CN105347790A - Zirconia ceramic bearing preparation method based on gel casting technology - Google Patents
Zirconia ceramic bearing preparation method based on gel casting technology Download PDFInfo
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Abstract
The invention provides a zirconia ceramic bearing preparation method based on a gel casting technology. The zirconia ceramic bearing preparation method comprises the following steps that yttria-stabilized tetragonal phase zirconia powder, aluminum oxide powder, silicon nitride powder, a dispersing agent, gel and a demoulding agent are supplied; after ball milling is performed on the yttria-stabilized tetragonal phase zirconia powder, the aluminum oxide powder, the silicon nitride powder, the dispersing agent and an appropriate amount of deionized water, ceramic powder suspended matter is prepared, ball milling is performed by adopting a wet ball milling technology, and zirconia balls are adopted as mill balls; the ceramic powder suspended matter is preheated; the gel is heated and dissolved to obtain a gel solution, the heated gel solution is immediately added into the preheated ceramic powder suspended matter, and stirring, mixing and defoaming are performed to obtain ceramic slurry; after the side wall of the interior of a mould is coated with the demoulding agent, the ceramic slurry is injected into the mould, standing forming is performed, and after demouding drying is performed, a bearing green body is obtained; the bearing green body is calcined to obtain a zirconia ceramic bearing. According to the preparation method, toxicity generated to the environment and operating personnel can be eliminated.
Description
Technical field
The present invention relates to Ceramic gel injection mold technical field, particularly relate to a kind of zirconia ceramics bearing preparation method based on Gel-casting process.
Background technology
At present, along with modern industrial technology develop rapidly, the performance of material requested is had higher requirement.Traditional metal materials hardness, wear-resisting, high temperature resistant in can not be applicable to high-technology field, therefore a lot of scholar starts to stupalith seeking solution.Stupalith is the material that in engineering materials, rigidity is best, hardness is the highest, and ultimate compression strength is very high.And stupalith generally has high-melting-point, and chemical stability is good in hot environment, has good resistance to corrosion to acid, alkali, salt.Pottery thermal conductivity is low, is good lagging material.When the temperature is changed, pottery has good dimensional stability.Therefore, stupalith is widely used as structured material.Some pottery also has special electricity, light, magnetic performance, can be used as function ceramics.Therefore, people extremely pay close attention to the raising of stupalith reliability and the reduction of manufacturing cost thereof
Especially it is to be noted, the reliability of stupalith preparation technology determines the reliability of its use properties substantially, preparation technology determines preparation cost, advanced technology of preparing not only can make product structure, shape, function to greatest extent close to actual operation requirements, reduce post-production cost, and scrap rate can be reduced, thus reduce production cost further.Shaping is exactly that ceramic powder processing is prepared into the base substrate with definite shape and size.
Wherein, dry-press process mainly comprises dry-pressing formed, hot-forming, isostatic pressing, mainly refers to traditional dry-pressing formed.Be exactly adopt pressure ceramic powder to be pressed into the ceramic body with definite shape when not adding water as the term suggests dry-pressing formed.Its essence uses external force that powder is real at mould inner pressure exactly, and make particle close to each other, now powder just can combine by internal friction securely, makes the powder flocked together have certain shape.Isostatic pressing, as a kind of special forming method, grows up based on conventional dry is molded.What difference was that its transmission of pressure utilizes is liquid, and liquid can apply pressure to the powder in mould from all directions.Because liquid has homogeneity, internal pressure has consistence, therefore, the pressure that powder is born in all directions has consistence, therefore, it is possible to eliminate the part difference of density in base substrate preferably, but it still cannot overcome the uneven problem of blank density for large size or heavy in section parts.
