CN1092170C - Process for preparing biscuit of ceramics by reaction induced gelatination - Google Patents
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- CN1092170C CN1092170C CN99125696A CN99125696A CN1092170C CN 1092170 C CN1092170 C CN 1092170C CN 99125696 A CN99125696 A CN 99125696A CN 99125696 A CN99125696 A CN 99125696A CN 1092170 C CN1092170 C CN 1092170C
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Abstract
The present invention relates to a method for preparing biscuits of ceramics by reaction induction gelation, which belongs to the field of ceramic molding. The present invention is characterized in that stable acidic slurry with the pH value smaller than 4 and stable slurry under the alkaline condition with the pH value larger than or equal to 8.5 are prepared firstly, and then a small quantity of silicon oxide colloid is introduced in the slurry. The reaction of different inorganic or organic matter used as coagulators makes the pH value of the slurry kept from 4 to 8 to prepare the biscuits of the ceramics, namely that the gelation of the silicon oxide can be carried out faster within the range. The content of the silicon oxide is 0.5 to 10% of the total weight of the solid phase. The inorganic reaction, which has the function of coagulation, can be the hydrolysis reaction of silicon nitride, aluminium nitride, etc. The organic reaction comprises various enzyme catalytic reactions and acid-base catalytic reactions, such as the hydrolysis reaction of urea, carboxylic acid ester, lactone, etc.
Description
The present invention relates to a kind of method of utilizing reaction induced sol-gel transition to prepare biscuit of ceramics, more precisely, is to utilize silica sol to change the method for preparing gel biscuit of ceramics into, belongs to the forming process of ceramics field.
Forming process of ceramics is a key link among the ceramic preparation technology.The defective of introducing in the forming process of ceramics process as reunion, crackle etc., is difficult in the elimination of sintering stage, therefore can produce serious influence to end properties.Over past ten years, many new colloidal shaping methods have appearred in succession, for the solution of this problem provides good thinking.
The current method that generally is used for the biscuit of ceramics moulding has following several:
1. dry-pressing and static pressure such as grade.Utilize external pressure will have mobile powder and be compressed to biscuit with certain tap density.
2. extrusion moulding.To have thermoplastic slurry and from spout, extrude, obtain waiting the parts of axle shape.
3. injection molding.To contain paraffin etc. and have thermoplastic slurry and inject in the mould, the cooling back demoulding can obtain having the biscuit of complicated shape.
4. slurry casting.Slurry is injected in the porous mold, and moisture obtains biscuit after mould absorbs.
These methods are widely used in many aspects, but they also respectively have shortcoming.Be difficult to eliminate the microdefects such as coacervate that powder itself is brought into as dry-pressing and the method that waits static pressure.Extrusion moulding and injection molding all need through long de-waxing process, and cause defectives such as cracking, gauffer easily in base substrate.The not only time-consuming length of slurry casting, and in biscuit, produce density gradient easily, in dehydration, also cause the uneven distribution of soluble component easily.
For solving traditional forming method at forming ceramic, especially problems that exist during high-performance ceramic, progressively developed ceramic in-situ consolidation forming technology over past ten years, can make slurry without dehydration, the realization original position is solidified in no punch die, thereby can obtain the more uniform biscuit of microtexture.This class technology has complicated shape in moulding, and during the large-size ceramic parts, especially has advantage.
At United States Patent (USP) U.S.Pat.4,894,194,5,208,362 and 5,145, in 908, people such as Janney propose gel pouring (Gelcasting) forming process, utilize the organic monomer crosslinking polymerization under action of evocating that adds in the slurry, particle realization original position in the slurry is solidified, obtain having the formed body of certain intensity.
At United States Patent (USP) U.S.Pat5, in 667,548, the neutral substance reaction that people such as Graule and Gauckler adopt utilization to add in advance produces electrolysis matter to increase the ionic concn in the slurry liquid phase, make the electrostatic double layer compression of particle surface, slurry solidifies the method for preparing biscuit of ceramics without dehydration.At United States Patent (USP) U.S.Pat.5 subsequently, in 788,891 and 5,948,335, they propose also can utilize reaction to change the particulate surface charge again to solidify realizing, and the colloidal sol that adds organic or inorganic in slurry is to improve the intensity of biscuit.
People such as Kosmac propose to utilize hydrolysis of aluminium nitride to change in the slurry particulate chemical environment so that its method of solidifying can be used for potteries such as formed alumina, silicon nitride.
