CN102757222A - Composite stable microcrystal zirconium oxide ceramic mixed powder and manufacturing process - Google Patents
Composite stable microcrystal zirconium oxide ceramic mixed powder and manufacturing process Download PDFInfo
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Abstract
The invention provides composite stable microcrystal zirconium oxide ceramic mixed powder and a manufacturing process. Industrial-grade zirconium oxide powder is used as a main material and a suitable amount of cerium oxide (CeO), yttrium oxide (Y2O3), aluminum oxide and calcium carbonate (CaCO3) are used as stabilizing agents; all the components are prepared according to the following percentage by weight: 10-12% of the cerium oxide (CeO), 1-2% of the yttrium oxide (Y2O3), 3-8% of the aluminum oxide (Al2O3), 1-2% of the calcium carbonate (CaCO3) and the balance of the industrial-grade zirconium oxide powder; and the powder materials are mixed according to the proportion and the composite stable microcrystal zirconium oxide ceramic mixed powder is prepared by the steps of physically mixing, super-thinning, calcining, dispersing and granulating. With the adoption of a plurality of the stabilizing agents, the stable composition of zirconium oxide is realized, and zirconium oxide ceramic which is stably composited has better physiochemical performances.
Description
Technical field
The present invention relates to a kind of prescription and manufacture craft thereof of non-metallic material, refer in particular to a kind of crystallite zirconia ceramics and make prescription and manufacture craft, belong to new material technology field.
Background technology
Zirconia ceramics is a kind of new ceramics that rises nearly decades, because zirconia ceramics has H.T., high-flexural strength and high-wearing feature, and excellent heat-proof quality, thermal expansivity approaches advantages such as steel, therefore is widely used in the structural ceramics field.Mainly contain: wear-resisting zero device of the light-duty bat of Y-TZP abrading-ball, dispersion and grinding medium, nozzle, ball valve core and ball seat, zirconium white mould, mini-fan axle center, optical fiber contact pins, optical fiber sleeve, wortle and parting tool, wear resistant cutters, watchcase and watchband, golf ball and other room temperature etc.In addition, because of zirconia ceramics has outstanding high temperature resistance, therefore also be commonly used to make induction heating pipe, refractory materials, Heating element; Zirconia ceramics has responsive unit for electrical property parameters, therefore also is applied to fields such as oxygen sensor, SOFC (SolidO xideFu elCe ll, SO FC) and high temperature heating element.In addition, zirconium white just is used widely in fields such as thermal barrier coating, support of the catalyst, medical treatment, health care, refractory materials, weavings.
Though zirconia ceramics has fine performance in many aspects, that the production requirement of zirconia ceramics prepares is high-purity, dispersing property good, particle is ultra-fine, the powder of narrow particle size distribution.The preparation method of zirconium oxide micro powder is a lot, and zirconic purification mainly contains chlorination and thermal decomposition method, basic metal oxygenolysis method, lime method, plasma arc method, the precipitator method, colloid method, hydrolysis method, spray pyrolysis etc.Powder process has coprecipitation method, sol-gel method, method of evaporation, overcritical synthesis method, microemulsion method, hydrothermal synthesis method net and vapour deposition process etc.That the production requirement of zirconia ceramics prepares is high-purity, dispersing property good, particle is ultra-fine, the powder of narrow particle size distribution.
Purified zirconium white is a white solid, can manifest grey or faint yellow when containing impurity, adds developer and also can show various other colors.The molecular weight of pure zirconia is 123.22, and theoretical density is 5.89g/cm3, and fusing point is 2715 ℃.Usually contain a spot of hafnia, be difficult to separate, but to the not significantly influence of zirconic performance.Zirconium white has three kinds of crystal habits: monocline, four directions, cube crystalline phase.Zirconium white only occurs with monocline mutually under the normal temperature, is heated to and changes cubic phase about 1100 ℃ into, is heated to higher temperature and can be converted into a cube phase.Owing to can produce bigger volume change in the tetragonal phase converting in opposite directions in monocline, in the time of refrigerative again bigger volume change can take place in the opposite direction, cause the cracking of product easily, limited the application of pure zirconia in the high temperature field.But after the interpolation stablizer, the four directions can be stablized mutually at normal temperatures, and therefore the sudden change of volume can not take place after heating, has expanded zirconic range of application greatly.Up to now; During the precipitator method of zirconia ceramics powder are produced; What adopt all is to adopt partially stabilized chemical coprecipitation; Its ultimate principle is that zirconium oxychloride and single stablizer (like cerium oxide, yttrium oxide, Natural manganese dioxide, quicklime etc.) are dissolved in certain density acidic liq again through precipitate reduction extraction, calcining, the high-purity uniform PSZ mixed powder of acquisition, is made into partial stabilization zirconium oxide ceramic through granulation then and uses powder.Its advantage is that purity is high, stablizer mixes, and original particle size is thin.Shortcoming is to adopt a large amount of soda acid solvents in the production process, and environmental pollution is bigger, adopts the single stable agent to make the crystalline phase transition rule of stupalith; Fatigue resistance is relatively poor, and production cost is higher, and sintering range is narrow; Usually have only ± 20 ℃; It is low to fire yield rate, and complex manufacturing is wayward, has therefore greatly limited its production and application.
