oxide, erbium oxide.
Step（1）In, the primary particle size of described nano composite oxides zirconium powder is 1 ~ 100 nanometer.
Step（1）In, the purity of described nano composite oxides zirconium powder is 99.5% ~ 99.999%.
Step（1）In, the percentage by weight of hafnium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the molar percentage of yittrium oxide is 3 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of cerium oxide is 0.1 ~ 20% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of calcium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of magnesia is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of aluminum oxide is 0.1 ~ 30% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of titanium oxide is 0.1 ~ 20% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of silica is 0.1 ~ 20% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of cobalt oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of iron oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of scandium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of vanadium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of manganese oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of nickel oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of cupric oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of zinc oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of niobium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of molybdenum oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of indium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of tin oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of barium monoxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of tantalum oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of tungsten oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of lanthana is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of praseodymium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of neodymia is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of tellurium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of terbium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of europium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the percentage by weight of erbium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Step（1）In, the noresidue dispersant of selection be in high straight alcohol, high-purity n-butanol, high-purity ethylene glycol at least It is a kind of.
Step（1）In, the noresidue binding agent of selection is at least one of high-purity polyvinyl alcohol, high-purity polyvinyl chloride.
Step（1）In, the noresidue surfactant of selection is high-purity octadecanoid acid, high-purity hexadecanoic acid, high-purity 18 At least one of olefin(e) acid.
Step（1）In, the noresidue lubricant of selection is high-purity glycerine, high-purity alkylbenzene oil, high-purity polyethers artificial oil, At least one of high-purity olein.
Step（1）In, the noresidue plasticizer of selection is propyleneglycoles, high-purity dioctyl phthalate, Gao Chunlin At least one of dicyclo-hexyl phthlate.
Step（1）In, high-purity purity of alcohol in the noresidue dispersant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity n-butanol purity in the noresidue dispersant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity ethylene glycol purity in the noresidue dispersant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity polyvinyl alcohol purity in the noresidue binding agent of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity polyvinyl chloride purity in the noresidue binding agent of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity octadecanoid acid purity in the noresidue surfactant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity hexadecanoic acid purity in the noresidue surfactant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity octadecenic acid purity in the noresidue surfactant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity glycerine purity in the noresidue lubricant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity alkylbenzene oil purity in the noresidue lubricant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity polyethers artificial oil purity in the noresidue lubricant of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity olein purity in the noresidue lubricant of selection is 99.9% ~ 99.999%.
Step（1）In, the high-pure propylene ethylene glycol purity in the noresidue plasticizer of selection is 99.9% ~ 99.999%.
Step（1）In, high-purity dioctyl phthalate purity in the noresidue plasticizer of selection for 99.9% ~ 99.999%。
Step（1）In, high-purity dicyclohexyl phthalate purity in the noresidue plasticizer of selection for 99.9% ~ 99.999%。
Step（1）In, the percentage by weight of described nano composite oxides zirconium powder is 20% ~ 99%, and surplus is noresidue point Powder, noresidue binding agent, noresidue surfactant, noresidue lubricant, the summation of noresidue plasticizer.
Step（1）In, described noresidue dispersant weight percentage is 0.6 ~ 40%.
Step（1）In, described noresidue weight of binder percentage is 0.1 ~ 10%.
Step（1）In, described noresidue surfactant percentage by weight is 0.1 ~ 10%.
Step（1）In, described noresidue lubricant weight percentage is 0.1 ~ 10%.
Step（1）In, described noresidue plasticizer percentage by weight is 0.1 ~ 10%.
Step（1）In, the described refining glue time is 2 ~ 48 hours.
Step（1）In, described glue furnacing temperature is 25 ~ 60 degree.
Step（1）In, described refining glue vacuum is 0.01 ~ 0.1atm.
Step（1）In, the refining compound viscosity that described refining glue processing is obtained is 10000-30000mPa.s.
