CN101182231B - Inorganic binder, preparation method and its application in preparation of porous ceramics - Google Patents
Inorganic binder, preparation method and its application in preparation of porous ceramics Download PDFInfo
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- CN101182231B CN101182231B CN2007101704948A CN200710170494A CN101182231B CN 101182231 B CN101182231 B CN 101182231B CN 2007101704948 A CN2007101704948 A CN 2007101704948A CN 200710170494 A CN200710170494 A CN 200710170494A CN 101182231 B CN101182231 B CN 101182231B
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- mineral binder
- binder bond
- aluminum oxide
- aluminium hydroxide
- phosphoric acid
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Abstract
The invention relates to an inorganic bond, a preparation method thereof and an application for the preparation of a porous ceramic thereof. The bond consists of alumina and/or aluminum hydroxide, phosphoric acid and boric acid, wherein, the weight percentage content of the alumina and/or the aluminum hydroxide is 70 percent to 99.5 percent, the weight percentage content of the phosphoric acid is30 percent to 0.5 percent, and additionally the weight percentage content of the boric acid is 0 percent to 15 percent. The weight percentage content of the aluminum hydroxide is converted into Al2O3. The mol ratio of phosphor and aluminum is less than one. When the bond is used for preparing for the porous ceramic, firstly the granular diameter of the alumina or the aluminum hydroxide used for preparing for the bond is confirmed, and the granular diameter of the alumina or the aluminum hydroxide for using is 0.01 time to 0.5 time of the granular diameter of ceramic powder material; non-oxideceramic powder material is mixed uniformly and mixed uniformly with pore-forming agent or vesicant to be molded and sintered, the sintering temperature is between 900 DEG C to 1600 DEG C. The sintering atmosphere is processed in air or under the inert atmosphere.
Description
Technical field
The present invention relates to a kind of preparation and the application in the porous ceramic film material preparation thereof of mineral binder bond.
Background technology
To various function ceramics, a large amount of ceramic products are accompanied by people's life from domestic ceramics.Burning till of pottery, especially high-performance ceramic burn till 1600 ℃ of general needs even higher temperature.High temperature burns till must need to consume a large amount of energy, and the kiln material is proposed harsh requirement.Therefore, the firing temperature that reduces pottery can directly reduce the cost of investment and the production cost of ceramic enterprise from aspects such as energy consumption, equipment purchasings.Under the situation of especially be on the rise at global energy crisis, environment protection is urgent day by day, the firing temperature that reduces pottery has great importance.
Up to the present, many bibliographical informations have been arranged in, the preparation and the application of low temperature mineral binder.Though in these, the kind of low temperature mineral binder is a lot, roughly can be divided into two big classes: 1. can in, produce the mixture of glassy phase under the low temperature; 2. aluminum phosphate class mineral binder bond.Produce glassy phase in, low temperature mineral binder and existing mineral binder bond be basic ingredient with the silicon oxide mostly, adds materials such as aluminum oxide and boron oxide again.Raw material directly uses through mixing the back, perhaps again through founding into glass and pulverizing the back and use.Material such as aluminum oxide and boron oxide can be regulated performances such as the melt temperature of glassy phase and intensity.The main component of aluminum phosphate class mineral binder bond is aluminium dihydrogen phosphate and condenses thereof, is mixed with the form of colloidal sol usually, also needs to add solidifying agent and anticracking agent etc. sometimes.Though all can reduce ceramic firing temperature significantly after using this two classes mineral binder bond, have significant disadvantages.The mineral binder bond disadvantage that the former produces glassy phase is that the glassy phase that they form can reduce the high-temperature behavior of pottery in pottery.The shortcoming of aluminum phosphate class binding agent then comprises: 1. acidity is too strong, can make equipment suffer heavy corrosion; 2. the easy moisture absorption of aluminium dihydrogen phosphate, adhesion makes the operability variation of material; 3. aluminium dihydrogen phosphate at high temperature decomposes and generates a large amount of water, forms bubble easily or make it distortion in pottery.