Through the domestic Searches of Patent Literature, only find to have the bibliographical information of the following zirconium white mixed powder production method, mainly relevant with the present invention having is following:
1, number of patent application is CN03132121.6, and denomination of invention is the patent of invention of " high glassy phase content crystallite zirconia ceramics material ", and this patent discloses a kind of high glassy phase content crystallite zirconia ceramics material, belongs to the oxide ceramic material field.It comprises the sintering aid selection, and characteristics are: (1) raw material: the superfine zirconia ceramic powder of prepared by co-precipitation, its primary particle size are 20 ~ 40nm; (2) stablizer; Y2O3, its add-on is 1.8 ~ 4mol%; (3) sintering aid: the glassy phase of MgO-Al2O3-SiO2 system is main composition, and its add-on is 10 ~ 30wt%; (4) sintering temperature: 1100 ~ 1300 ℃, 0.5 hour time.
2, number of patent application is CN200580034769.4, and denomination of invention is the patent of invention of " zirconia ceramics ", and this patent discloses a kind of the description and has been used for fixed polycomponent powder with the sinterable green bodies that forms zirconia ceramics.This polycomponent powder comprises at least 80 volume % nano-scale zirconia particles and the stablizer of 20 volume % at the most, and this stablizer can around the nano-scale zirconia particles, form coating layer and it is chosen as particulate form.The polycomponent slurry that forms through suspended powder in liquid has also been described, and the green compact that form by this slurry or this powder.The zirconia ceramics that forms through these green compact of sintering has also been described.
3, number of patent application is CN200910188008.4; Denomination of invention is the patent of invention of " a kind of preparation method of superfine zirconia powder "; This patent discloses a kind of preparation method of superfine zirconia powder; Wherein precipitation agent is selected quaternary ammonium hydroxide for use, and adopts the special precipitator method preparation superfine zirconia powder that combines.The special precipitator method are about to two kinds of solution adding simultaneously in the reaction kettle under the condition of stirring fast, react nucleation rapidly, without ageing, and directly washing, thus reach the purpose that control nuclear is grown up.Quaternary ammonium hydroxide is that alkaline matter can be separated out oxidizing aqueous zirconium (zirconium hydroxide gel) from zirconium salt solution; Also be thereby that surface-modifying agent can change IT and reaches the dispersive effect; Saved the interpolation of dispersion agent; Practice thrift cost, under the situation of needs, can also prepare simultaneously through the amount that the compound that contains yttrium is added in control the four directions mutually with cube mutually Zirconium powder.
3, number of patent application is CN200610024361.5; Denomination of invention is the patent of invention of " ytterbium oxide and yttrium oxide co-stabilized zirconia ceramics material and preparation method "; This patent discloses a kind of ytterbium oxide and yttrium oxide co-stabilized zirconia ceramics and preparation method; It is characterized in that: use two kinds of oxide compounds of ytterbium oxide and yttrium oxide simultaneously as stablizer; Adopt the nano zirconium oxide powder of the common parcel of two kinds of stablizers of technique for packing preparation, the pressureless sintering in air of gained powder obtains tetragonal zirconia polycrystal (TZP) and complete stable cubic zirconia ceramics (FSZ) respectively under low stabiliser content.The raw material that adopts is that purity (mass percent) is not less than 99.9 ytterbium oxide (Yb2O3), yttrium oxide (Y2O3) and monoclinic zirconia powder (average grain size is less than 100 nanometers); The molar percentage of ytterbium oxide (Yb2O3) is in the 1.0-2.0% scope in the final TZP pottery that obtains, and the molar percentage of yttrium oxide (Y2O3) is in the 1.0-2.0% scope; The molar percentage of ytterbium oxide in the FSZ pottery (Yb2O3) is in the 3.0-4.0% scope, and the molar percentage of yttrium oxide (Y2O3) is in the 1.0-2.0% scope.