Preferably, step（1）In, the primary particle size of described nano composite oxides zirconium powder is 10 ~ 40 nanometers.
Preferably, step（1）In, the purity of described nano composite oxides zirconium powder is 99.99% ~ 99.999%.
Preferably, step（1）In, the percentage by weight of hafnium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the molar percentage of yittrium oxide is 3 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of cerium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of calcium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of magnesia is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of aluminum oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of titanium oxide is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of silica is 0.1 ~ 10% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of cobalt oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of iron oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of scandium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of vanadium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of manganese oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of nickel oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of cupric oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of zinc oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of niobium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of molybdenum oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of indium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of tin oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of barium monoxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of tantalum oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of tungsten oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of lanthana is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of praseodymium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of neodymia is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of tellurium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of terbium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of europium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, the percentage by weight of erbium oxide is 0.1 ~ 5% in the nano composite oxides zirconium powder of selection.
Preferably, step（1）In, high-purity purity of alcohol in the noresidue dispersant of selection is 99.99% ~ 99.999%.
Preferably, step（1）In, high-purity n-butanol purity in the noresidue dispersant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity ethylene glycol purity in the noresidue dispersant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity polyvinyl alcohol purity in the noresidue binding agent of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity polyvinyl chloride purity in the noresidue binding agent of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity octadecanoid acid purity in the noresidue surfactant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity hexadecanoic acid purity in the noresidue surfactant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity octadecenic acid purity in the noresidue surfactant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity glycerine purity in the noresidue lubricant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity alkylbenzene oil purity in the noresidue lubricant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity polyethers artificial oil purity in the noresidue lubricant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity olein purity in the noresidue lubricant of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-pure propylene ethylene glycol purity in the noresidue plasticizer of selection for 99.99% ~ 99.999%。
Preferably, step（1）In, high-purity dioctyl phthalate purity in the noresidue plasticizer of selection is 99.99%~99.999%。
Preferably, step（1）In, high-purity dicyclohexyl phthalate purity in the noresidue plasticizer of selection is 99.99%~99.999%。
Preferably, step（1）In, the percentage by weight of described nano composite oxides zirconium powder is 40% ~ 86%, and surplus is nothing Remain dispersant, noresidue binding agent, noresidue surfactant, noresidue lubricant, the summation of noresidue plasticizer.
Preferably, step（1）In, described noresidue dispersant weight percentage is 10 ~ 40%.
Preferably, step（1）In, described noresidue weight of binder percentage is 1 ~ 5%.
Preferably, step（1）In, described noresidue surfactant percentage by weight is 1 ~ 5%.
Preferably, step（1）In, described noresidue lubricant weight percentage is 1 ~ 5%.
Preferably, step（1）In, described noresidue plasticizer percentage by weight is 1 ~ 5%.
Preferably, step（1）In, the described refining glue time is 4 ~ 24 hours.
Preferably, step（1）In, described glue furnacing temperature is 40 ~ 60 degree.
Preferably, step（1）In, described refining glue vacuum is 0.01 ~ 0.03atm.
Preferably, step（1）In, the refining compound viscosity that described refining glue processing is obtained is 10000-20000mPa.s.
Step（2）In, described curtain coating treatment temperature is 25 ~ 60 degree.
Step（2）In, described curtain coating processing needs mould carrying out uniform smearing surface lubrication oil processing.
Step（2）In, the surface lubrication oil of described curtain coating processing mould is high-purity glycerine, high-purity alkylbenzene oil, At least one of high-purity polyethers artificial oil, high-purity olein.
Step（2）In, described curtain coating processing needs to ensure the fully horizontal of plane.
Step（2）In, the scraper material of described curtain coating processing be in polytetrafluoroethylene (PTFE), polyvinyl chloride, Teflon extremely Few one kind.
Step（2）In, the drying temperature of described constant temperature and humidity drying is 100 ~ 200 degree.
