CN1151094C - Method and special mold for preparing unfired ceramic element sheet - Google Patents
Method and special mold for preparing unfired ceramic element sheet Download PDFInfo
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- CN1151094C CN1151094C CNB01104148XA CN01104148A CN1151094C CN 1151094 C CN1151094 C CN 1151094C CN B01104148X A CNB01104148X A CN B01104148XA CN 01104148 A CN01104148 A CN 01104148A CN 1151094 C CN1151094 C CN 1151094C
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Abstract
The present invention relates to the improvement for a ceramic forming method and a forming mould, which has the technical steps: proportioning, mixing and ball milling, plasticizer and suspending agent adding, deaerating, initiator adding, assembled mould preparing, mould gelation injecting, demoulding and drying. The problem of environment pollution is solved, and the cost of raw materials is greatly reduced. The equipment investment expense is greatly reduced, and the quality of products is high.
Description
The invention belongs to field of inorganic nonmetallic material, relate to improvement ceramics forming method and shaping dies.
The core technology of sheet type ceramic component production is the shaping of high quality thin slice base substrate.Traditional ceramic green sheet forming technique mainly contains dry pressing, hot drape process, rolls embrane method, casting method.Dry pressing and hot drape process can't prepare the slim base sheet of large size and surface smoothness relatively poor.Roll modulus method and make blank and caking agent occur inevitably aligning, folk prescription is big to shrinkage during sintering, and dimensional precision is difficult for guaranteeing that performance also anisotropy can occur.At present, all adopt casting method shaping thin ceramic base sheet in the suitability for industrialized production both at home and abroad.
Casting method (tape casting) is called the skill in using a kitchen knife in cookery (doctor blading) or the pocket knife coating method (knife coating) of scraping again, it is the technology of U.S.'s middle forties invention, and in nineteen fifty-two obtain first relevant patent (G.N.Howatt: the production method of high insulated ceramic plates, U.S.Patent2582993).This patent has mainly covered the shaping of the flat ceramic of using in electronics and the wireless field.The J.L.Park Jr. of the U.S. in 1961 has obtained about continuous casting method patent (Production of Ceramics method, U.S.Patent 2966719), to the effect that how with scraping skill in using a kitchen knife in cookery continuous molding chip ceramic body on impermeable organic carrier.Mention first in this patent so far still at caking agent polyvinyl butyral acetal (PVB) commonly used.1967, H.W.Stetson and W.J.Gyurk have delivered first part of document " development of two microinch calcined oxide aluminium substrates " (Am.Ceram.Soc.Bull that makes ultrathin alumina substrate about development with casting method, 16[4], 387,) and in (the aluminum oxide substrate that patents in 1972, U.S.Patent 3698923), key content is to make dispersion agent with fish oil, improve fine alumina powder content in the slip, so that make slim base sheet that casting method produces can direct sintering go out the alumina substrate of high-compactness.After this two during the last ten years, and the curtain coating technology is updated development, become a kind of Technology of comparative maturity, and the curtain coating production line that matches with this method also is gradually improved.But casting method shaped ceramic base sheet need use high volatile volatile organic solvent preparation slip usually, and the most frequently used have toluene, dimethylbenzene, trieline, a propyl carbinol etc., causes environmental pollution serious.Simultaneously, casting method production unit costliness, starting material and consumable material price height, it is low that sintering process is got rid of a large amount of organic binder bond efficient, the energy consumption height.
For this reason, the recent two decades people are devoted to the research of aqueous slurries casting method always.Nineteen eighty-two, the U.S. has authorized two patents (M.Kemr.and H.Miguhara, flexible ceramic band and production method thereof, U.S.Patent No.4329271 simultaneously; K.Kita, J.Fukuda, H.Ohmura andT.Sakai, ceramic green band and production method thereof, U.S.Patent No.4353958).But owing to have the equipment complex and expensive equally, residual organic matter content height, particularly aqueous slurries get rid of that water solvent is slow, and efficient is low, and it is easy to crack and the surface imperfection reason occurs to dehydrate process base sheet, and suitability for industrialized production still has very big difficulty at present.
