CN101497524A - Preparation of compact magnesia partial stabilized zirconia ceramic - Google Patents
Preparation of compact magnesia partial stabilized zirconia ceramic Download PDFInfo
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- CN101497524A CN101497524A CNA2008100102955A CN200810010295A CN101497524A CN 101497524 A CN101497524 A CN 101497524A CN A2008100102955 A CNA2008100102955 A CN A2008100102955A CN 200810010295 A CN200810010295 A CN 200810010295A CN 101497524 A CN101497524 A CN 101497524A
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- stabilized zirconia
- compact
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Abstract
The invention relates to a method for preparing compact partially stabilized zirconia ceramics by using magnesium oxide. The method comprises the following steps: utilizing the magnesium oxide as a stabilizing agent, and introducing additives such as aluminum oxide, silicon oxide, calcium oxide and the like by adopting a coprecipitation method to synthesize nano-scale/sub-micron-scale powder; and then heating the components at a lower temperature by using liquid-phase sintering to obtain a compact zirconia ceramic material. The method has the main characteristics that the method can accurately control contents of the stabilizing agent and each additive so as to disperse the stabilizing agent and the additives evenly; the synthesized powder has even granularity and small grain size; and under the condition of the lower sintering temperature, a sinter with good compactness can be obtained. The method has the advantages of simple process and low equipment investment, and is favorable for industrialized mass production.
Description
What the present invention relates to is a kind of method for preparing compact magnesia partial stabilized zirconia ceramic, belongs to the oxide ceramic material field.
Zirconium white is the novel texture stupalith that grows up the seventies in 20th century, owing to have wear-resistant, corrosion-resistant, characteristics such as intensity is big, fusing point height, has a wide range of applications in fields such as metallurgy, electronics, chemical industry, machineries.Mainly there are three kinds of different crystal formations in zirconium white: cube phase, four directions phase and monocline are mutually.Transforming relationship between zirconia polycrystalline type and the temperature is expressed as follows:
It should be noted that wherein there is the volumetric expansion effect of 7-9% in the four directions in the phase transition process of monocline phase, thereby produce big stress, in the zirconium white structure, can produce tiny crack, in addition cracked.But, after adding stablizers such as suitable oxidizing yttrium, magnesium oxide, calcium oxide, strontium oxide, aluminum oxide, cube phase of high-temperature stable also can at room temperature stablize mutually with the four directions or meta exists, reduced transformation stress, thereby made zirconia ceramics bring into play important role in a lot of fields.Wherein, the magnesia partial stabilized zirconia ceramic material is widely used in disposable sensing device as electrochemical sensor and measures dissolved oxygen amount in the molten steel.This material in order to prevent the infiltration of gas molecule, also has structural requirements such as high-compactness except requiring as electric properties such as hyperoxia transference number of ions and specific conductivity.But, zirconium white is a kind of extremely difficult agglomerating material, at present both at home and abroad the preparation magnesia partial stabilized zirconia ceramic generally adopts electricity to melt the Zirconium oxide powder that zirconium white or other method make to be raw material, to make the stablizer solid solution advance zirconium white crystal grain in high-temperature sintering process.For the widespread use and the suitability for industrialized production of material, their subject matter has the following aspects:
(1) raw material granularity is bigger, the sintering temperature height, and to the requirement height of equipment, energy consumption is big;
(2) adopt high temperature solid-phase sintering, its grain-size size is difficult to control;
(3) zirconium white crystal grain is advanced in solid solution under the stablizer condition of high temperature, and it distributes in zirconium white crystal grain and is easy to inhomogeneously, influences the performance of material.
Studies show that nano level/sub-micron powder has high specific surface area, sintering activity is big, utilizes these powder also can reduce sintering temperature as raw material, improves the compactness of sintered specimen.Research and production practice show that it is the method that a kind of production technique is simple, raw materials cost is cheap, the gained powder characteristic is good that coprecipitation method prepares in the powder body material at wet chemical method.Compare with some other traditional inorganic materials preparation method, coprecipitation method has following advantage:
(1) technology and equipment are comparatively simple, can finish synthesizing with refinement during the precipitation, help industrialization;
(2) can accurately control each components contents, make the uniform mixing of realizing molecule/atomic level between the different components;
(3) in precipitation process, can control purity, granular size, dispersiveness and the phase composite of gained powder by control deposition condition and next step sedimentary calcinating system;
(4) the sample calcining temperature is low, stable performance and favorable reproducibility.
In addition, classical sintering theory shows that lqiuid phase sintering method is a kind of method of widespread use acceleration of sintering, and it can reduce sintering temperature significantly, improves sintered specimen compactness.