For the problems referred to above, comparatively speaking, equipment is fairly simple and Application comparison extensive, and shaping requirement is lower, and in wet moulding, slurry mixes, and make shaping rear base substrate uniform composition, defect is few for wet therapy forming process.Wherein, gel casting forming is as a kind of forming process of ceramics technology of novel near net-shape, and slurry has good mobility, mould can be filled well, therefore be easy to the base substrate preparing complicated shape, avoid later stage mechanical workout, can suitable shape be reached, reduce costs.In addition, because monomer and linking agent are organism, can get rid of completely in sintering process, therefore, the parts high purity after sintering.Compare other colloid forming method, gel injection molding and forming technology has obvious advantage.Higher, not easy to crack by the shaping ceramic body intensity obtained of acrylamide polymerization, can not be out of shape during the demoulding
But traditional gel injection molding and forming technology still exists following defect: because monomeric acrylamide has toxicity, therefore, while guaranteeing blank strength, can produce environment again and pollute, and threat is created to the health of human body of operator.In addition, monomeric acrylamide, in polymerization process, likely can be subject to the impact of oxygen, and make base substrate produce the problems such as cracking or peeling, moulding process controllability is poor.
Summary of the invention
Based on this, be necessary to provide a kind of toxicity lower and the zirconia ceramics bearing preparation method based on Gel-casting process of the higher zirconia ceramics of physical strength can be obtained.
Based on a zirconia ceramics bearing preparation method for Gel-casting process, comprise the steps:
Yttrium is provided to stablize tetragonal phase zirconium oxide powder, alumina powder jointed, beta-silicon nitride powder, dispersion agent, gelifying agent, releasing agent;
Described yttrium is stablized tetragonal phase zirconium oxide powder, described alumina powder jointed, beta-silicon nitride powder, described dispersion agent and appropriate amount of deionized water put into after ball grinder carries out ball milling operation, prepare ceramic powder suspended substance, wherein, described ball milling is wet ball grinding technique, and adopts zirconia ball as mill ball;
Described ceramic powder suspended substance is carried out preheating;
Described gelifying agent heating for dissolving is obtained gelling agent solution, while hot described gelling agent solution is added in the described ceramic powder suspended substance of preheating, is uniformly mixed, and carry out de-bubble, obtain ceramic size;
After die inside wall coating releasing agent, in described mould, inject described ceramic size, leave standstill shaping, after demoulding drying, obtain bearing green compact;
Described bearing green compact are calcined, obtains described zirconia ceramics bearing.
Wherein in an embodiment, described ball milling carries out with the rotating speed of 700r/min ~ 800r/min.
Wherein in an embodiment, the time length of described ball milling is 12 hours ~ 48 hours.
Wherein in an embodiment, the mass ratio of described mill ball and described ceramic powder suspended substance is 1:(2 ~ 3).
Wherein in an embodiment, the diameter of described mill ball is 5 ~ 20mm.
Wherein in an embodiment, also alumina balls are adopted to be mill ball.
Wherein in an embodiment, described dispersion agent comprises ammonium polyacrylate.
The above-mentioned zirconia ceramics bearing preparation method based on Gel-casting process adopts the gelifying agent of nontoxicity and environmental protection, Gel-casting process is carried out relative to the virose monomeric acrylamide polymerization of traditional employing, above-mentioned preparation method can eliminate to the toxicity that environment and operator produce in preparation process, environmental protection.In addition, the zirconia ceramics bearing mechanical intensity for preparing of above-mentioned preparation method is higher.
Accompanying drawing explanation
Fig. 1 is the schema of the zirconia ceramics bearing preparation method based on Gel-casting process of an embodiment.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
As shown in Figure 1, the zirconia ceramics bearing preparation method based on Gel-casting process of an embodiment, comprises the steps:
S110: provide yttrium to stablize tetragonal phase zirconium oxide powder, alumina powder jointed, beta-silicon nitride powder, dispersion agent, gelifying agent, releasing agent.
In order to improve better Gel-casting process shaping after the intensity of green compact, such as, the median size that described yttrium stablizes tetragonal phase zirconium oxide powder is 0.6 μm ~ 5 μm; And for example, described alumina powder jointed median size is 0.5 μm ~ 5 μm; And for example the median size of described beta-silicon nitride powder is 0.5 μm ~ 5 μm, like this, adopt above-mentioned particle diameter, as, adopt that the yttrium of Nano Particle stablizes tetragonal phase zirconium oxide powder, alumina powder jointed, beta-silicon nitride powder can improve better Gel-casting process shaping after the intensity of green compact, meanwhile, when being also conducive to follow-up making slurry, three's is dispersed.