U.S.'s Oak Ridge National Laboratory in 1991 invented a kind of new ceramic body Precision Forming Technology-water base notes coagulate method (Janney M A, the water base notes of the Omatete O O. ceramic powder shape method of congealing into, U.S.Pat.5028362).Its principle is that the organic monomer and the linking agent that can form hydrogel are mixed with premixed liquid, with be mixed with water base ceramic slurry after ceramic powder mixes, make it in-situ polymerization under certain condition, form to intersect chain structure gelinite and make the ceramic body typing, therefore applicable to the shaping of various complicated shape ceramic parts.But, not see so far with water base notes and coagulate the research report that legal system is equipped with thin slice shape ceramic component aspect, its main difficulty is that the production of thin slice shape ceramic component is different with general ceramic part.Its large-sized base sheet that at first requires to be shaped is cut out the base sheet bar and is carried out Punching Technology with corresponding punch die according to the component shape difference then, carries out lamination sintering and leveling processing at last.This base sheet that just requires to be produced has snappiness and dimensional stability, so that can carry out the dimensional precision after Punching Technology is burnt till with assurance.Though the base substrate that above-mentioned U.S.Patent 5028362 patents are shaped has certain flexibility before its moisture drying, but then become hard and crisp after removing moisture, can't carry out Punching Technology, die-cut meeting sticking to mould when water content is high, die-cutly when water content is low easily break, simultaneously, dehydrate that the base substrate size changes in the process, guarantee that by the water-content in the control base sheet the die-cut back size of component precision difficulty of burning till is bigger, and only depend on its snappiness of the remaining moisture of base sheet also difficult satisfy contain aperture, the requirement of complicated shape sheet type element Punching Technology such as cutter seam.
The objective of the invention is, overcome organic slip casting method shaped ceramic base sheet equipment complex and expensive, the material cost height, energy consumption is big, the problem that environmental pollution is serious, improve the ceramic slurry preparation and the manufacturing process of water base gel-casting method, the base sheet that still has good snappiness and Punching Technology performance after obtaining to dehydrate, the preparation cost of reduction thin slice shape ceramic component.Another object of the present invention is the uniformity consistency for the base sheet thickness of enhancing productivity and guarantee to be shaped, and has proposed to be adapted to the base sheet shaping assembling die design of this process characteristic.
Technical scheme of the present invention is: a kind of method for preparing unfired ceramic element sheet, it is characterized in that,
1, batching, according to the composition requirement of prepared ceramic green sheet, the accurate various ceramic powders of weighing; Weighing deionized water or distilled water to scale; Take by weighing dispersion agent, it is one of following material: polyacrylate, poly-methyl acrylate, carbonyl hydrochlorate, Citrate trianion, its add-on are 0.5～2.0% of ceramic powder weight; Take by weighing softening agent, it is one of following material: glycerol, polyoxyethylene glycol, fourth Bian Ji phthalate, its add-on are 0.5～5% of ceramic powder weight; Take by weighing suspension agent, it is one of following material: polyvinyl alcohol, and polyacrylamide, Sudan Gum-arabic, its add-on is 0.1～0.5% of a ceramic powder weight; Take by weighing organic monomer and linking agent, organic monomer is water soluble propene's acid amides or Methacrylamide, linking agent is methylene-bisacrylamide or many ethyleneglycol dimethacrylates, the ratio of organic monomer and linking agent can be chosen between 10: 1～30: 1, and total add-on is 10～30% of a water weight;
2, mixing and ball milling,
Above-mentioned ceramic powder, deionized water or distilled water, dispersion agent, organic monomer and linking agent are put into fully ball milling of ball mill, form ceramic slurry, the ball milling time is 2～30h, and ratio of grinding media to material is 1: 1～2: 1;
3, add softening agent and suspension agent, after the uniform ceramic slurry of mix grinding is taken out from ball mill, add softening agent and suspension agent, mix;
4, degasification is carried out vacuum stirring or vibration degasification to ceramic slurry, adds the defoamer of slip total amount 0.5～2%;
5, add initiator, add the initiator ammonium persulfate aqueous solution in the ceramic slurry after the vacuum stirring degasification, stir, the add-on of initiator is 0.2～0.6% of an organic monomer weight;
6, assembling die is prepared, moulding stock is selected the material that plate glass, metal, polymer (plastics) etc. do not seep water and surfacing is bright and clean for use, the sealed strip of laying desired thickness between the template can adopt top teeming process or the method particular manufacturing craft of making a bet with control base sheet thickness.