In order to solve the problem that present preparation densification magnesia partial stabilized zirconia ceramic exists, the PSZ that the present invention adopts the coprecipitation method synthetic to contain certain additive composition is a raw material, utilizes liquid phase sintering to obtain fine and close magnesia partial stabilized zirconia ceramic material in 1300 ℃-1800 ℃ heating.Specific implementation method is:
1. the following material dissolution that will comprise additive is in the aqueous solution that contains dispersion agent or alcohol solution:
A: zirconium-containing material, as ZrOCl
28H
2O or Zr (NO
3)
22H
2O etc.;
B: contain magnesium raw material, as Mg (NO
3)
26H
2O or MgCl
26H
2O etc.;
C: contain the additive of elements such as aluminium, silicon, calcium, as Al (NO
3)
39H
2O, Ca (NO
3)
24H
2O, AlCl
3, Na
2SiF
6Perhaps CaCl
2Deng.
Wherein, after each material was converted into oxide compound, their molar contents in sintered compact were respectively:
ZrO
2：80-98％；MgO：2-10％；Al
2O
3：0-6％，SiO
2：0-5％；CaO：0-5％.
2. after treating that raw material dissolves fully, under the intensively stirred condition of employing, obtain precipitation of hydroxide by following dual mode:
A: directly add ammoniacal liquor or sodium hydroxide solution, make the precipitation from homogeneous solution simultaneously of various elements;
B: heated solution is to certain temperature (50-75 ℃), makes that zr element generates post precipitation fully in the solution, continues to stir (0-5 hour) behind the certain hour, adds ammoniacal liquor or sodium hydroxide solution, and other element is evenly separated out around zirconium is sedimentary.
3. after the precipitation that will obtain is recycled washed with de-ionized water, adopt alcohol wash again.
4. after the precipitation after will cleaning (80-120 ℃) drying, (400-800 ℃) calcining is pulverized then at a certain temperature, and is levigate.
5. with behind the levigated powder compacting, after calcining once more prior to low temperature (600-1100 ℃), sintering under 1300-1800 ℃ of condition, (1000-1500 ℃) then at a certain temperature) processing back acquisition compact magnesia partial stabilized zirconia sintered compact (relative density〉95%).
The present invention has the following advantages:
(1) accurately control stabilization agent and various content of additive are disperseed them very uniformly, and the epigranular of synthetic powder, tiny.
(2) under lower sintering temperature condition, can obtain sinter with good compactness.Both energy-conserving and environment-protective have improved production efficiency again.
(3) technology is simple, and facility investment is few, helps large-scale industrialization production.
Description of drawings:
Fig. 1 be synthetic powder and sintered compact the dry back of diffraction result (a) powder, (b) 400 ℃ of calcined powders, (c) 1700 ℃ of sintered compacies
Fig. 2 is the scanned photograph of 400 ℃ of calcined powders
Further set forth characteristics of the present invention below by specific embodiment, what must state is that the present invention is confined to this embodiment absolutely not.
Example
According to certain proportioning with ZrOCl
28H
2O, Mg (NO
3)
26H
2O, Al (NO
3)
39H
2O, Na
2SiF
6, CaCl
2In the alcohol solution that contains the polyoxyethylene glycol dispersion agent, wherein the volume ratio of the second alcohol and water of alcohol solution is 5:1 etc. substance dissolves; After treating that raw material dissolves fully, slowly the solution that obtains is heated to 75 ℃ under the intensively stirred condition of employing, zr element generates post precipitation fully in solution, continues to stir half an hour; Then, adding ammoniacal liquor is 10 until the pH value; Then, the precipitation that obtains recycled washed with de-ionized water after, use AgNO
3There is not Cl in the detection paper precipitation
-After, adopt alcohol wash again.Then,, pulverize then 400 ℃ of calcinings at a certain temperature after the precipitation drying after cleaning, levigate.Then, behind the powder compacting that obtains, after 1100 ℃ of calcinings of low temperature, sintering under 1700 ℃ of conditions can obtain relative density 1400 ℃ of following thermal treatments then and reach 98% compact magnesia partial stabilized zirconia sintered compact.
Fig. 1 shows the diffraction result of synthetic powder and sintered compact.Wherein (a) is 105 ℃ of dry back powder, (b) is 400 ℃ of calcined powders, (c) is 1700 ℃ of sintered compact samples.As can be seen,, there is not other to exist mutually from the figure except crystal of zirconium oxide.After 105 ℃ of dryings, crystallization phases does not appear in the sample.After 400 ℃ of calcinings, all be converted into cubic, and the halfwidth of diffraction peak is bigger, then the particle diameter of explanation calcining back acquisition powder is little, helps sintering.Behind the high temperature sintering, both existed high conductivity cube phase in the sample, also had the monocline phase that can significantly improve material property, so this sintered compact physicochemical property of deducibility should compare well with mutually cubic.