In one embodiment, described yttrium stablizes tetragonal phase zirconium oxide powder, described mass ratio that is alumina powder jointed and beta-silicon nitride powder is (80 ~ 95): (5 ~ 20): (5 ~ 10), preferably, described yttrium stablizes tetragonal phase zirconium oxide powder, described mass ratio that is alumina powder jointed and beta-silicon nitride powder is 90:10:10, like this, when adopting that the yttrium of above-mentioned mass ratio stablizes tetragonal phase zirconium oxide powder, alumina powder jointed, beta-silicon nitride powder can be beneficial to follow-up making slurry, three's is dispersed.In addition, adopt the yttrium of above-mentioned mass ratio stablizes tetragonal phase zirconium oxide powder, alumina powder jointed, beta-silicon nitride powder makes green compact after firing, the advantage that physical strength is higher can be had.
S120: described yttrium is stablized tetragonal phase zirconium oxide powder, described alumina powder jointed, beta-silicon nitride powder, described dispersion agent and appropriate amount of deionized water put into after ball grinder carries out ball milling operation, prepare ceramic powder suspended substance.
By described yttrium being stablized tetragonal phase zirconium oxide powder, described alumina powder jointed, beta-silicon nitride powder and dispersant, and utilize dispersion agent to the dissemination of three kinds of powders, described yttrium can be made to stablize tetragonal phase zirconium oxide powder, described alumina powder jointed, beta-silicon nitride powder disperses better, thus the ceramic powder suspended substance of high solid loading can be prepared, i.e. the in-situ solidifying process of this suspensoid of ceramic powder suspended substance.
Be appreciated that green compact prepared by the ceramic powder suspended substance of high solid loading are when calcinations and sintering, the situation that can reduce strain cracking occurs, and namely can realize the sintering effect of dead size.Such as, the solid content of the described ceramic powder suspended substance prepared is 50vol% ~ 65vol%, and preferably, the solid content of the described ceramic powder suspended substance prepared is 65vol%, like this, can realize the sintering effect of dead size.
In one embodiment, ceramic powder suspended substance comprises each component of following mass parts: the dispersion agent of 0.4 part ~ 0.6 part; The yttrium of 80 parts ~ 95 parts stablizes tetragonal phase zirconium oxide powder; The beta-silicon nitride powder of 5 parts ~ 20 parts alumina powder jointed and 5 parts ~ 10 parts; And appropriate deionized water, the consumption of deionized water is to guarantee that ball milling carries out smoothly.
In one embodiment, described ball milling is wet ball grinding technique, and adopts zirconia ball as mill ball; And for example, described ball milling carries out with the rotating speed of 700r/min ~ 800r/min; And for example, the time length of described ball milling is 12 hours ~ 48 hours; And for example, the mass ratio of described mill ball and described ceramic powder suspended substance is 1:(2 ~ 3); And for example, the diameter of described mill ball is 5 ~ 20mm; And for example, also adopt alumina balls to be mill ball, like this, be conducive to obtaining the better and particle diameter of dispersion effect evenly ceramic powder suspended substance.
In one embodiment, described dispersion agent comprises at least one in ammonium polyacrylate and ammonium citrate, and and for example, it is 1:(2 ~ 3 that described dispersion agent comprises mass ratio) ammonium polyacrylate and ammonium citrate; And for example, described dispersion agent comprises the ammonium polyacrylate and ammonium citrate that mass ratio is 1:1.5.