7, gel-casting, can adopt following two kinds of methods one of them:
7.1, in ceramic slurry, add the catalyzer Tetramethyl Ethylene Diamine, the back cast that stirs is advanced individual layer or the lamination assembling die made by plate material and is treated its natural gelation, the add-on of catalyzer is 0.05～0.5% of an organic monomer weight;
7.2, ceramic slurry poured into a mould into the individual layer of being made by plate material or lamination assembling die after, be heated to 40～80 ℃ and make ceramic slurry gelization;
8, demoulding drying, after ceramic slurry gelization was finished, the ceramic gel base sheet on every layer of template was taken in the demoulding off, was positioned on the gas-pervious mesh screen or on the smooth plasterboard it is dehydrated, and drying mode can adopt seasoning, blowing drying or heat drying.
When selecting raw material, increase powder such as MgO, the CaO etc. of slip viscosity for easy generation hydration reaction, should use their more stable material such as MgCO in water
3, CaCO
3Deng, or they are synthesized the stable compound of required composition in advance, as with MgO and Al
2O
3, Y
2O
3And La
2O
3Synthetic respectively MgAlO
3, LaYO
3Use the back.
A kind of special combination mould that is used for preparation unfired ceramic element sheet method as claimed in claim 1, it is characterized in that, mould is by two exterior sheathings 1, between two exterior sheathings 1, the folded mutually some inner formwords 2 that lean on, sealed strip 3 between adjacent two templates and binding clasp 4 are formed, each template is essentially identical square of physical dimension or rectangle, the upper limb of every inner formword 2 has an arc groove, sealed strip 3 is placed along the template periphery, its thickness is by required thickness decision of watering the injection sheet, the sealed strip of inner formword 2 lower rims tightly cooperates with the sealed strip of two lateral edges, in the both sides of inner formword 2 upper limb arc grooves a sealed strip 3 is arranged respectively, the sealed strip of it and lateral edges keeps the gap of 5～10mm, by several binding clasps 4 whole template clampings is become as a whole.
Another kind is used for the special combination mould of preparation unfired ceramic element sheet method as claimed in claim 1, it is characterized in that, mould is by an exterior sheathing 1, one in the bottom one jiao of exterior sheathing 1a that has the sprue gate, between two exterior sheathings 1 and 1a, the folded mutually some inner formwords 2 that lean on, sealed strip 3 between adjacent two templates and binding clasp 4 are formed, each template is essentially identical square of physical dimension or rectangle, every inner formword 2 position corresponding with the sprue gate on the exterior sheathing 1a has through hole, at the place, diagonal angle of this through hole a circular groove is arranged, sealed strip 3 is 4 smooth bright and clean thin bars, its thickness is by required thickness decision of watering the injection sheet, periphery along inner formword 2 is placed, two sealed strip junctions tightly cooperate, and by several binding clasps 4 whole template clampings are become as a whole.
But the invention solves the forming technique of the ceramic green sheet of Punching Technology, and proposed special-purpose assembling die, make it to be adapted to the suitability for industrialized production requirement.Its advantage mainly shows as:
1, compares with at present general both at home and abroad organic slip casting method, toluene, dimethylbenzene, trieline have been replaced with deionized water, high volatile volatile noxious solvents such as propyl carbinol, other organism (binding agent, softening agent, dispersion agent, suspension agent etc.) also only is 1/3～1/4 of organic curtain coating slurry, has solved problem of environmental pollution substantially and material cost is reduced greatly.
2, the water base notes method of coagulating has been saved the casting machine product line device of complex and expensive, and use the lamination assembling die instead, easily manufactured, the production efficiency height, and get final product the base sheet of the convenient, flexible above all thickness of production 0.2mm by the change of filler strip thickness, base sheet thick consistency is good, and under the condition of identical throughput, the facility investment expense reduces significantly.
3, the ceramic green sheet produced of the water base notes method of coagulating is to dehydrate naturally after the first gel setting demoulding,
3, the ceramic green sheet produced of the water base notes method of coagulating is to dehydrate naturally after the first gel setting demoulding, be different from casting method need first heated volatile to go out behind the organic solvent in the slip could peel, simultaneously, remaining organic content is low in the base sheet, base sheet density height, the remaining organism of sintering process is got rid of easily, shrinkage is little, be not prone to cracking phenomena, therefore batch improves (number of laminations increase), sintering time shortens (organism burn off process is very short), and sintering temperature reduces (base sheet density height), and energy conservation and consumption reduction effects is very remarkable.
Description of drawings.
Fig. 1 is the process flow sheet that has comprised preparation thin slice ceramic component of the present invention.
The top teeming process assembling die wiring layout that Fig. 2 designs for the present invention.
Fig. 3 is top teeming process assembling die intermediate die plate and sealed strip disposing way.