Fig. 2 shows the scanned photograph of 400 ℃ of calcined powders.Powder diameter after the calcining is very little as can be seen from the figure, and in conjunction with not too tight, it is not serious to reunite between each particle.The sintering character of the powder that this explanation employing coprecipitation method obtains is superior.Sample behind the sintering is dense, and its relative density reaches 98%.
From embodiment as can be seen, the magnesia partial stabilized zirconia of the present invention's preparation is dense, and sintering temperature is lower, and technology controlling and process is simple, is fit to large-scale commercial production.
Claims (2)
1. method for preparing compact magnesia partial stabilized zirconia ceramic comprises kind, introducing method and the addition of additive.It is characterized in that:
1) kind of additive: the various materials that contain elements such as aluminium, silicon, calcium, and they are dissolved in and are neutral or acid behind the water.As Al (NO
3)
39H
2O, Ca (NO
3)
24H
2O, AlCl
3, Na
2SiF
6Perhaps CaCl
2Deng.
2) additive introducing method: in the process of coprecipitation method synthesis nano/submicron order powder, add various additives, make their homodisperse.
3) addition: require the molar content of oxide compound in sintered compact of each element of additive to be respectively Al
2O
3: 0-6%, SiO
2: 0-5%; CaO:0-5%.
2. the method for preparing compact magnesia partial stabilized zirconia ceramic according to claim 1 is characterized in that the molar content of oxide compound in sintered compact of each element of additive is respectively Al
2O
3: 0.5-2%, SiO
2: 0.5-2%; CaO:0.05-0.5%.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102245008A (en) * | 2010-05-10 | 2011-11-16 | 陈惠敏 | Circuit noise inhibiting method and inhibiting object thereof |
| CN105967687A (en) * | 2016-07-14 | 2016-09-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Grain-composition zirconia powder preparation and ceramic sintering method |
| CN109285985A (en) * | 2017-07-20 | 2019-01-29 | 天津凯普瑞特新能源科技有限公司 | A kind of PVDP lithium battery diaphragm |
| CN109336590A (en) * | 2018-10-22 | 2019-02-15 | 深圳市商德先进陶瓷股份有限公司 | Magnesia partial stabilized zirconia, magnesia partial stabilized zirconia ceramic and its preparation method and application |
| CN110903086A (en) * | 2019-12-10 | 2020-03-24 | 中钢集团洛阳耐火材料研究院有限公司 | High-performance magnesium-stabilized zirconia raw material |
| CN112876243A (en) * | 2021-02-20 | 2021-06-01 | 宁波泰科先进陶瓷有限公司 | Ceramic material, preparation method thereof and capsule coffee machine puncture needle made of ceramic material |
-
2008
- 2008-01-31 CN CNA2008100102955A patent/CN101497524A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102245008A (en) * | 2010-05-10 | 2011-11-16 | 陈惠敏 | Circuit noise inhibiting method and inhibiting object thereof |
| CN102245008B (en) * | 2010-05-10 | 2015-06-03 | 陈惠敏 | Circuit noise inhibiting method and inhibiting object thereof |
| CN105967687A (en) * | 2016-07-14 | 2016-09-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Grain-composition zirconia powder preparation and ceramic sintering method |
| CN105967687B (en) * | 2016-07-14 | 2019-04-12 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of the Zirconium powder preparation and ceramic post sintering method of grain composition |
| CN109285985A (en) * | 2017-07-20 | 2019-01-29 | 天津凯普瑞特新能源科技有限公司 | A kind of PVDP lithium battery diaphragm |
| CN109336590A (en) * | 2018-10-22 | 2019-02-15 | 深圳市商德先进陶瓷股份有限公司 | Magnesia partial stabilized zirconia, magnesia partial stabilized zirconia ceramic and its preparation method and application |
| CN109336590B (en) * | 2018-10-22 | 2021-12-03 | 深圳市商德先进陶瓷股份有限公司 | Magnesia partially stabilized zirconia, magnesia partially stabilized zirconia ceramic, and preparation method and application thereof |
| CN110903086A (en) * | 2019-12-10 | 2020-03-24 | 中钢集团洛阳耐火材料研究院有限公司 | High-performance magnesium-stabilized zirconia raw material |
| CN112876243A (en) * | 2021-02-20 | 2021-06-01 | 宁波泰科先进陶瓷有限公司 | Ceramic material, preparation method thereof and capsule coffee machine puncture needle made of ceramic material |
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