But above-mentioned patent does not still have to solve existing chemical coprecipitation zirconia ceramics powder produces existing deficiency, so for how the existing chemical coprecipitation zirconia ceramics powder system of customer service is made existing deficiency, still remain further to be studied.
Summary of the invention
The objective of the invention is to the existing existing deficiency of chemical coprecipitation zirconium white mixed powder production method; Propose a kind ofly can effectively improve zirconium white mixed powder zirconium white mixed powder fatigue resistance; And cost of manufacture is low, new physics ultra-fine method zirconium white mixed powder prescription and the production method thereof little to environmental pollution; The physical and chemical performance that zirconium white mixed powder prescription that this kind method is made and production method thereof not only can greatly improve partial stabilization zirconium oxide ceramic, and can under the working condition that no any soda acid pollutes, realize.
For realizing the object of the invention, the technical scheme that is proposed is: a kind of stable composition crystallite zirconia ceramics mixed powder is made prescription, adopts the compound preparation crystallite of the stablizer zirconia ceramics mixed powder more than three kinds;
With the technical grade zirconia powder is major ingredient, and mixes an amount of cerium oxide (CeO), yttrium oxide (Y
2O
3), aluminum oxide and lime carbonate (CaCO
3) as stablizer, and each component is prepared according to following weight per-cent:
Cerium oxide (CeO) 10%-12%, yttrium oxide (Y
2O
3) 1%-2%, aluminum oxide (AL
2O
3) 3%-8%, lime carbonate (CaCO
3) 1%-2%, all the other are the technical grade zirconia powder;
Above-mentioned powder is carried out assembly according to proportioning, process stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation.
Further, described major ingredient is the technical grade zirconia powder, also can be baddeleyite or electric smelting method zirconia powder, or the three is according to the mixture of any group mode preparation.
The process method of processing stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation of above-mentioned stable composition crystallite zirconia ceramics mixed powder is: prepare starting material by above-mentioned prescription; Batch mixing was greater than 10 hours in blender; In super-fine-ground equipment that mixed material is ultra-fine to require the to burn till big or small 1/5-1/10 of crystalline size; Be generally the 100-1000 nanometer; In temperature is to calcine 90-120 minute in the 900-1200 ℃ of stove, and the powder that calcining is good wet method in ultra tiny dispersing apparatus is disperseed, and adds the diffusing agent of organic branch ≦ 1%; Add the 0.3-1% sticker at last and carry out spraying drying, obtain the zirconia ceramics powder of stable composition.Described organic dispersing agent comprises triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, SEPIGEL 305, guar gum, fatty acid polyglycol ester: described sticker is the conventional sticker of zirconia powder, can be PanaviaTMF resin glue (Japanese Kuraray company); Multilink Sprint resin glue (Deng Sidunyi Huojia County company is disbursed from the cost and expenses): the reinforced glass ion sticker of RelyXTMLuting resin (Minnesota Mining and Manufacturing Company): the reinforced glass ion sticker of Fu ji plus resin (Japanese GC company).
Further, described ultra-fine be ultra-fine in super-fine-ground equipment, be D90＜1 micron to the powder superfine fineness that becomes porcelain crystal grain＜5 microns; D50＜0.5 micron; To becoming the powder of porcelain crystal grain＜2 microns, ultra-fine to D90＜0.4 micron, D50＜0.2 micron; Have only the ultra-fine described requirement of arriving, just can make the zirconia ceramics powder of making reach required requirement.
Further, it is that calcining powder wet method in the ultra-fine dispersing apparatus of high speed is disperseed that described wet method is disperseed, and adds organic dispersing agent≤1%.Solid-liquid ratio is 4.5:5.5, adds organic binder bond 0.3-1% then.
