CN103739207B - A kind of manufacture method of the glass-ceramic clad plate with antistatic glass layer - Google Patents
A kind of manufacture method of the glass-ceramic clad plate with antistatic glass layer Download PDFInfo
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- CN103739207B CN103739207B CN201310699074.4A CN201310699074A CN103739207B CN 103739207 B CN103739207 B CN 103739207B CN 201310699074 A CN201310699074 A CN 201310699074A CN 103739207 B CN103739207 B CN 103739207B
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Abstract
The present invention relates to technical field of inorganic nonmetallic materials, be specifically related to a kind of manufacture method of the glass-ceramic clad plate with antistatic glass layer, it comprises the steps: step 1) manufacture antistatic glass frit: selecting mass fraction is that 24%～50% inorganic conductive powder and mass fraction are that 50%～76% glass dust is made particle diameter≤4 object antistatic glass frit after melting, shrend, broken process as raw material; Step 2) charity frit: the antistatic glass frit that charity step 1) is manufactured on Ceramic Tiles base substrate and the mixed frit of simple glass frit, wherein the quality of simple glass frit is 0～3 times of antistatic glass frit quality, then spray bonding agent mixed frit is fixed, and the mixed frit of charity is flattened with roller; Step 3) enters klining; The processing of step 4) rubbing down; Obtain having the glass-ceramic clad plate of antistatic glass layer.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, relate in particular to glass and ceramic composite,Relate more specifically to a kind of manufacture method of the glass-ceramic clad plate with antistatic glass layer.
Background technology
Static is a kind of objectively natural phenomena, and the mode of generation is multiple, as contact, friction etc. Static pairSome responsive instrument and places, may cause fatal harm. As the electromagnetism that static produces in the time discharging is imitatedShould (electromagnetic interference or Electro Magnetic Compatibility) can disturb the normal work of precision instrument, cause automation equipmentMisoperation; The gathering of electric charge may produce point discharge phenomenon, may burn precision instrument, the electricity fire of generationSpend the dust that may ignite, cause explosion accident. Therefore electrostatic defending technology as electronics industry, petroleum industry,Weapon industry, textile industry, rubber industry and space flight and military field are all received very big attention, make every effort to seekAsk and reduce the loss that static causes.
Simple glass material has very high resistivity, easily gathers electric charge, and gathering of these electric charges mayBring multiple harm described above. There is every year the damnous report of relevant electrostatic hazard, be therefore badly in need of onePlant the construction material that can overcome the above problems.
Research shows, when the specific insulation of material exceedes 1 × 1010When Ω m, the energy of material dissipation electric chargePower obviously weakens; Consider from the angle of eliminating static, the specific insulation of material should be higher than 1 × 1010Ω m. When material surface resistance is 104～109When Ω, the electric charge of accumulation can discharge as soon as possible, therebyReach the effect of antistatic.
Our common simple glass is a kind of insulator under normal conditions, thereby surface easily gathers electric charge, long-pendingTired static. People have researched and developed the technique of a lot of production antistatic glass for this reason, for example, in glass, add conductionIon, at glass surface additional guide electrolemma etc. In glass, add conductive ion mainly for the manufacture of solid electricitySeparate matter glass, electrocondution slurry antistatic glass powder, above main application is lithium ion battery etc.; At glassSurface additional guide electrolemma is mainly for the manufacture of antistatic glass fiber and have the glass system of surface conductance abilityProduct, it is mainly used in FPD field, the ITO(tin oxygen being for example widely used in FPDChange indium) glass. The antistatic glass cost of above two kinds of mode manufacturings is high, and the scope of application is substantially solidFixed, particularly ito glass manufacturing equipment costliness, needs plasma sputtering equipment, and manufacture is anti-quietElectricity glass only has the conducting film that one deck sputter forms on surface. The antistatic glass that above two kinds of modes makeAll be not suitable for as building and ornament materials.
In building and ornament materials, glassware occupies very large ratio. Along with entering of production technology and materialStep, except traditional building glass, glass Mosaic, devitrified glass brick, glass-ceramic clad plate,Throw the new product such as brilliant brick, throwing glazed brick and continue to bring out, in building internal and external ornament, bringing into play more and more importantEffect. If by antistatic glass material for above product, can obtain there is electro-magnetic screen function,The building decorative product of electrostatic-proof function, avoids electrostatic hazard. People constantly research and develop to have and are applicable in batches for this reasonProduce antistatic glass for building and goods thereof with low cost.
Summary of the invention
The antistatic glass that the object of the invention is to propose a kind of cheapness, it has with low cost, workerThe features such as skill is simple, and can or set it as a kind of basic material manufacture building and ornament materials, energy by itProvide comfortable, healthy living space to people. And using this kind of antistatic glass as material, Hai NengshengProducing for example antistatic plate glass, antistatic glass vessel, antistatic glass mosaic, antistatic glass meltsPiece, the antistatic product such as the glass micro-crystalline ceramic composite plate of antistatic.