The proposition of these methods is for the colloidal formation of pottery has increased new content.But these methods all have its limitation.Though gel pouring moulding can obtain having the biscuit of higher-strength owing to must use the bigger polymerization single polymerization monomer of toxicity of more amount, therefore the casting process of biscuit with and subsequent organism take off bigger murder by poisoning all arranged in row's process.Though can reduce this toxicity to a certain extent by improvement, fundamentally not address this problem to polymerization reaction formulation.Comparatively speaking, directly solidifying casting (DCC) is the lower technology of a kind of pollution, but the resulting biscuit intensity of this technology is relatively low.The method of adding aluminium nitride then only is suitable in a few system.These technologies process of solidifying is slower mostly in addition, and setting rate is subjected to Temperature Influence, mostly need be at injection molding with post-heating to improve setting rate, again can be in the inner difference that produces setting rate of formed body, cause new inhomogeneously, therefore be difficult in actual procedure, be widely used.
The inventor notices that industrial, silicon oxide colloid has been widely used in fields such as paint, coating as binding agent etc.Because it has good adhesive effect to particles of inorganic material, be widely used in the moulding of sand mo(u)ld etc.Because the silicon oxide component is present in the ceramic raw material widely, and the colloidal sol of silicon oxide very easily forms gel, so inventor's gelling of proposing to control silicon oxide component in the raw material can realize the curing of ceramic size.
What the gelling of silica sol was had the greatest impact is the pH value of system and the ionic concn in the solution, and Fig. 1 demonstrates the influence of pH value to silica gel speed, and X-coordinate is the pH value, and ordinate zou is relative gelation rate.Curve 1 no ionogen adds, and curve 2 has ionogen to add.As seen from Figure 1, with the difference of pH value and ionic concn, silica sol agglomerative speed can change in the larger context.In fact, the speed of silicon oxide gelling can fade to a few hours by several minutes.Near pH value 6-7, the speed of gel is the highest, only is several minutes, and reaches 8.5-9 when above in the pH value, and gelling does not then take place, and utilizes these characteristics of silica gel, can be used for realizing the curing of various materials.
At United States Patent (USP) U.S.Par.2, in 603,570, Bole proposes a technology: regulate the pH value of the alkalescence of silicate sol to a little higher than agglomerative condition, this colloidal sol is mixed for the tart ceramic powder with the surface, and the pH value is reduced to the gelling scope behind the injection molding, reaches the purpose that original position is solidified.But because the pH value of system will be regulated by adding strong acid, final result will be decided by the acidic-group of powder surface and the effect of basic component, and accuracy requirement is higher, and curing speed is slow, limitation is bigger, and only is applicable to that the surface is the moulding of tart ceramic powder.
In the moulding of sand mo(u)ld, for ease of regulating the curing action of silicate systems binding agent, can adopt various organic and inorganic reagents to change its solidified condition, reach self cure agglutinating effect.At United States Patent (USP) U.S.Pat.4, in 357,165, people such as Helferich have summarized the various various self cure silicate bonding systems that are used for sand mold molding.In the moulding of sand mo(u)ld, water glass can reach the purpose of self cure in conjunction with cement, Sodium Silicofluoride, Pure Silicon Metal, ferrosilicon (Ferrosilicon) or organic ester.
At United States Patent (USP) U.S.Pat.5, in 242.494, the gelling that Callaghan proposes to utilize the hydrolysis of organic ester to regulate the water glass component realizes solidifying the foam materials of preparation silicate.
At United States Patent (USP) U.S.Pat.5, in 851,465, Bredt has designed a kind of technology, solidifying of the citric acid controlled oxidation silica sol binder system that utilization adds in slurry in advance reaches the purpose of three-dimensional spray (Threedimensional printing) aluminum oxide or zirconia ceramics material.
In above-mentioned these patents relevant, all need to adopt the silicate or the silicon oxide of high level, to reach the agglutinating effect with this patent.As United States Patent (USP) U.S.Pat.5,242.494 require the ratio of silicate component in batching is formed to be at least 20%.United States Patent (USP) U.S.Pat.5,851,465 require the content of silicon oxide to account for 10vol% at least in binder system, or 17.5wt%.