The invention has the advantages that; Discover through of the present invention; When with stablizer and zirconia powder simultaneously ultra-fine to 90% particle diameter (being D90) less than the partial stabilization zirconium oxide ceramic crystal grain that burns till 1/5 the time; Median size (being D50) adopted multiple stablizer can reach the same stabilising effect of partially stabilized zirconia ceramics that chemical coprecipitation obtains fully less than 1/10 o'clock of the partial stabilization zirconium oxide ceramic crystal grain that burns till, and for example will obtain the partial stabilization zirconium oxide ceramic of 5 microns article grains; It is ultra-fine to D90＜1 micron that multiple stablizer and zirconium white are mixed the back, and D50＜0.5 micron can reach stable effect fully.And can adopt multiple stablizer that zirconium white is realized stable composition, the zirconia ceramics of stable composition has better physical and chemical performance usually.
The production technology and the equipment of nearly ten years especially nearly 2 years super-fine powders develop rapidly, and people can be without the methods of chemistry and adopted the mode of physics can produce all kinds of powders less than 200 nanometers.The development of this technology makes stablizer and zirconium white adopt the mode of physics to carry out mixed preparing with ripe the application, again through ultra tiny, calcine and can produce the PSZ mixed powder and become possibility, the present invention is exactly wherein a kind of.Its biggest advantage is no any pollution in the production process; The 2nd, overcome the defective that chemical coprecipitation can only adopt the single stable agent; Can adopt physics and the chemical property of multiple stablizer with the lift portion stabilization zirconium oxide ceramic, the 3rd, reduced raw-material cost and production cost significantly.
Description of drawings
Fig. 1 is conventional formulation and technological process of production figure;
Fig. 2 is invention prescription and technological process of production figure.
Embodiment
To combine accompanying drawing and embodiment that the present invention is done further description below.
As can be seen from Figure 2, the present invention relates to a kind of stable composition crystallite zirconia ceramics mixed powder, be major ingredient with the technical grade zirconia powder, and mix an amount of cerium oxide (CeO), yttrium oxide (Y
2O
3), aluminum oxide and lime carbonate (CaCO
3) as stablizer, and each component is prepared according to following weight per-cent:
Cerium oxide (CeO) 10%-12%, yttrium oxide (Y
2O
3) 1%-2%, aluminum oxide (AL
2O
3) 3%-8%, lime carbonate (CaCO
3) 1%-2%, all the other are the technical grade zirconia powder;
Above-mentioned powder is carried out assembly according to proportioning, process stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation.
Further, described major ingredient is the technical grade zirconia powder, also can be baddeleyite or electric smelting method zirconia powder, or the three is according to the mixture of any group mode preparation.
The process method of processing stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation of above-mentioned stable composition crystallite zirconia ceramics mixed powder is: prepare starting material by above-mentioned prescription; Batch mixing was greater than 10 hours in blender; In super-fine-ground equipment that mixed material is ultra-fine to require the to burn till big or small 1/5-1/10 of crystalline size; Being generally 100-1000 nanometer (D90＜1 micron, D50＜0.5 micron), is calcining 90-120 minute in the 900-1200 ℃ of stove in temperature; The powder that calcining is good wet method in ultra tiny dispersing apparatus is disperseed; Add the diffusing agent of organic branch ≦ 1%, add the 0.3-1% sticker at last and carry out spraying drying, obtain the zirconia ceramics powder of stable composition.Described organic dispersing agent comprises triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, SEPIGEL 305, guar gum, fatty acid polyglycol ester: described sticker is the conventional sticker of zirconia powder, can be PanaviaTMF resin glue (Japanese Kuraray company); Multilink Sprint resin glue (Deng Sidunyi Huojia County company is disbursed from the cost and expenses): the reinforced glass ion sticker of RelyXTMLuting resin (Minnesota Mining and Manufacturing Company): the reinforced glass ion sticker of Fu ji plus resin (Japanese GC company).
Further, described ultra-fine be ultra-fine in super-fine-ground equipment, be D90＜1 micron to the powder superfine fineness that becomes porcelain crystal grain＜5 microns; D50＜0.5 micron; To becoming the powder of porcelain crystal grain＜2 microns, ultra-fine to D90＜0.4 micron, D50＜0.2 micron; Have only the ultra-fine described requirement of arriving, just can make the zirconia ceramics powder of making reach required requirement.