The present invention intends providing a kind of and above-mentioned mineral binder bond and sintering aid that significant mineral binder bond is arranged from chemical constitution and physical aspect, thereby can effectively avoid occurring the shortcoming similar to it.
Summary of the invention
One of purpose of the present invention is the mineral binder bond that provides a kind of, by aluminum oxide or/and aluminium hydroxide, small amounts of phosphoric acid and a small amount of boric acid, through mixing, reaction and obtaining.Phosphoric acid in the binding agent and boric acid can reduce the firing temperature of porous ceramics.
Mineral binder bond provided by the invention is made up of aluminum oxide and/or aluminium hydroxide, phosphoric acid and boric acid, wherein the quality percentage composition of aluminum oxide and/or aluminium hydroxide is 70%-99.5%, the quality percentage composition of phosphoric acid is 30%-0.5%, and the quality percentage composition of the boric acid that adds is 0%-15%; The quality percentage composition of aluminium hydroxide is amounted to into the Al2O3 meter; The mol ratio of phosphorus and aluminium is less than 1.Aspect the composition of mineral binder bond of the present invention, the mole number ratio that its maximum characteristics are phosphorus and aluminium is less than 1.And in common aluminum phosphate binder, the mol ratio of phosphorus and aluminium is between 1-3.2, and the most frequently used mol ratio is 3.1-3.2.In fact, in existing aluminum phosphate binder, aluminum oxide or aluminium hydroxide have dissolved fully and have formed phosphoric acid salt, and independently aluminum oxide or aluminum hydroxide particles do not exist.On the contrary, in mineral binder bond of the present invention,, be not enough to disappear fully molten aluminum oxide or aluminum hydroxide particles because the consumption of phosphoric acid is few, so still the existing with the particulate form of aluminum oxide and/or aluminium hydroxide, just at each Al
2O
3Or Al (OH)
3The particulate surface has formed the aluminum phosphate sol gel film.This mineral binder bond has two outstanding advantages:
1. aluminum oxide or aluminum hydroxide particles can play bridge joint between ceramic particle, and the crystal boundary bonded area of ceramic particle is increased, thereby the intensity of ceramic product is improved, and keep the high pore texture (see figure 1) of pottery simultaneously again.
2. the acidity of aluminum phosphate sol gel film is less than the acidity of aluminium dihydrogen phosphate, and moisture absorption is also not obvious.This is because in mineral binder bond of the present invention, do not have free phosphoric acid, and the content of phosphalugel is lower.
In mineral binder bond of the present invention, employed phosphoric acid quality percentage concentration is 85%, can suitably add boric acid (adding).Boric acid and phosphatase reaction generate borophosphoric acid.For boric acid and phosphoric acid are fully reacted, can be earlier the phosphoric acid and the boric acid of formula ratio be generated colloidal sol 100-120 ℃ of reaction, and then add Al to
2O
3And/or Al (OH)
3In.In binding agent, the content of boron is high more, and then the binding agent temperature of having an effect is also low more.But, the practical function temperature of binding agent should be not less than 900 ℃.Because below the temperature, the crystalline phase of aluminum phosphate and borophosphoric acid can not change fully at this.
When mineral binder bond of the present invention is applied to prepare porous ceramics, at first need to determine the grain diameter of preparation employed aluminum oxide of binding agent or aluminium hydroxide according to the grain diameter of ceramic powder, secondly will prepare material and mix by grinding, ball milling or other hybrid mode, one or more in the reagent that needs sometimes to add entry, ethanol and have the surfactivity effect are as dispersion medium or prevent particle agglomeration.