Step（2）In, the humidity of described constant temperature and humidity drying is vapor content 0.1 ~ 30%.
Step（2）In, the processing time of described constant temperature and humidity drying is 4 ~ 48 hours.
Preferably, step（2）In, described curtain coating treatment temperature is 25 ~ 40 degree.
Preferably, step（2）In, the drying temperature of described constant temperature and humidity drying is 120 ~ 200 degree.
Preferably, step（2）In, the humidity of described constant temperature and humidity drying is vapor content 0.1 ~ 10%.
Preferably, step（2）In, the processing time of described constant temperature and humidity drying is 8 ~ 24 hours.
Step（3）In, described dumping treatment temperature is 400 ~ 800 degree.
Step（3）In, described dumping processing heating rate is 10 ~ 200 degree/hour.
Step（3）In, described dumping processing rate of temperature fall is 10 ~ 200 degree/hour.
Step（3）In, described dumping processing soaking time is 12 ~ 72 hours.
Step（3）In, described dumping processing atmosphere is air.
Step（3）In, described sintering processes temperature is 1200 ~ 1500 degree.
Step（3）In, described sintering processes soaking time is 1 ~ 10 hour.
Step（3）In, described sintering processes atmosphere is air.
Step（3）In, described sintering processes are divided into three phases.
Step（3）In, the target temperature of the first stage of the temperature rise period of described sintering processes is 600 ~ 800 degree.
Step（3）In, the heating rate of the first stage of the temperature rise period of described sintering processes for 10 ~ 100 degree/it is small When.
Step（3）In, the target soaking time of the first stage of the temperature rise period of described sintering processes is small for 0.5 ~ 2 When.
Step（3）In, the target temperature of the second stage of the temperature rise period of described sintering processes is 850 ~ 1100 degree.
Step（3）In, the heating rate of the second stage of the temperature rise period of described sintering processes for 50 ~ 100 degree/it is small When.
Step（3）In, the target soaking time of the second stage of the temperature rise period of described sintering processes is small for 0.5 ~ 2 When.
Step（3）In, the target temperature of the phase III of the temperature rise period of described sintering processes is 1200 ~ 1500 degree.
Step（3）In, the heating rate of the phase III of the temperature rise period of described sintering processes for 50 ~ 100 degree/it is small When.
Step（3）In, the target soaking time of the phase III of the temperature rise period of described sintering processes is 1 ~ 10 hour.
Step（3）In, the temperature-fall period of described sintering processes has two stages.
Step（3）In, the target temperature of the first stage of the temperature-fall period of described sintering processes is 800 ~ 1000 degree.
Step（3）In, the rate of temperature fall of the first stage of the temperature-fall period of described sintering processes is 10 ~ 50 degree/hour.
Step（3）In, the target temperature of the second stage of the temperature-fall period of described sintering processes is 20 ~ 80 degree.
Step（3）In, the rate of temperature fall of the second stage of the temperature-fall period of described sintering processes is 10 ~ 80 degree/hour.
Preferably, step（3）In, described dumping treatment temperature is 500 ~ 600 degree.
Preferably, step（3）In, described dumping processing heating rate is 30 ~ 150 degree/hour.
Preferably, step（3）In, described dumping processing rate of temperature fall is 20 ~ 150 degree/hour.
Preferably, step（3）In, described dumping processing soaking time is 24 ~ 60 hours.
Preferably, step（3）In, described sintering processes temperature is 1300 ~ 1450 degree.
Preferably, step（3）In, described sintering processes soaking time is 2 ~ 4 hours.
Preferably, step（3）In, the target temperature of the first stage of the temperature rise period of described sintering processes for 700 ~ 800 degree.
Preferably, step（3）In, the heating rate of the first stage of the temperature rise period of described sintering processes is 30 ~ 50 Degree/hour.
Preferably, step（3）In, the target soaking time of the first stage of the temperature rise period of described sintering processes for 1 ~ 2 hours.