The present invention proposes a kind of novel method of utilizing reaction induced sol-gel transition to prepare biscuit of ceramics.Its technological process is at first to prepare ceramic size stable under acidity or alkaline condition, in slurry, only introduce a spot of silicon oxide colloid, regulate pH value of slurry by controlled chemical reaction, reach and make silica sol have the neutral range of higher gelation rate, and the electrolyte ion concentration in the corresponding increase system, by the gelling of silica sol, make slurry in the required time scope, realize solidifying to obtain biscuit.Owing to contain the composition of silicon oxide in many ceramic raw materials, so this method can be used for the multiple stupalith of moulding, obtains having the biscuit of ceramics of complicated shape.For increasing the intensity of biscuit, can in slurry, add colloidal organic or inorganic particle.Superfine silicon oxide micelle and other fine particle play good cohesive action in biscuit, make the gained biscuit have higher intensity.And the low toxicity organic substance of minute quantity is not used or only used to whole technology substantially, therefore can avoid the shortcoming of top described method to a great extent.
The present invention is applicable to the ceramic powder moulding, to obtain having the ceramic molding of definite shape and intensity.
Characteristics of the present invention are that the ceramic powder raw material is made outstanding slurry, utilize the gelation of slurry self silica sol that generate or that add to realize outstanding curing of starching.Because the stable dlvo theory that does not meet DCC institute foundation of silica sol, it can gelling at basic region, it is also highly stable in pH is the zone of 2-3, and the easiest acquisition of these most of just inorganic powders is than the zone of higher surface charge, therefore, can in this scope, prepare stable slurry.The stability of silicon oxide colloid is minimum near neutrality, and solution forms gel, therefore in the present invention, by add chemical substance in system, utilizes the reaction of these materials to change change pH values, impels system to solidify.The gelling of colloidal sol makes outstanding slurry become the wet formed body with certain intensity, and drying obtains biscuit then.Biscuit is sintering densification further.
The present invention requires ceramic powder to disperse, and the preparation of slurry is finished in the acid or alkaline aqueous solution.When under acidic conditions, preparing slurry, require the pH value less than 4; When preparing under alkaline condition, pH value of slurry is at least 8.5.For reaching purposes such as dispersion, can comprise certain amount of organic solvent or reagent in the slurry, as addings such as dispersion agents.
In slurry, introduce silica sol or silicate component, can introduce by three kinds of approach:
1. directly add silicate solutions, silicic acid or silica sol;
2. introduce by being reflected in the outstanding slurry, as utilize the hydrolysis of compound in outstanding slurry such as tetraethyl orthosilicate;
3. produce by processes such as the dissolving of respective components in the powder raw material in liquid phase, hydrolysis, as the dissolving and the hydrolysis of silicon nitride in liquid phase of silicon carbide, silicon nitride surface zone of oxidation.
The content of silicon oxide is the 0.5-10% of solid phase gross weight in the system, is preferably 0.5-5%.
Before the injection molding, add peptizer, the conditions such as ionic concn that change pH value of slurry and corresponding change slurry by reaction make the silica sol gelling or make contained silicate component or silicon oxide change the concurrent rubber of silica sol into fixed attention, thereby system is solidified.
Because silica sol is stablized and near the easiest gelling neutrality in acidity and alkaline environment, and significantly be subjected to electrolytical the influence, therefore the reaction of the present invention by the chemical substance that adds changes near pH value in the slurry makes it to shift to neutrality from acidity or alkaline range, and negatively charged ion in the corresponding change solution or cationic concentration, thereby realize solidifying.
The reaction that slurry is solidified can be various inorganicss or organic reaction, its effect mainly is to make the pH value of slurry system fade to silica gel gelling scope faster by alkalescence or acidity, be pH4-8, therefore this class reactant is called peptizer again in this patent.The hydrolysis reaction of the reaction of inorganics such as silicon nitride, aluminium nitride, magnesium nitride, magnesiumcarbonate, zinc oxide etc. can make the pH value of system fade to neutrality or weakly alkaline by acidity.Organic reaction comprises the reaction of various enzyme catalysiss or acid-base catalysis, as the hydrolysis reaction of urea, carboxylicesters, lactone, and the oxidizing reaction of all kinds of carbohydrate etc.Wherein, the formic acid of the material of organic class, especially binary, ternary and polyvalent alcohol and acetic ester have the application of particularly important in this curing process.Along with the difference of ester structure and the difference of consumption, the hydrolysis of ester can make the slurry for preparing under alkaline condition through reducing certain numerical value after the regular hour.Reach near neutral zone, thereby system is solidified with certain speed.Because under alkaline condition, esterolytic activity is high more, the amount of adding is many more.The speed of its hydrolysis is just fast more, and the pH value that can reach is just low more, and it makes the speed of slurry curing also just big more.Fig. 2 is for dividing the adjusting to 0.06mol/L Tetramethylammonium hydroxide (under the alkaline condition) pH value of ester or lactone.X-coordinate be the time (minute), ordinate zou is the pH value, and curve 1-5 is respectively glucono-lactone, glycol diformate, glycerol diacetate esters, propylene glycol dicarboxylic acid esters and γ-Wu Neizhi among the figure. the speed that the cited various esters of Fig. 2 solidify slurry is glucono-lactone＞glycol diformate＞glycerol diacetate esters＞propylene glycol dicarboxylic acid esters＞γ-Wu Neizhi in proper order.The add-on of ester is determined by the basicity in the system.