Further, it is that calcining powder wet method in the ultra-fine dispersing apparatus of high speed is disperseed that described wet method is disperseed, and adds organic dispersing agent≤1%.Solid-liquid ratio is 4.5:5.5, adds organic binder bond 0.3-1% then.
Embodiment one
A kind of stable composition crystallite zirconia ceramics mixed powder and preparation method thereof is a major ingredient with the technical grade zirconia powder, and mixes an amount of cerium oxide (CeO), yttrium oxide (Y
2O
3), aluminum oxide and lime carbonate (CaCO
3) as stablizer, and each component is prepared according to following weight per-cent:
Cerium oxide (CeO) 10%, yttrium oxide (Y
2O
3) 1%, aluminum oxide (AL
2O
3) 3%, lime carbonate (CaCO
3) 1%, all the other are the technical grade zirconia powder;
Above-mentioned powder is carried out assembly according to proportioning, process stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation.
Described major ingredient is the technical grade zirconia powder;
The process method of processing stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation of above-mentioned stable composition crystallite zirconia ceramics mixed powder is: prepare starting material by above-mentioned prescription; Batch mixing is 11 hours in blender; In super-fine-ground equipment that mixed material is ultra-fine to require the to burn till big or small 1/5-1/10 of crystalline size; Be generally the 100-1000 nanometer; In temperature is to calcine 90-120 minute in the 900-1200 ℃ of stove, and the powder that calcining is good wet method in ultra tiny dispersing apparatus is disperseed, and adds the diffusing agent of organic branch ≦ 1%; Add the 0.3-1% sticker at last and carry out spraying drying, obtain the zirconia ceramics powder of stable composition.
Described organic dispersing agent is a kind of in triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, SEPIGEL 305, guar gum or the fatty acid polyglycol ester.
Described sticker is the conventional sticker of zirconia powder, can be in PanaviaTMF resin glue (Japanese Kuraray company), Multilink Sprint resin glue (Deng Sidunyi Huojia County company is disbursed from the cost and expenses), the reinforced glass ion sticker of RelyXTMLuting resin (Minnesota Mining and Manufacturing Company) or the reinforced glass ion sticker of Fu ji plus resin (Japanese GC company) any one.
Described ultra-fine be ultra-fine in super-fine-ground equipment; To the powder superfine fineness that becomes porcelain crystal grain＜5 microns is D90＜1 micron, and D50＜0.5 micron is to becoming the powder of porcelain crystal grain＜2 microns; Ultra-fine to D90＜0.4 micron; D50＜0.2 micron has only ultra-finely to described requirement, just can make the zirconia ceramics powder of making reach required requirement.
It is that calcining powder wet method in the ultra-fine dispersing apparatus of high speed is disperseed that described wet method is disperseed, and adds organic dispersing agent≤1%.Solid-liquid ratio is 4.5:5.5, adds organic binder bond 0.3% then.
Embodiment two
A kind of stable composition crystallite zirconia ceramics mixed powder and preparation method thereof is a major ingredient with the technical grade zirconia powder, and mixes an amount of cerium oxide (CeO), yttrium oxide (Y
2O
3), aluminum oxide and lime carbonate (CaCO
3) as stablizer, and each component is prepared according to following weight per-cent:
Cerium oxide (CeO) 12%, yttrium oxide (Y
2O
3) 2%, aluminum oxide (AL
2O
3) 8%, lime carbonate (CaCO
3) 2%, all the other are the technical grade zirconia powder;
Above-mentioned powder is carried out assembly according to proportioning, process stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation.
Described major ingredient is baddeleyite or electric smelting method zirconia powder.
The process method of processing stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation of above-mentioned stable composition crystallite zirconia ceramics mixed powder is: prepare starting material by above-mentioned prescription; Batch mixing is 15 hours in blender; In super-fine-ground equipment that mixed material is ultra-fine to require the to burn till big or small 1/5-1/10 of crystalline size; Be generally the 100-1000 nanometer; In temperature is to calcine 90-120 minute in the 900-1200 ℃ of stove, and the powder that calcining is good wet method in ultra tiny dispersing apparatus is disperseed, and adds the diffusing agent of organic branch ≦ 1%; Add the 0.3-1% sticker at last and carry out spraying drying, obtain the zirconia ceramics powder of stable composition.Described organic dispersing agent comprises triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, SEPIGEL 305, guar gum, fatty acid polyglycol ester: described sticker is the conventional sticker of zirconia powder, can be PanaviaTMF resin glue (Japanese Kuraray company); Multilink Sprint resin glue (Deng Sidunyi Huojia County company is disbursed from the cost and expenses): the reinforced glass ion sticker of RelyXTMLuting resin (Minnesota Mining and Manufacturing Company): the reinforced glass ion sticker of Fu ji plus resin (Japanese GC company).