The method of the making a bet assembling die wiring layout that Fig. 4 designs for the present invention.
Fig. 5 is method assembling die intermediate die plate and the sealed strip disposing way of making a bet.
Below in conjunction with accompanying drawing the present invention is described in further details.
Fig. 1 provides the complete process flow of preparation thin slice ceramic component, and the water base notes of employing of the present invention coagulate legal system and are equipped with thin slice shape (technical process of thickness 0.2～3mm) ceramic component base sheet is till dehydrate.
The technology point of the inventive method is:
One, batching.
According to the composition requirement of required stupalith, the accurate various ceramic powders of weighing.Increase powder such as MgO, the CaO etc. of slip viscosity for easy generation hydration reaction, should use their more stable material such as MgCO in water
3, CaCO
3Deng, or they are synthesized the stable compound of required composition in advance, as with MgO and Al
2O
3, Y
2O
3And La
2O
3Synthetic respectively MgAlO
3, LaYO
3Use the back.
Take by weighing used deionized water or distilled water by prescription, add-on is 30～60vol% of ceramic powder volume, be consumption and the raising ceramic slurry flowability that reduces water, should add simultaneously raw material weight 0.5～2.0% do not introduce impurity and at when calcining all kinds of dispersion agents of burn off fully, as organic electrolyte dispersion agents such as polyacrylate, poly-methyl acrylate, carbonyl hydrochlorate, Citrate trianions.For make still keep after the base sheet dehydration pliable and tough can die-cut property, should add the softening agent of ceramics powder body weight 0.5～5%, as glycerol, polyoxyethylene glycol, fourth Bian Ji phthalate etc.Be the double obdurability that improves shaping base sheet of the suspension stability that further improves slip, also need add the organic polymer such as the polyvinyl alcohol of ceramic powder weight 0.1～0.5%, polyacrylamide, Sudan Gum-arabic etc.Organic monomer is selected water soluble propene's acid amides or Methacrylamide for use, linking agent is selected methylene-bisacrylamide or many ethyleneglycol dimethacrylates for use, the ratio of organic monomer and linking agent can be chosen between 10: 1～30: 1, and total add-on is 10～30% of a deionized water weight.
Two, mixing and ball milling.
At first above-mentioned ceramic powder raw material, deionized water or distilled water, dispersion agent, organic monomer and linking agent are put into fully ball milling of ball mill, guaranteed that further refinement of ceramic powder and batch mixing are even.Ball mill intermediate roll liner and abrading-ball should adopt with the ceramic material of producing close or do not introduce the wear-resisting organic polymer material of impurity.Ratio of grinding media to material can be chosen between 1: 1～2: 1 according to the principle of levigate and mixing.
Three, add softening agent and suspension agent.
The uniform ceramic slurry of mix grinding adds softening agent and organic suspending agent according to aforementioned proportion after taking out from ball mill, mixes.
Four, degasification.
After adding softening agent and suspension agent or when adding, carry out vacuum stirring or vibration degasification, and adding accounts for the defoamer of ceramic slurry gross weight 0.5～2%, for example propyl carbinol and ethylene glycol mixtures, the micro-bubble that is present in the slip in assurance ball milling and the blowing process is thoroughly got rid of, and pore or pinprick defective occur in order to avoid cause with postforming base sheet surface.
Five, add initiator
With adding initiator such as ammonium persulfate aqueous solution in the slip after the vacuum stirring degasification, stir, the add-on of initiator is 0.2～0.6% of an organic monomer weight.
Six, assembling die is prepared
1, top teeming process assembling die wiring layout is seen Fig. 2, is made up of two exterior sheathings 1, some inner formwords 2, sealed strip 3, binding clasps 4.Fastener 5 compresses each template and makes it to become one.Exterior sheathing 1 is square or rectangular flat, and size can be according to the size decision of required preparation base sheet.The quantity of inner formword 2 can be 1～50 flat board, and its physical dimension and two side templates are basic identical.The upper limb of every inner formword 2 is left a width and is no more than template width 1/2, the circular groove of the about 10～30mm of the degree of depth.The material that the material selection plate glass of template, metal, polymer (plastics) etc. do not seep water and surfacing is bright and clean is made.Sealed strip is generally smooth bright and clean by 5, and width is that the thin bar of 5～20mm is formed, and its thickness is by required thickness decision of watering the injection sheet.Sealed strip 3 is placed along the periphery of inner formword 2, keeps flat a sill strip at lower rim, and each vertically puts a side slat two side rims, and side slat must tightly cooperate with sill strip.Respectively put a sealed strip in the both sides of inner formword 2 upper limb circular grooves, every length is no more than 1/3 of sill strip, and its putting position should leave the gap of 5～10mm with side slat.Above-mentioned sealed strip can be when matched moulds temporarily putting, but also predetermined fixed on inner formword 2, as shown in Figure 3.