It should be noted that, on the one hand, in ceramic powder suspended substance system, the zeta current potential (eletrokinetic potential) of alumina suspension changes with the change of pH value, alumina suspension in acid condition zeta current potential be on the occasion of, along with the rising of pH value, the zeta current potential of ceramic powder suspended substance system can be impelled to reduce gradually, when pH value is near 9, reach iso-electric point, zeta current potential will be less than zero subsequently, therefore, when not adding dispersion agent, alumina suspension is dispersed relatively good in acid condition.But, when to add dispersion agent be mass ratio is 1:(2 ~ 3) ammonium polyacrylate and ammonium citrate time, it is larger on the impact of the zeta current potential of ceramic powder suspended substance system, in the basic conditions, as, when the pH of ceramic powder suspended substance system is 9 ~ 10, the zeta current potential absolute value of ceramic powder suspended substance system is larger than zeta current potential absolute value when not adding dispersion agent, that is, adopt the dispersion agent of above-mentioned mass ratio, can make ceramic powder suspended substance system dispersedly evenly.That is, zeta current potential absolute value is larger, then illustrate that the electrostatic repulsion forces between powder is larger, namely the dispersiveness of ceramic powder suspended substance system is better.So, when the pH of ceramic powder suspended substance system is 9 ~ 10, and to adopt dispersion agent to comprise mass ratio be 1:(2 ~ 3) ammonium polyacrylate and ammonium citrate time, its dispersion effect is better.On the other hand, in ceramic powder suspended substance system, the dispersiveness of Concentrated Zirconium Suspension is not as alumina suspension.When not adding dispersion agent, Concentrated Zirconium Suspension in acid condition zeta current potential be on the occasion of, along with the rising of pH value, the zeta current potential of suspension reduces gradually, and be reach iso-electric point near 9 in pH value, zeta current potential will be less than zero subsequently.Therefore, when not adding dispersion agent, Concentrated Zirconium Suspension is dispersed relatively good in acid condition.But, when to add dispersion agent be mass ratio is 1:(2 ~ 3) ammonium polyacrylate and ammonium citrate time, it is larger on the impact of Concentrated Zirconium Suspension zeta current potential, in the basic conditions, as, when the pH of ceramic powder suspended substance system is 9 ~ 10, Concentrated Zirconium Suspension is near 9 in pH value, as, when pH is 9 ~ 10, its zeta current potential absolute value increases to about 50 by zero, and this illustrates the Concentrated Zirconium Suspension adding dispersion agent, and dispersiveness is more better in the basic conditions.
Therefore, be 1:(2 ~ 3 by adding mass ratio) ammonium polyacrylate and the dispersion agent of ammonium citrate, and regulate the pH of ceramic powder suspended substance to be 9 ~ 10, each particle dispersion homogeneity can be obtained better, the good ceramic powder suspended substance of in-situ solidifying effect, be more conducive to the carrying out of follow-up Gel-casting process, to obtain the higher ceramic green of quality.
In one embodiment, the pH of described ceramic powder suspended substance is regulated to be 9 ~ 10; And for example, the pH of the described ceramic powder suspended substance of described adjustment is the operation of 9 ~ 10, adopts hydrochloric acid soln and ammonia soln to regulate; And for example, the volumetric molar concentration of described hydrochloric acid soln and described ammonia soln is 2mol/L, like this, is beneficial to the pH value regulating described ceramic powder suspended substance, and can not introduces foreign ion.
S130: described ceramic powder suspended substance is carried out preheating.
By ceramic powder suspended substance is carried out preheating, be conducive to follow-up blended with gelling agent solution.
S140: described gelifying agent heating for dissolving is obtained gelling agent solution, is added to described gelling agent solution in the described ceramic powder suspended substance of preheating while hot, is uniformly mixed, and carry out de-bubble, obtain ceramic size.
In one embodiment, described gelifying agent comprises at least one in gelling gum and card Derain glue, and and for example, it be mass ratio is 1:(1 ~ 1.5 that described gelifying agent comprises mass ratio) gelling gum and card Derain glue; And for example, gelling gum and the card Derain glue of described gelifying agent comprises mass ratio to be mass ratio be 1:1.5.It should be noted that, described gelling gum is a kind of natural foodstuff additive, can add use in right amount, nontoxicity, do not injure human body in varieties of food items by normal need of production, and its molecular formula is (C
6h
12o
6)
n, molecular weight is 2 × 10
5~ 3 × 10
5; Described card Derain glue is a kind of safe edible gel, and its molecular formula is (C
6h
10o
5)
n, molecular weight is 7 × 10
4.Therefore, adopt edible polysaccharide gel to replace traditional monomeric acrylamide polymerization to carry out Gel-casting process, can eliminate to the toxicity that environment and operator produce in preparation process, environmental protection.