In the employed mineral binder bond, the grain diameter of aluminum oxide or aluminium hydroxide should be less than 0.5 times of ceramic powder grain diameter, but the former should be not little to 0.01 times of the latter.If the grain diameter of aluminum oxide or aluminium hydroxide is too big in the binding agent, just can not guarantee that ceramic particle has the adhesive particle of sufficient amount on every side.Otherwise if the granularity of aluminum oxide or aluminium hydroxide is too little in the binding agent, adhesive particle is just reunited easily so.Both of these case all is unfavorable for the bonding of binding agent to ceramic particle, thereby can't obtain high-intensity stupalith or product.
In order to guarantee the thorough mixing of mineral binder bond and ceramic powder, can make water, ethanol and have surface-active chemical reagent as dispersion medium, methods such as granulation and spraying drying also can be used for improving material dispersed and moulding.In addition, when the preparation porous ceramics, add pore-forming material or whipping agent if desired, so just should earlier mineral binder bond be mixed with ceramic powder, and then add pore-forming material or whipping agent, and mix.
Behind ceramic powder and the binding agent mixing moulding, can under environment such as air, inert atmosphere and vacuum, burn till.For oxide ceramics, perhaps use to hang down and burn till the non-oxide ceramics of temperature, can in air atmosphere, burn till.For non-oxide ceramics,, so just need to select inert atmosphere or vacuum environment if under higher temperature, burn till.In sintering process, the aluminum phosphate in the mineral binder bond, borophosphoric acid and precursor thereof can pass through complicated process such as decomposition, fusion, crystallization, with the alumina particle clinkering in the binding agent to ceramic particle, thereby ceramic particle is bonded together.Because mineral binder bond exists with the powder form, therefore, just can make bonding interface have very big area, thereby guarantee that pottery has high-intensity characteristic as long as the particle size of aluminum oxide wherein or aluminium hydroxide is suitable.In addition, when use in the mineral binder bond be aluminium hydroxide the time, a series of processes such as aluminium hydroxide also can decompose in the sintering process of pottery, fusion, crystallization, this also helps the binding agent clinkering to ceramic particle.Prepared porous ceramic matrices suitable is Al
2O
3, ZrO
2, SiC, Si
3N
4Or AlN etc.
In the present invention, owing to do not use silicon-dioxide, the consumption of phosphoric acid and boron oxide is also fewer simultaneously, therefore can not generate a large amount of glassy phases in the binding agent reacting phase.In the binding agent reacting phase, main composition is aluminum oxide, aluminum phosphate and borophosphoric acid crystalline phase.The shortage of glassy phase has guaranteed ceramic high-temperature behavior.
In an embodiment, the porous ceramics sample that burns till is made the sample of 5 * 8 * 50mm.The open porosity of sample and volume density are measured according to Chinese Industrial Standards (CIS) GB-T 1966-1996, usefulness Archimedes method.The bending strength of sample is tested on material-testing machine with three-point bending method.
In oxide compound or non-oxide ceramics powder, add this mineral binder bond, add pore-forming material, organic polymer binding agent and water as required again, obtain base substrate through mixing, moulding.The exsiccant base substrate burns till in 900-1600 ℃ air, inert atmosphere or vacuum, obtains porous ceramics.
When being used to prepare porous silicon carbide ceramic, the binding agent that uses aluminum oxide or aluminium hydroxide and phosphoric acid, boric acid to form is a pore-forming material with graphite, burns till under 1300 ℃ of air atmosphere, and obtained porous silicon carbide ceramic porosity is 30-50%.
Description of drawings
Fig. 1 plays bridge joint effect synoptic diagram for aluminum oxide or the aluminum hydroxide particles in the mineral binder bond of the present invention between ceramic particle:
A. be the direct sintering of ceramic particle when not using binding agent;
B. be the particle bridge joint synoptic diagram between ceramic particle behind the use binding agent provided by the invention.