For satisfying the requirement of ceramic formula, sol system can be the mixing of silica sol and other inorganics colloidal sol.As using silicon-aluminum sol to replace simple silica sol.
For the performance of regulating slurry and make the solid particulate in the slurry reach good dispersion, can in slurry, add other solvent or reagent.As can in the outstanding slurry of aluminum oxide, zirconium white etc., adding polyacrylate, poly-methyl acrylate, citric acid, 2,3, dispersion agents such as 4-trihydroxybenzoic acid, add-on is the 0.5-10% of system solid phase gross weight.。In the pulp preparation process, also can add defoamer (as silicone oil) and wait other various additives.
For improving the performances such as intensity of biscuit, can in slurry, additionally add the organic or inorganic material of cohesive action.They can be various organic polymers, as the latex or the styrene-butadiene latex of polyoxyethylene glycol, polyacrylonitrile, polyacrylic acid, polymethyl acrylic acid, polyacrylamide, PMAm; Also can be various inorganicss, as the colloidal sol of aluminum oxide, zirconium white etc.Add-on is the 0.5-10% of system solid phase gross weight.For satisfying the requirement of each side such as technology, can add other additive.
The present invention is also applicable to other ceramic, as the moulding of refractory materials, sand mold etc.
To describe the present invention with example below, further illustrate substantive distinguishing features of the present invention and marked improvement.Obviously the present invention never only limits to described embodiment, and embodiment is then only in order to illustrate creativeness of the present invention.
Embodiment:
Example 1. carborundum powders (Norton 10 NLC) 100g adds in the 24ml water (containing the 5ml10% Tetramethylammonium hydroxide), continues to stir 2 hours, adds peptizer, and degassing back is injected in the mould, about 5-60min after fixing.Dry after the demoulding, linear shrinkage ratio is about 1%, and the biscuit volume fraction is about 57-60%.With the difference of peptizer, the setting time difference is as table 1.
Table 1 adopts different peptizer to prepare the needed setting time of silicon carbide biscuit
| Peptizer | Glucono-lactone | Glycol diformate | The glycerol diacetate esters | The propylene glycol dicarboxylic acid esters | Valerolactone |
| Consumption (g) | 0.5 | 0.3 | 0.4 | 0.4 | 0.4 |
| Time (min) | 5 | 5-10 | 10-15 | 20-30 | 40-60 |
Example 2. silicon nitride powder 100g add in the 29ml water (containing 1g9 water water glass as the source of silica sol and simultaneously as the dispersion agent of silicon nitride slurry), add γ-Wu Neizhi 1.0ml as solidifying agent, degassing back is injected in the mould, is warming up to 30-40 ℃, and about 40-60min solidifies.Dry after the demoulding, linear shrinkage ratio is about 1-2%.The biscuit volume fraction is about 53-55%.
Example 3 0.01mol/L hydrochloric acid soln 20ml add tetraethyl orthosilicate 5ml, stir 2 hours, and tetraethyl orthosilicate is hydrolyzed to silica sol substantially, adds aluminum oxide (d then
50=0.3 μ m) 110g adds aluminum nitride powder 2g as peptizer, the degassing, injection molding.Be warming up to 45 ℃.About 30min after fixing.
Add 10% Tetramethylammonium hydroxide 5ml in the example 4 20ml water, tetraethyl orthosilicate 5ml, the basic hydrolysis of tetraethyl orthosilicate generates silica sol behind the stirring 30min.Add the dispersion agent of citric acid 0.5g, stir adding aluminum oxide powder (d down as aluminum oxide powder
50=0.3 μ m) 150g adds glycol diformate 0.4ml as solidifying agent, about 20min after fixing.
Example 5. 5ml10% Tetramethylammonium hydroxide add the 0.5g metallic aluminium powder, dissolve fully to aluminium powder.Add 18g water, add unformed silicon oxide 0.8g, to form the sial mixed sols.Add mullite powder (d50=1.2 μ m) 100g under stirring, be cooled to 5-10 ℃, add 0.5g glycerol diacetate esters as solidifying agent, injection molding.About 15min solidifies.