Described ultra-fine be ultra-fine in super-fine-ground equipment; To the powder superfine fineness that becomes porcelain crystal grain＜5 microns is D90＜1 micron, and D50＜0.5 micron is to becoming the powder of porcelain crystal grain＜2 microns; Ultra-fine to D90＜0.4 micron; D50＜0.2 micron has only ultra-finely to described requirement, just can make the zirconia ceramics powder of making reach required requirement.
It is that calcining powder wet method in the ultra-fine dispersing apparatus of high speed is disperseed that described wet method is disperseed, and adds organic dispersing agent≤1%.Solid-liquid ratio is 4.5:5.5, adds organic binder bond 1% then.
Embodiment three
A kind of stable composition crystallite zirconia ceramics mixed powder and preparation method thereof is a major ingredient with the technical grade zirconia powder, and mixes an amount of cerium oxide (CeO), yttrium oxide (Y
2O
3), aluminum oxide and lime carbonate (CaCO
3) as stablizer, and each component is prepared according to following weight per-cent:
Cerium oxide (CeO) 11%, yttrium oxide (Y
2O
3) 1.2%, aluminum oxide (AL
2O
3) 5%, lime carbonate (CaCO
3) 1.5%, all the other are the technical grade zirconia powder;
Above-mentioned powder is carried out assembly according to proportioning, process stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation.
Described major ingredient is technical grade zirconia powder, baddeleyite and electric smelting method zirconia powder, and the three is according to the mixture of any group mode preparation.
The process method of processing stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation of above-mentioned stable composition crystallite zirconia ceramics mixed powder is: prepare starting material by above-mentioned prescription; Batch mixing is 12 hours in blender; In super-fine-ground equipment that mixed material is ultra-fine to require the to burn till big or small 1/5-1/10 of crystalline size; Be generally the 100-1000 nanometer; In temperature is to calcine 90-120 minute in the 900-1200 ℃ of stove, and the powder that calcining is good wet method in ultra tiny dispersing apparatus is disperseed, and adds the diffusing agent of organic branch ≦ 1%; Add the 0.3-1% sticker at last and carry out spraying drying, obtain the zirconia ceramics powder of stable composition.Described organic dispersing agent comprises triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, SEPIGEL 305, guar gum, fatty acid polyglycol ester: described sticker is the conventional sticker of zirconia powder, can be PanaviaTMF resin glue (Japanese Kuraray company); Multilink Sprint resin glue (Deng Sidunyi Huojia County company is disbursed from the cost and expenses): the reinforced glass ion sticker of RelyXTMLuting resin (Minnesota Mining and Manufacturing Company): the reinforced glass ion sticker of Fu ji plus resin (Japanese GC company).
Described ultra-fine be ultra-fine in super-fine-ground equipment; To the powder superfine fineness that becomes porcelain crystal grain＜5 microns is D190＜2.5 micron, and D50＜1 micron is to becoming the powder of porcelain crystal grain＜2 microns; Ultra-fine to D90＜1 micron; D50＜0.5 micron has only ultra-finely to described requirement, just can make the zirconia ceramics powder of making reach required requirement.
It is that calcining powder wet method in the ultra-fine dispersing apparatus of high speed is disperseed that described wet method is disperseed, and adds organic dispersing agent≤1%.Solid-liquid ratio is 4.5:5.5, adds organic binder bond 0.5% then.