Embodiment
Embodiment 1
1.20g boric acid is mixed with 3.00g phosphoric acid solution (mass concentration is 85%), and be heated to 100 ℃ and make colloidal sol.Then 100g aluminium hydrate powder (the meta particle diameter is 4.10 μ m) is joined in the refrigerative colloidal sol, ground and mixed obtains mineral binder bond.Get the 2.00g mineral binder bond, mix with 18g carborundum powder (the meta particle diameter is 20 μ m).Afterwards, add 3g Graphite Powder 99 (the meta particle diameter is 10 μ m) and 1g Walocel MT 20.000PV solution (mass concentration is 2%), and mix.The carborundum powder mixture that obtains is dry-pressing formed with the pressure of 50MPa.Base substrate burns till in 1300 ℃ air atmosphere, and soaking time is 2h.The result shows that the bending strength of sample is 12.6MPa, and porosity is 46.8%.
Embodiment 2
With embodiment 1, just do not add the pore-forming material Graphite Powder 99.The bending strength of the porous ceramics sample that obtains is 28.9MPa, and porosity is 37.5%.
Embodiment 3
With embodiment 1, wherein aluminium hydrate powder is replaced by aluminum oxide powder (the meta particle diameter is 1.49 μ m), the consumption of boric acid is 1.80g.The bending strength of the porous ceramics sample that obtains is 10.1MPa, and porosity is 45.3%.
Embodiment 4
With embodiment 1, do not add boric acid, do not add pore-forming material graphite.The bending strength of the porous ceramics sample that obtains is 21.4MPa, and porosity is 38.3%.
Embodiment 5
The preparation porous Al
2O
3Or ZrO
2Material uses binding agent provided by the invention with embodiment 1,2,3 or 4, makes porous Al
2O
3, ZrO
2Pottery.
Claims (7)
1. mineral binder bond, it is characterized in that its raw material is made up of aluminum oxide and/or aluminium hydroxide, phosphoric acid and boric acid, wherein the quality percentage composition of aluminum oxide and/or aluminium hydroxide is 70%-99.5%, the quality percentage composition of phosphoric acid is 30%-0.5%, and the quality percentage composition of the boric acid that adds is 0%-15%; The quality percentage composition of aluminium hydroxide is amounted to into Al
2O
3Meter; The mol ratio of phosphorus and aluminium is less than 1;
Wherein, described aluminum oxide or aluminium hydroxide are to exist with particle form; And the surface at each aluminium hydroxide or alumina particle forms the aluminum phosphate sol gel film.
2. by the described mineral binder bond of claim 1, it is characterized in that described binding agent is made up of aluminum oxide, aluminum phosphate and borophosphoric acid crystalline phase.
3. the method for preparing mineral binder bond as claimed in claim 1 is characterized in that concrete steps are:
(1) by the described proportioning weighing of claim 1;
(2) aluminum oxide and/or aluminium hydroxide and phosphoric acid, boric acid is mixed by ball milling or lapping mode; Perhaps boric acid earlier and phosphoric acid be heated to 100 ℃-120 ℃ and make and add aluminum oxide again behind the colloidal sol and/or aluminium hydrate powder is made mineral binder bond.
4. by the preparation method of the described mineral binder bond of claim 3, the mass percentage concentration that it is characterized in that described phosphoric acid is 85%.
5. the application of the described mineral binder bond of claim 1, when it is characterized in that being used to prepare porous ceramics, at first determine the grain diameter of preparation aluminum oxide that binding agent uses or aluminium hydroxide, the aluminum oxide that uses or the grain diameter of aluminium hydroxide are 0.01-0.5 times of the ceramic powder particle diameter; Mineral binder bond and ceramic powder is evenly mixed, add again pore-forming material or whipping agent mixed evenly after, moulding, sintering, sintering temperature is between 900 ℃-1600 ℃, sintering atmosphere is carried out under air or inert atmosphere.
6. press the application of the described mineral binder bond of claim 5, when it is characterized in that being used to prepare porous silicon carbide ceramic, the binding agent that uses aluminum oxide or aluminium hydroxide and phosphoric acid, boric acid to form, with graphite is pore-forming material, burn till under 1300 ℃ of air atmosphere, obtained porous silicon carbide ceramic porosity is 30-50%.