It should be noted that, because gelling gum normal temperature is water insoluble, and can not form suspension, stirring or ball milling can make the mixture of gelling gum and water form the flexible glue state of thickness, therefore gelling gum directly can not be added in the process of preparation ceramic size.In addition, gelling gum is only only solution state when comparatively high temps, just has good mobility, and gel property is very responsive to temperature, by described ceramic powder suspended substance is carried out preheating, such as, the temperature of described preheating is 65 DEG C ~ 75 DEG C, and preferably, the temperature of described preheating is 70 DEG C.Afterwards, while hot described gelling agent solution is added in the described ceramic powder suspended substance of preheating, thus good mixed effect can be played, and can viscosity be reduced, be beneficial to follow-up injection molding.Be appreciated that heat setting colloidality is the specific physical properties that card Derain glue has, can gel be formed after the heating of its suspension liquid, and in different temperature ranges, there is different gelling properties.When temperature is higher than 54 DEG C, card Derain suspension liquid starts to become as clear as crystal state, be heated to 60 DEG C start to carry out cooling and just can form gel, if continue to be heated to 80 DEG C, now solution transparence will decline, again form gel gradually, therefore, the temperature choosing the preheating of described ceramic powder suspended substance is 65 DEG C ~ 75 DEG C, and the temperature controlling described gelling agent solution is 65 DEG C ~ 75 DEG C, like this, but when both mix, just can guarantee the mixing of described gelifying agent and described ceramic powder suspended substance, when injecting mould, also the shaping of green compact is more conducive to.
Further, also add calcium ion and magnesium ion to described gelling agent solution, such as, the volumetric molar concentration of the magnesium ion in described ceramic size is 18mmol/L, and the volumetric molar concentration of the calcium ion in described ceramic size is 6mmol/L.Like this, the formation of gel can be promoted, and the intensity of gel can be made to improve, be conducive to making gel irreversible, like this, when by described ceramic size injection molding, be conducive to the intensity and the uniformity coefficient that improve green compact, when after described green sintering, the physical strength of ceramic product can be improved.
Be appreciated that, when described ceramic powder suspended substance and gelling agent solution temperature be mix under the condition of 65 DEG C ~ 75 DEG C time, moisture in ceramic size can volatilize fast, cause the solid content of ceramic size excessive, even local dehydration is solidified, thus significantly reduce the mobility of ceramic size, be unfavorable for follow-up mould injection moulding operation.In order to reduce the volatilization of moisture, and then improve the mobility of ceramic size, such as, described in the operation that is uniformly mixed be specially constant-temperature vacuum and be uniformly mixed, like this, the volatilization of moisture can be reduced, and then improve the mobility of ceramic size.
S150: after die inside wall coating releasing agent, inject described ceramic size in described mould, leave standstill shaping, after demoulding drying, obtain bearing green compact.
High in order to prepare density, good mechanical properties and the described green compact being suitable for dead size processing, such as, described operation of injecting described ceramic size in described mould, also comprises the steps: described mould to shake, and discharges bubble; And for example, also utilize sharp shaped material, e.g., the bubble that concussion rear mold sidewall produces is introduced into the surface of ceramic size by the tip of iron wire, and removes, and like this, can prepare density high, good mechanical properties and the described green compact being suitable for dead size processing.
In one embodiment, described gelifying agent comprises at least one in Vaseline and vegetables oil, and preferably, described releasing agent is vegetables oil.Be appreciated that, due to the described gelifying agent that adopts, to comprise mass ratio be mass ratio is 1:(1 ~ 1.5) gelling gum and card Derain glue, described green compact after solidifying can stick together with the inner side-wall of mould, be unfavorable for the carrying out of the demoulding, further, also can there is the adhesion of lighter degree with green compact in Vaseline, adopt vegetables oil then can avoid this adhesion problems as releasing agent, to guarantee the planeness of described green compact sidewall, thus the quality of described green compact can be improved.
S160: calcined by described bearing green compact, obtains described zirconia ceramics bearing.