Example 6. 2ml10% Tetramethylammonium hydroxide and 10g50% commodity silica sol add in the 12ml water.Add mullite powder (d50=1.2 μ m) 100g, be cooled to 5-10 ℃, add 0.3g glycerol diacetate esters as solidifying agent, injection molding.About 15min solidifies.
Example 7. carborundum powder 100g add in the 24ml water (contain 5ml10% Tetramethylammonium hydroxide and 2g content and be 47% butadiene-styrene rubber emulsion as organic binder bond), frozen water cooling.Add glycol diformate 0.5ml, injection molding solidified in about 10 minutes.Dry after the demoulding, linear shrinkage ratio is about 1%, and the biscuit volume fraction is about 57-60%.
Example 8. 20ml water (containing the 3ml10% Tetramethylammonium hydroxide) add the 3ml tetraethoxy, stir 30min, and the consistent basic hydrolysis of positive silicic acid generates silica sol.Add 110g aluminum oxide (d50=0.3 μ m), add 0.5ml propylene glycol dicarboxylic acid esters, about 15min after fixing.
More than be the application example that the present invention is used for the moulding of part high-performance ceramic, in fact, the present invention can be used for any compatible with silicon oxide, and can be under acidity or alkaline condition dispersive inorganic materials system, as various refractory materialss, the manufacturing of sand mo(u)ld etc.
Claims (2)
1. a method of utilizing reaction induced gelatination to prepare biscuit of ceramics comprises dispersion agent, binding agent, and its characteristics are:
(1) preparation is at least stable slurry under 8.5 the alkaline condition less than 4 acidity or pH value in the pH value;
(2) introduce silicon oxide colloid or silicate component in slurry, the content of silicon oxide is the 0.5-10% of solid phase gross weight;
(3) by inorganics or organic reaction, make pH value of slurry fade to silica gel scope faster, i.e. pH value 4-8, and the electrolyte ion concentration in the corresponding increase system by acidity or alkalescence as peptizer; Reaction or silicon nitride or aluminium nitride or magnesium nitride or the magnesiumcarbonate or the hydrolysis reaction of zinc oxide as inorganics; As organic reaction, or the hydrolysis reaction of urea or carboxylicesters or lactone;
(4) as dispersion agent, or for polyacrylate or for poly-methyl acrylate or be citric acid or be 2,3, the 4-trihydroxybenzoic acid, add-on is the 0.1-5% of solid phase gross weight; As the organic polymer of binding agent, or the latex or the styrene-butadiene latex of polyoxyethylene glycol or polyacrylonitrile or polyacrylic acid or polymethyl acrylic acid or polyacrylamide or PMAm; As the inorganics of binding agent, or aluminum oxide or zirconic colloidal sol; Add-on is the 0.5-10% of system solid phase gross weight.
2. by the described method for preparing biscuit of ceramics of claim 1, it is characterized in that silicon oxide colloid or the silicate component introduced, or (1) directly adds silicate solutions, silicic acid or silica sol; Or (2) utilize the hydrolysis reaction introducing of organic reagents such as tetraethyl orthosilicate; Or introduce by the dissolving or the hydrolysis of silicon nitride in the aqueous solution of the surface oxide layer of silicon carbide or silicon nitride (3); The content of silicon oxide is the 0.5-5% of solid phase gross weight.
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| CN109456024A (en) * | 2018-12-11 | 2019-03-12 | 山东理工大学 | The modified full information surface silica gel mould red mud waste material of aluminium powder infuses solidification forming method |
| CN113248263B (en) * | 2021-05-25 | 2022-11-22 | 西北工业大学 | Si 3 N 4w Si preform and preparation of Si using the same 3 N 4w /Si 3 N 4 Method for compounding materials |
| CN116143502A (en) * | 2022-10-31 | 2023-05-23 | 中钢集团洛阳耐火材料研究院有限公司 | Silica sol combined iron runner prefabricated member and preparation method thereof |
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Assignee: Taizhou Zhuxin New Material Technology Co., Ltd. Assignor: Shanghai Silicates Institute, the Chinese Academy of Sciences Contract record no.: 2012320000540 Denomination of invention: Process for preparing biscuit of ceramics by reaction induced gelatination Granted publication date: 20021009 License type: Exclusive License Open date: 20000628 Record date: 20120425 |
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