Assembling die binding clasp 4 is the rigidity slot-type device that have fastener 5, and its groove width is greater than whole template (containing sealed strip) total thickness 5～20mm, and after binding clasp 4 blocked template, fastener 5 should be in the position at sealed strip place.Fastener 5 is bolts of being convenient to turn, and after binding clasp 4 blocks template, tights a bolt, and withstands template and promptly finishes fastening effect.Every cover assembling die uses 2～3 binding clasps 4.Assembling die can be stood up on platform during cast, from the arc groove injection slip of inner formword 2.The accurately weighing of slip volume guarantees behind the casting complete that slip can be full of between each piece template and can be at arc groove place levelling.The advantage of this mould is easy and simple to handle, does not have difficulty for thicker base sheet, but requires the operating process stable and continuous to continue to flow, in order to avoid entrain into bubble.
2, the method assembling die wiring layout of making a bet is seen Fig. 4, by exterior sheathing 1, exterior sheathing 1, one in the bottom one jiao of exterior sheathing 1a that has a sprue gate, between two exterior sheathings 1 and the 1a, the folded some inner formwords 2 that lean on, sealed strip 3 and the binding clasp 4 between adjacent two templates are formed mutually.Two exterior sheathings 1 and 1a are square or rectangular flat, and size can be according to the size decision of required preparation base sheet.Wherein exterior sheathing 1a needs to bore at place, one angle the through hole of φ a 10～20mm, can also an embedded internal diameter be the hollow circular sprue gate of 5～15mm in this hole.The quantity of inner formword 2 can be 1～50 flat board, and its physical dimension and exterior sheathing are basic identical.One jiao of inner formword 2 with exterior sheathing 1a on the corresponding position of through hole, need to bore a through hole, the aperture is identical with through hole or hollow circular sprue gate internal diameter.Leave a degree of depth at another place, diagonal angle and radius is the circular groove of 10～30mm.Sealed strip 3 is 4 smooth bright and clean thin bars, and its thickness is by required thickness decision of watering the injection sheet, and width is 5～20mm, places along the inner formword periphery, requires the place of contacting with each other tightly to cooperate.Above-mentioned sealed strip can be when matched moulds temporarily putting, but also predetermined fixed on inner formword 2, as shown in Figure 5.Binding clasp 4 is the same with the described situation of top teeming process assembling die Fig. 2 with fastener 5.
The assembling die vertical side can be changeed 45 ° during cast and stand up on a troffer, make the sprue gate be positioned at the below.The slip conduit is filled in the sprue gate, make slip bottom-up mobile, until being full of the die clearance, at last at inner formword 2 circular groove place levellings.The advantage of this mould is can pressure casting or the suction of bleeding from the top, the base sheet relatively thinner to cast (＜0.5mm) favourable.Simultaneously, bottom pouring can avoid entraining into bubble, base tablet quality height.But this method operation is loaded down with trivial details relatively, needs valve-off after cast finishes, and assembling die was fallen gelation in order to avoid the slip outflow.
Seven, gel-casting.
Can adopt with any method in following two kinds of methods and carry out the gel-casting operation:
First kind, add the catalyzer Tetramethyl Ethylene Diamine, add-on is 0.05～0.5% of an organic monomer weight, the back cast that stirs is advanced assembling die and is treated its natural gelation.The add-on of catalyzer can influence the slurry gel time, can realize to finish behind the pouring operation that gelation was advisable in 5～20 minutes usually.
Second kind, slip is injected assembling die post-heating to 40～80 ℃ make ceramic slurry gelization, type of heating can adopt modes such as electrically heated, heating in water bath.
Eight, demoulding drying.
After slurry gelization is finished, the water-setting compound blank sheet on every layer of template is taken in the demoulding off, being positioned on the gas-pervious mesh screen or on the smooth plasterboard dehydrates it, drying mode can adopt seasoning, blowing drying or heat drying, but require full wafer base sheet evenly to dewater, avoid base sheet generation gross distortion.Can obtain having enough snappinesies after the base sheet dehydrates, any surface finish is smooth, the thickness uniformity can satisfy the ceramic green sheet of Punching Technology.