The invention has the advantages that; Discover through of the present invention; When with stablizer and zirconia powder simultaneously ultra-fine to 90% particle diameter (being D90) less than the partial stabilization zirconium oxide ceramic crystal grain that burns till 1/5 the time; Median size (being D50) adopted multiple stablizer can reach the same stabilising effect of partially stabilized zirconia ceramics that chemical coprecipitation obtains fully less than 1/10 o'clock of the partial stabilization zirconium oxide ceramic crystal grain that burns till, and for example will obtain the partial stabilization zirconium oxide ceramic of 5 microns article grains; It is ultra-fine to D90＜1 micron that multiple stablizer and zirconium white are mixed the back, and D50＜0.5 micron can reach stable effect fully.And can adopt multiple stablizer that zirconium white is realized stable composition, the zirconia ceramics of stable composition has better physical and chemical performance usually.
The production technology and the equipment of nearly ten years especially nearly 2 years super-fine powders develop rapidly, and people can be without the methods of chemistry and adopted the mode of physics can produce all kinds of powders less than 200 nanometers.The development of this technology makes stablizer and zirconium white adopt the mode of physics to carry out mixed preparing with ripe the application, again through ultra tiny, calcine and can produce the PSZ mixed powder and become possibility.Its biggest advantage is no any pollution in the production process; The 2nd, overcome the defective that chemical coprecipitation can only adopt the single stable agent; Can adopt physics and the chemical property of multiple stablizer with the lift portion stabilization zirconium oxide ceramic, the 3rd, reduced raw-material cost and production cost significantly.
Claims (10)
1. stable composition crystallite zirconia ceramics mixed powder, it is characterized in that: with the technical grade zirconia powder is major ingredient, and mixes an amount of cerium oxide (CeO), yttrium oxide (Y
2O
3), aluminum oxide and lime carbonate (CaCO
3) as stablizer, and each component is prepared according to following weight per-cent:
Cerium oxide (CeO) 10%-12%, yttrium oxide (Y
2O
3) 1%-2%, aluminum oxide (AL
2O
3) 3%-8%, lime carbonate (CaCO
3) 1%-2%, all the other are the technical grade zirconia powder;
Above-mentioned powder is carried out assembly according to proportioning, process stable composition crystallite zirconia ceramics mixed powder through physics batch mixing, ultra-fine, calcining, dispersion, granulation.
2. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 1 is characterized in that: described major ingredient is technical grade zirconia powder, baddeleyite or electric smelting method zirconia powder.
3. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 1 is characterized in that: described major ingredient is technical grade zirconia powder, baddeleyite and the electric smelting method zirconia powder three mixture according to any group mode preparation.
4. the preparation method of a stable composition crystallite zirconia ceramics mixed powder as claimed in claim 1; It is characterized in that: the process method of stable composition crystallite zirconia ceramics mixed powder is: the prescription by claim 1 prepares starting material; Batch mixing was greater than 10 hours in blender; In super-fine-ground equipment that mixed material is ultra-fine to require the to burn till big or small 1/5-1/10 of crystalline size; In temperature is to calcine 90-120 minute in the 900-1200 ℃ of stove, and the powder that calcining is good wet method in ultra tiny dispersing apparatus is disperseed, and adds the diffusing agent of organic branch ≦ 1%; Add the 0.3-1% sticker at last and carry out spraying drying, obtain the zirconia ceramics powder of stable composition.
5. the preparation method of stable composition crystallite zirconia ceramics mixed powder as claimed in claim 4 is characterized in that: described organic dispersing agent comprises triethyl hexyl phosphoric acid, sodium lauryl sulphate, methyl amyl alcohol, derivatived cellulose, SEPIGEL 305, guar gum, fatty acid polyglycol ester.
6. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 4 is characterized in that: described sticker is the reinforced glass ion sticker of resin glue or resin.
7. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 4 is characterized in that: described ultra-fine be ultra-fine in super-fine-ground equipment.
8. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 7 is characterized in that: described ultra-fine be to be D90＜1 micron to the powder superfine fineness that becomes porcelain crystal grain＜5 microns, D50＜0.5 micron.
9. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 4 is characterized in that: described ultra-fine be to becoming the powder of porcelain crystal grain＜2 microns, ultra-fine to D90＜0.4 micron, D50＜0.2 micron.
10. stable composition crystallite zirconia ceramics mixed powder as claimed in claim 4 is characterized in that: it is that calcining powder wet method in the ultra-fine dispersing apparatus of high speed is disperseed that described wet method is disperseed, and adds organic dispersing agent≤1%; Solid-liquid ratio is 4.5:5.5, adds organic binder bond 0.3-1% then.
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