7. by the application of the described mineral binder bond of claim 5, it is characterized in that described ceramic powder is Al
2O
3, ZrO
2, SiC, Si
3N
4Or AlN.
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| CN2007101704948A CN101182231B (en) | 2007-11-16 | 2007-11-16 | Inorganic binder, preparation method and its application in preparation of porous ceramics |
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| CN2007101704948A CN101182231B (en) | 2007-11-16 | 2007-11-16 | Inorganic binder, preparation method and its application in preparation of porous ceramics |
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| CN101182231B true CN101182231B (en) | 2010-10-20 |
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| CN108483965A (en) * | 2018-05-18 | 2018-09-04 | 萧县沃德化工科技有限公司 | A kind of technique preparing accelerator using industrial waste phosphoric acid |
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| CN109680365B (en) * | 2019-01-24 | 2021-04-27 | 南京理工大学 | Method for preparing hollow aluminum borate ceramic fiber by using pampas grass fiber |
| CN110317020A (en) * | 2019-06-27 | 2019-10-11 | 合肥丰德科技股份有限公司 | A kind of bonding material of ceramic filter element and preparation method thereof |
| CN110665342B (en) * | 2019-10-06 | 2021-10-22 | 湖北大学 | Preparation method of mixed hydrophilic and hydrophobic material surface for efficiently collecting water mist based on spraying |
| CN113134893A (en) * | 2020-01-20 | 2021-07-20 | 西部宝德科技股份有限公司 | Preparation method of ceramic fiber filter tube for high-temperature flue gas purification |
| CN114804631B (en) * | 2022-03-16 | 2022-11-01 | 佛山市帆思科材料技术有限公司 | Matte antibacterial digital ink-jet printing glaze |
| CN116239383B (en) * | 2023-05-08 | 2023-08-15 | 苏州拓瓷科技有限公司 | Silicon carbide ceramic preform and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0097944A2 (en) * | 1982-06-29 | 1984-01-11 | Kabushiki Kaisha Toshiba | Method for directly bonding ceramic and metal members and laminated body of the same |
| CN1356966A (en) * | 1998-12-08 | 2002-07-03 | 威廉·J·小麦克纳尔蒂 | Inorganic cementatious material |
| CN1433345A (en) * | 1999-12-02 | 2003-07-30 | 福塞科国际有限公司 | Binder compositions for bonding particulate material |
| CN101014552A (en) * | 2004-07-12 | 2007-08-08 | 通用电气公司 | Ceramic bonding composition, method of making, and article of manufacture incorporating the same |
-
2007
- 2007-11-16 CN CN2007101704948A patent/CN101182231B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0097944A2 (en) * | 1982-06-29 | 1984-01-11 | Kabushiki Kaisha Toshiba | Method for directly bonding ceramic and metal members and laminated body of the same |
| CN1356966A (en) * | 1998-12-08 | 2002-07-03 | 威廉·J·小麦克纳尔蒂 | Inorganic cementatious material |
| CN1433345A (en) * | 1999-12-02 | 2003-07-30 | 福塞科国际有限公司 | Binder compositions for bonding particulate material |
| CN101014552A (en) * | 2004-07-12 | 2007-08-08 | 通用电气公司 | Ceramic bonding composition, method of making, and article of manufacture incorporating the same |
Non-Patent Citations (1)
| Title |
|---|
| JP特开平4-265280 1992.09.21 |
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Effective date of registration: 20121206 Address after: 333000, Jiangxi Jingdezhen hi tech Industrial Development Zone on the south side of Indus Avenue Patentee after: Jiangxi hi ring ceramic Polytron Technologies Inc Address before: 333000, room 618, 308 porcelain Road, Jingdezhen, Jiangxi Patentee before: Shanghai Institute of Ceramics, Chinese Academy of Sciences |