By by after described green compact calcinations and sintering, the ceramic bearing of better mechanical property can be obtained.The dry body ultimate compression strength of ceramic bearing can reach 4.5 ~ 5.1MPa, and the bending strength of sintered compact can reach 280 ~ 320MPa, and sintered density can reach more than 98.3%, better mechanical property.
In one embodiment, the described green compact after solidification at 80 DEG C ~ 100 DEG C dry 24 hours ~ 30 hours, then with at the ramp to 1550 of 5 DEG C/min DEG C, are incubated 2 hours ~ 3 hours, then, cool with furnace temperature.
The above-mentioned zirconia ceramics bearing preparation method based on Gel-casting process adopts the gelifying agent of nontoxicity and environmental protection, Gel-casting process is carried out relative to the virose monomeric acrylamide polymerization of traditional employing, above-mentioned preparation method can eliminate to the toxicity that environment and operator produce in preparation process, environmental protection.In addition, the zirconia ceramics bearing mechanical intensity for preparing of above-mentioned preparation method is higher.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1., based on a zirconia ceramics bearing preparation method for Gel-casting process, it is characterized in that, comprise the steps:
Yttrium is provided to stablize tetragonal phase zirconium oxide powder, alumina powder jointed, beta-silicon nitride powder, dispersion agent, gelifying agent, releasing agent;
Described yttrium is stablized tetragonal phase zirconium oxide powder, described alumina powder jointed, beta-silicon nitride powder, described dispersion agent and appropriate amount of deionized water put into after ball grinder carries out ball milling operation, prepare ceramic powder suspended substance, wherein, described ball milling is wet ball grinding technique, and adopts zirconia ball as mill ball;
Described ceramic powder suspended substance is carried out preheating;
Described gelifying agent heating for dissolving is obtained gelling agent solution, while hot described gelling agent solution is added in the described ceramic powder suspended substance of preheating, is uniformly mixed, and carry out de-bubble, obtain ceramic size;
After die inside wall coating releasing agent, in described mould, inject described ceramic size, leave standstill shaping, after demoulding drying, obtain bearing green compact;
Described bearing green compact are calcined, obtains described zirconia ceramics bearing.
2. the zirconia ceramics bearing preparation method based on Gel-casting process according to claim 1, it is characterized in that, described ball milling carries out with the rotating speed of 700r/min ~ 800r/min.
3. the zirconia ceramics bearing preparation method based on Gel-casting process according to claim 2, is characterized in that, the time length of described ball milling is 12 hours ~ 48 hours.
4. the zirconia ceramics bearing preparation method based on Gel-casting process according to claim 1, is characterized in that, the mass ratio of described mill ball and described ceramic powder suspended substance is 1:(2 ~ 3).
5. the zirconia ceramics bearing preparation method based on Gel-casting process according to claim 1, is characterized in that, the diameter of described mill ball is 5 ~ 20mm.
6. the zirconia ceramics bearing preparation method based on Gel-casting process according to claim 1, is characterized in that, also adopts alumina balls to be mill ball.
7. the zirconia ceramics bearing preparation method based on Gel-casting process according to claim 1, it is characterized in that, described dispersion agent comprises ammonium polyacrylate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699138A (en) * | 2017-01-24 | 2017-05-24 | 山东倍辰新材料有限公司 | Ceramic slag separator and gel injection molding manufacturing process thereof |
| CN108101534A (en) * | 2018-01-03 | 2018-06-01 | 王春梅 | The method of gel casting forming yttrium oxide partial stabilization zirconium oxide ceramic crucible |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072182A (en) * | 2013-01-08 | 2013-05-01 | 清华大学 | Gellan gum gel-based ceramic gel injection molding method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103072182A (en) * | 2013-01-08 | 2013-05-01 | 清华大学 | Gellan gum gel-based ceramic gel injection molding method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106699138A (en) * | 2017-01-24 | 2017-05-24 | 山东倍辰新材料有限公司 | Ceramic slag separator and gel injection molding manufacturing process thereof |
| CN108101534A (en) * | 2018-01-03 | 2018-06-01 | 王春梅 | The method of gel casting forming yttrium oxide partial stabilization zirconium oxide ceramic crucible |
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Application publication date: 20160224 |