Preferably, step（3）In, the target temperature of the second stage of the temperature rise period of described sintering processes for 900 ~ 1050 degree.
Preferably, step（3）In, the heating rate of the second stage of the temperature rise period of described sintering processes is 50 ~ 80 Degree/hour.
Preferably, step（3）In, the target soaking time of the second stage of the temperature rise period of described sintering processes for 1 ~ 2 hours.
Preferably, step（3）In, the target temperature of the phase III of the temperature rise period of described sintering processes for 1300 ~ 1450 degree.
Preferably, step（3）In, the heating rate of the phase III of the temperature rise period of described sintering processes is 50 ~ 80 Degree/hour.
Preferably, step（3）In, the target soaking time of the phase III of the temperature rise period of described sintering processes for 1 ~ 4 hours.
Preferably, step（3）In, the target temperature of the first stage of the temperature-fall period of described sintering processes for 900 ~ 1000 degree.
Preferably, step（3）In, the rate of temperature fall of the first stage of the temperature-fall period of described sintering processes is 30 ~ 50 Degree/hour.
Preferably, step（3）In, the target temperature of the second stage of the temperature-fall period of described sintering processes is 20 ~ 50 Degree.
Preferably, step（3）In, the rate of temperature fall of the second stage of the temperature-fall period of described sintering processes is 20 ~ 50 Degree/hour.
Step（4）In, described density measuring instrument is Archimedes's drainage density of solid detector.
Step（4）In, described purity detecting instrument is inductively coupled plasma atomic emission spectrometer.
Step（4）In, described crystallite dimension measuring instrument is SEM.
Step（4）In, described bending strength measuring instrument measures testing machine for three-point bending.
Step（4）In, described hardness measurement instrument is Vickers.
Step（4）In, the relative density of described high-purity zirconia composite ceramics is 90 ~ 99%.
Step（4）In, the purity of described high-purity zirconia composite ceramics is 99.5 ~ 99.999%.
Step（4）In, the crystallite dimension of described high-purity zirconia composite ceramics is 0.1 ~ 20 micron.
Step（4）In, the bending strength of described high-purity zirconia composite ceramics is 400 ~ 2000MPa.
Step（4）In, the hardness of described high-purity zirconia composite ceramics is HV2000 ~ 20000.
The present invention is high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof, by present invention process system The following beneficial effect of ceramic ultra-thin plate made.
（1）Due to having used superfine nano powder, finished product crystallite dimension is smaller, and more preferably, wear extent is small for intensity.
（2）Due to used multicomponent coordinate scheme, allow ultra thin plate toughness more preferably, shock resistance is more preferably.
（3）Due to using the dumping sintering process become more meticulous, making the density of finished product higher.
Embodiment
The present invention relates to a kind of high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof, specific implementation step It is rapid as follows.
（1）It is 3% from yittrium oxide molar content, hafnium oxide percentage by weight is 1%, alumina weight percentage is 3%, Silica percentage by weight is 2%, and cerium oxide percentage by weight is 1%, and the percentage by weight of europium oxide is answered for 0.5% zirconium oxide Powder is closed, the host element purity of zirconium oxide composite powder is 99.999%, the primary particle size of zirconium oxide composite powder is 3.4 nanometers, will be compound Powder and 99.99% ethanol percentage by weight 40%, 99.99% polyvinyl alcohol weight percentage 2%, 99.99% octadecanoid acid Percentage by weight 3%, 99.99% olein percentage by weight 2%, 99.99% propyleneglycoles percentage by weight 3% exists 45 degree of refining glues 14 hours, vacuum remains 0.02atm, and the refining compound viscosity of acquisition is 15218mPa.s.
（2）By step（1）The refining glue material material of middle acquisition is put into tape casting machine, by flow casting molding mould oleic Fat carries out surface lubrication processing, and by mould level-off, carries out flow casting molding at 50 degree of temperature, is carried out with polytetrafluoroethylene (PTFE) knife Strike off three times, and be put into drying baker 130 degree and dry 12 hours, the humidity of drying process is vapor content 5.7%.