Subsequently, can earlier the snappiness base sheet of aforesaid method production be gone out required shape with mould on punch press by the production method of general chip ceramic component.For enhancing productivity, the slice component ceramic green sheet generally adopts the lamination sintering, needs during lamination to spread between every to apply the high temperature resistant and insulating powder that do not react with this chip stupalith of one deck.After sintering porcelain under certain sintering process condition, way with rubbing down or blast is removed insulating powder, push down with smooth slick refractory slab behind the lamination once more, flatten processing being lower than sintering temperature but can making under the temperature of chip ceramic component creep, just obtain required thin slice shape ceramic component at last.
Embodiment.
The preparation of embodiment 1,96% aluminum oxide electronic ceramic substrate
Starting material adopt purity greater than 99.5%, α-Al of median size 2.84 μ m
2O
3Powder, sintering agent adopts CaCO
3, kaolin and particle diameter be the SiO of 30nm
2Powder, its proportioning are Al
2O
3: CaO: SiO
2=96.7: 1.5: 1.8.With above-mentioned raw materials and expect that the dispersion agent that heavy 15% deionized water, 2.5% acrylamide, 0.125% methylene-bisacrylamide and 1% prepare voluntarily adds ball mill, and regulate slip pH=9 with ammoniacal liquor, blend mill 20h, discharging is to the vacuum stirring jar, add 1.5% glycerol, 1.0% polyoxyethylene glycol, 0.5% polyacrylamide, press the defoamer (propyl carbinol and ethylene glycol mixture) that the 1000ml slip adds 1ml simultaneously, be evacuated to the following 0.5h of stirring of 1KPa, promptly obtain having the slip of good fluidity and suspension stability.According to 8% ammonium persulfate aqueous solution that every 1000ml slip adding 2ml Tetramethyl Ethylene Diamine and 2ml prepare in advance, 15 layers of assembling die that sheet glass is made shown in Figure 2 are injected in the back that stirs, and placing after about 10 minutes naturally is gelation.Taking gel base sheet after the demoulding off places to dehydrate naturally on the nylon cloth mesh screen and promptly obtains the base sheet that snappiness is good, can carry out Punching Technology.
Above-mentioned base sheet cuts out bar by the essentially identical production technique of alumina ceramic substrate and punch die processing, stucco, lamination, sintering densification, rubbing down are removed parting sand, leveling is handled, and has promptly finished the production of ceramic substrate.Be noted that above-mentioned base sheet be stacked at most 50 and finally behind 1520 ℃ of insulation 3h sintering density can reach 3.77g/cm
3, this base sheet that is casting method is produced is beyond one's reach.Table 1 has been listed the measured performance of the thick alumina ceramic substrate of being produced of 1mm.
Table 1 alumina-ceramic (96 porcelain) substrate salient features
| Project | Standard GB/T 14619-93 | Kyocera's standard | The actual measurement of boat material institute | ||
| State | Fine and closely woven | ||||
| Color | White | ||||
| Volume density | g/cm 3 | ≥3.70 | 3.70 | 3.77 | |
| Bending strength | MPa | 274 | 314 | 296.5 | |
| Linear expansivity | ℃ -1(20～500℃) | (6.5～7.5)×10 -6 | 7.2×10 -6 | 6.62×10 -6 | |
| ℃ -1(20～800℃) | (6.5～8.0)×10 -6 | 7.9×10-6 | 7.2×10 -6 | ||
| Thermal conductivity | W/m·K | ≥20.9 | 27 | 28.9 | |
| Disruptive strength | kv/mm | ≥12 | 12 | 50 | |
| Volume specific resistance | Ω·cm(20℃) | ≥10 14 | ＞10 14 | 3.4×10 16 | |
| Ω·cm(300℃) | ≥10 11 | 10 10 | 1.4×10 14 | ||
| Ω·cm(500℃) | ≥10 9 | 10 8 | 4.7×10 10 | ||
| Specific inductivity (1MHz) | 9～10 | 9.4 | 9.8 | ||
| Dielectric loss angle tangent (1MHz) | 3×10 -4 | 4×10 -4 | 1.5×10 -4 | ||
| Surface roughness Ra | μm | 0.3～0.8 | 0.2～0.75 | 0.45～0.75 | |
| Angularity | (0.05/25 length) | (0.08/25 length) | 0.003～ 0.02/40 | ||
It is the SiC powder of 1.4 μ m that starting material adopt median size, and with Y
2O
3And La
2O
3Powder is as sintering agent, and three's ratio is 8: 1: 1, Y
2O
3And La
2O
3Powder mixes high-temperature calcination and synthesizes YLaO
3Use the back.The deionized water that adds above-mentioned material weight 30%, add the organic monomer acrylamide of deionized water weight 15%, 0.8% linking agent methylene-bisacrylamide, 2% dispersion agent JA-281, adjust slip pH=8 with Tetramethylammonium hydroxide, put into planetary ball mill, ball: material=1.5: 1, mix grinding 3h, the softening agent glycerol of adding 2% after the discharging, through the vacuum stirring degasification, add the initiator (5% ammonium persulfate aqueous solution for preparing in advance) of slip weight 0.5% again, 5 layers of assembling die that metal sheet is made are as shown in Figure 3 injected in the back that stirs, keep flat into 50 ℃ of baking ovens after closing the sprue gate valve, all gelations after about 15 minutes, the demoulding are taken gel base sheet off and are placed on the smooth plasterboard and dehydrate naturally, make the thick snappiness base of 0.4mm sheet.