（3）By step（2）The ultra thin plate blank of middle acquisition is put into dumping sintering furnace, and heating rate is 40 degree/hour, row Glue treatment temperature is 500 degree, and the dumping time is 18 hours, cold with stove, and the blank that dumping is finished is put into the first rank in sintering furnace Section heating rate be 40 degree/hour, target temperature be 750 degree, soaking time be 1 hour, second stage heating rate for 60 degree/ Hour, target temperature is 1000 degree, and soaking time is 1 hour, and phase III heating rate is 60 degree/hour, and target temperature is 1350 degree, soaking time is 4 hours, and first stage rate of temperature fall is 40 degree/hour, and target temperature is 1000 degree, second stage Rate of temperature fall is 30 degree/hour, and target temperature is 30 degree, produces high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate.
（4）Measuring process（3）The relative density of middle high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 93.51%, pure Spend for 99.9911%, grain size is 0.9 micron, and bending strength is 869MPa, and hardness is HV4010.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention.It is all according to the present invention The equivalent change or modification that Spirit Essence is made, should all cover within the scope of the present invention.

Claims (10)

1. a kind of high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof, it is characterised in that specific steps are such as Under：
（1）Nano level zirconia powder is chosen by specific proportioning to adulterate the nano composite oxides zirconium powders of other oxides, is being received Ground rice is put into noresidue dispersant, noresidue binding agent, noresidue surfactant, noresidue lubricant, noresidue plasticizer Carry out vacuum refining glue；
（2）By step（1）Middle acquisition refining glue material carries out curtain coating processing, and curtain coating thin plate is carried out striking off processing three times, and carries out Constant temperature and humidity drying；
（3）By step（2）Middle acquisition flow casting molding blank carries out dumping and sintering processes, produces high-purity high-strength high-ductility zirconium oxide and answers Close ceramic ultra-thin plate；
（4）Measuring process（3）The density of middle high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate, purity, crystallite dimension, bending resistance Intensity and hardness.
2. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（1）In, adulterated in described nano composite oxides zirconium powder hafnium oxide, yittrium oxide, cerium oxide, calcium oxide, oxidation Magnesium, aluminum oxide, titanium oxide, silica, cobalt oxide, iron oxide, scandium oxide, vanadium oxide, manganese oxide, nickel oxide, cupric oxide, oxidation Zinc, niobium oxide, molybdenum oxide, indium oxide, tin oxide, barium monoxide, tantalum oxide, tungsten oxide, lanthana, praseodymium oxide, neodymia, oxidation At least one of tellurium, terbium oxide, europium oxide, erbium oxide.
3. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（1）In, the host element purity of described nano composite oxides zirconium powder is 99.9% ~ 99.999%.
4. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（1）In, the primary particle size of described nano composite oxides zirconium powder is 1 ~ 100 nanometer.
5. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（2）In, described constant temperature and humidity drying temperature is 100-200 degree.
6. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（4）In, the purity of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 99.5 ~ 99.999%.
7. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（4）In, the relative density of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 90 ~ 99%.
8. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（4）In, the crystallite dimension of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 0.1 ~ 20 micron.
9. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（4）In, the bending strength of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is 400 ~ 2000MPa.
10. high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate according to claim 1 and preparation method thereof, its feature It is：Step（4）In, the hardness of described high-purity high-strength high-ductility zirconia composite ceramics ultra thin plate is HV2000 ~ 20000.
CN201710201806.0A 2017-03-30 2017-03-30 High-purity high-strength high-ductility zirconia composite ceramics ultra thin plate and preparation method thereof Pending CN106977201A (en)

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CN114804894A (en) * 2022-07-01 2022-07-29 中国人民解放军国防科技大学 Multi-element complex-phase micro-nano ceramic fiber and preparation method and application thereof
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