This base sheet is cut into desired shape, and spraying interlayer slip is (by BN, SiC, Al
2O
3Adding the ethanol mix grinding forms), put into graphite jig after the drying piecewise, hot pressed sintering 2h under 1820 ℃ of nitrogen protection conditions obtains main stor(e)y 0.2mm, the multilayer structure ceramics matrix material of interlayer 0.02mm, its room temperature bending strength after tested
Fracture toughness property K
IC=20.9MPam
1/2, 1250 ℃ of high-temperature bending strengths
Take by weighing 200g with Y
2O
3Adulterated (Ba
0.85Pb
0.15) Ti
1.01O
3The PTC powder, add the 26ml deionized water again, the 4g Methacrylamide, the neutral dispersion agent of multicomponent that 0.6g methylene-bisacrylamide, 15ml are prepared voluntarily, keeping slip be neutrality (pH=7).In planetary ball mill mix grinding 2h, discharging is to glass beaker, add the 3ml glycerol, 0.5g Sudan Gum-arabic, place ultrasonator vibration degasification 10 minutes, add the 5% concentration ammonium persulfate aqueous solution that 0.5ml prepares in advance then, 3 layers of assembling die that plastic plate is made are as shown in Figure 2 injected in the back that stirs, and vertically immerse gelation in about 5 minutes in 70 ℃ of hot water baths.Gel base sheet places on the nylon cloth mesh screen and dehydrates after the demoulding, makes the thick flexible base sheet of 1.35mm.
This base sheet is cut into the base bar, places that lamination buries powder in the corundum crucible, spaciously earlier be placed on 600 ℃ of insulation 1h and remove organism.Add a cover again with suitable sintering process densification and semiconductor, promptly obtain the thick PTC pottery of big sheet 1.2mm, it is cut into 70 * 3mm shape on the diamond wheel cutting machine, two sides burning infiltration Al electrode materials, the resistance value that finally records this PTC thermal sensing element is 15.5 Ω, about 180 ℃ of Curie temperature.
Claims (4)
1, a kind of method for preparing unfired ceramic element sheet is characterized in that,
1.1, batching, according to the composition requirement of prepared ceramic green sheet, accurate various ceramic powders of weighing; Weighing deionized water or distilled water to scale; Take by weighing dispersion agent, it is one of following material: polyacrylate, poly-methyl acrylate, carbonyl hydrochlorate, Citrate trianion, its add-on are 0.5～2.0% of ceramic powder weight; Take by weighing softening agent, it is one of following material: glycerol, polyoxyethylene glycol, fourth Bian Ji phthalate, its add-on are 0.5～5% of ceramic powder weight; Take by weighing suspension agent, it is one of following material: polyvinyl alcohol, and polyacrylamide, Sudan Gum-arabic, its add-on is 0.1～0.5% of a ceramic powder weight; Take by weighing organic monomer and linking agent, organic monomer is water soluble propene's acid amides or Methacrylamide, linking agent is methylene-bisacrylamide or many ethyleneglycol dimethacrylates, the ratio of organic monomer and linking agent can be chosen between 10: 1～30: 1, and total add-on is 10～30% of a water weight;
1.2, mixing and ball milling,
Above-mentioned ceramic powder, deionized water or distilled water, dispersion agent, organic monomer and linking agent are put into fully ball milling of ball mill, form ceramic slurry, the ball milling time is 2～30h, and ratio of grinding media to material is 1: 1～2: 1;
1.3, add softening agent and suspension agent, after the uniform ceramic slurry of mix grinding is taken out from ball mill, add softening agent and suspension agent, mix;
1.4, degasification, ceramic slurry is carried out vacuum stirring or vibration degasification, add the defoamer of slip total amount 0.5～2%;
1.5, add initiator, add the initiator ammonium persulfate aqueous solution in the ceramic slurry after the vacuum stirring degasification, stir, the add-on of initiator is 0.2～0.6% of an organic monomer weight;
1.6, gel-casting, can adopt following two kinds of methods one of them:
1.6.1, in ceramic slurry, add the catalyzer Tetramethyl Ethylene Diamine, the back cast that stirs is advanced individual layer or the lamination assembling die made by plate material and is treated its natural gelation, the add-on of catalyzer is 0.05～0.5% of an organic monomer weight;
1.6.2, ceramic slurry poured into a mould into the individual layer of being made by plate material or lamination assembling die after, be heated to 40～80 ℃ and make ceramic slurry gelization;
1.7, demoulding drying, after ceramic slurry gelization was finished, the ceramic gel base sheet on every layer of template was taken in the demoulding off, was positioned on the gas-pervious mesh screen or on the smooth plasterboard it is dehydrated, drying mode can adopt seasoning, blowing drying or heat drying.
2, the method for preparing unfired ceramic element sheet according to claim 1, it is characterized in that, composition requirement according to required stupalith, the accurate various ceramic powders of weighing, increase powder such as MgO, the CaO etc. of slip viscosity for easy generation hydration reaction, should use their more stable material such as MgCO in water
3, CaCO
3Deng, or they are synthesized the stable compound of required composition in advance, as with MgO and Al
2O
3, Y
2O
3And La
2O
3Synthetic respectively MgAlO
3, LaYO
3Use the back.
3, a kind of special combination mould that is used for preparation unfired ceramic element sheet method as claimed in claim 1, it is characterized in that, mould is by two exterior sheathings [1], be positioned between two exterior sheathings [1], the folded mutually some inner formwords [2] that lean on, sealed strip [3] between adjacent two templates and binding clasp [4] are formed, each template is essentially identical square of physical dimension or rectangle, the upper limb of every inner formword [2] has an arc groove, sealed strip [3] is placed along the template periphery, its thickness is by required thickness decision of watering the injection sheet, the sealed strip of inner formword [2] lower rim tightly cooperates with the sealed strip of two lateral edges, respectively there is a sealed strip [3] both sides at inner formword [2] upper limb arc groove, the sealed strip of it and lateral edges keeps the gap of 5～10mm, by several binding clasps [4] whole template clampings is become as a whole.
4, a kind of special combination mould that is used for preparation unfired ceramic element sheet method as claimed in claim 1, it is characterized in that, mould is by an exterior sheathing [1], one in the bottom one jiao of exterior sheathing [1a] that has the sprue gate, be positioned between two exterior sheathings [1] and [1a], the folded mutually some inner formwords [2] that lean on, sealed strip [3] between adjacent two templates and binding clasp [4] are formed, each template is essentially identical square of physical dimension or rectangle, the position that every inner formword [2] is corresponding with the sprue gate on the exterior sheathing [1a] has through hole, at the place, diagonal angle of this through hole a circular groove is arranged, sealed strip [3] is 4 smooth bright and clean thin bars, its thickness is by required thickness decision of watering the injection sheet, periphery along inner formword [2] is placed, two sealed strip junctions tightly cooperate, and by several binding clasps [4] whole template clampings are become as a whole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01104148XA CN1151094C (en) | 2001-02-22 | 2001-02-22 | Method and special mold for preparing unfired ceramic element sheet |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01104148XA CN1151094C (en) | 2001-02-22 | 2001-02-22 | Method and special mold for preparing unfired ceramic element sheet |
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| Publication Number | Publication Date |
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| CN1370759A CN1370759A (en) | 2002-09-25 |
| CN1151094C true CN1151094C (en) | 2004-05-26 |
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| CNB01104148XA Expired - Lifetime CN1151094C (en) | 2001-02-22 | 2001-02-22 | Method and special mold for preparing unfired ceramic element sheet |
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2001
- 2001-02-22 CN CNB01104148XA patent/CN1151094C/en not_active Expired - Lifetime
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| CN1370759A (en) | 2002-09-25 |
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