For reaching this object, the present invention by the following technical solutions: a kind of antistatic glass, it is at least by matterThe amount umber inorganic conductive powder that is 24%～50% and 50%～76% glass dust as raw material blending after meltingCooling making, the one or two in the titanate that described inorganic conductive powder is inorganic conductive oxide, conductionPerson's mixture.
Further, in above-mentioned antistatic glass, inorganic conductive oxide is for including but not limited to conduct electricity oxygenChange one or more mixing in tin, conductive zinc oxide, conductive titanium oxide, electric conductive oxidation iron.
Further, in above-mentioned antistatic glass, the titanate of conduction is for including but not limited to conduct electricity metatitanic acidOne or more mixing in barium, conduction lead titanates.
Further, in above-mentioned antistatic glass, glass dust can be cryogenic glass powder, common building glassOne or more combinations in glass powder, ware glass powder, microcrystalline glass powder, glass frit powder.
Cryogenic glass powder refers to the glass dust that melt temperature is lower, for example lead glass powder; Common building glass dustRefer to the powder that the discarded rear fragmentation of door and window plate glass used is made; Ware glass powder refer to vial, tank,The powder that cup, the discarded rear fragmentation of dish are made; Microcrystalline glass powder refers to the powder of making after devitrified glass fragmentation,Glass frit powder refers to cooling the glass direct-water-quenching of the molten state block making is broken into the powder that powder is madeMaterial. In addition, glass frit is also usually used as the glaze raw material of Production of Ceramics, and main rising done flux and raisingGlaze quality effect, glass frit also can be used as the raw material of producing glass-ceramic clad plate in addition.
Certainly, above glass dust component also can adopt the form of raw mineral materials to add, but melt temperature wants highIn 1400 DEG C.
Above-mentioned antistatic glass can be made antistatic plate glass, antistatic glass vessel, antistatic glassMosaic, antistatic glass frit.
The present invention also provides a kind of method of manufacturing antistatic glass, and it comprises the steps:
Step 1) batch mixing: by a kind of in the titanate by inorganic conductive oxide, conduction or both is mixedThe inorganic conductive powder of compound composition mixes with glass dust, makes compound, wherein inorganic conductive powderMass fraction be 24%～50%, the mass fraction of glass dust is 50%～76%;
Step 2) found: the compound that step 1) is made is founded in kiln, glass melting temperature be 1200 DEG C～1600 DEG C, obtain the glass paste of molten state;
Step 3) moulding is cooling: by step 2) the cooling antistatic glass system that obtains of glass paste moulding that obtainsProduct.
Further, in said method, the conductive oxide using in step 1) includes but not limited toOne or more mixing in conductive tin oxide, conductive zinc oxide, conductive titanium oxide, electric conductive oxidation iron.
Further, in said method, the titanate of the conduction using in step 1) comprises but does not limitOne or more mixing in conduction barium titanate, conduction lead titanates.
Further, in said method, in step 1) by the metatitanic acid by inorganic conductive oxide, conductionIt is to adopt dry method that the inorganic conductive powder of a kind of in salt or both compositions of mixtures mixes with glass dustThe mode of mixing is carried out. Certainly the mixed mode of wet method is also passable, but need to increase by a step by wet-mixingAfter the dry operation of compound, can increase like this energy consumption.
Further, in said method, dry mixed equipment is vibrating ball-mill or is dry mixed ball mill, mixedTime is >=30 minutes.
In said method, step 2) found before, the compound that can first step 1) be mixed dispensesOn supporting body, then found. So, the antistatic glass of making can be with supporting body surface topographyExisting different shape, for example supporting body surface topography is plane, can make antistatic plate glass; CarryingSurface has latticed grid, can make antistatic glass mosaic.
Further, in said method, the material of supporting body can be refractory material, ceramic green body,One in pottery biscuiting base substrate, high-temperature metal.
Further, in said method, between supporting body and compound, be provided with adherent layer, like this after sintering,Antistatic glass just can be easy to take off from supporting body. The material of adherent layer can be aluminium oxide, mullite,The refractory materials such as aluminium vanadine, cordierite, carborundum, silicon nitride; Particularly, can be by above-mentioned refractory materialBall milling form slurry, is coated on supporting body, and then dispenses compound.
Further, the present invention also provides a kind of method of manufacturing antistatic plate glass, and it comprises following stepSuddenly;
Step 1) batch mixing: by a kind of in the titanate by inorganic conductive oxide, conduction or both is mixedThe inorganic conductive powder of compound composition mixes with glass dust, makes compound, wherein inorganic conductive powderMass fraction be 24%～50%, the mass fraction of glass dust is 50%～76%;
Step 2) to found: the compound that step 1) is made evenly dispenses in fireproof die, described mouldOn there is the die cavity of depression, the smooth and die cavity bottom surface of cavity surface is plane, in kiln, founds, and foundsTemperature is 1200 DEG C～1600 DEG C, obtains the glass paste of molten state;
Step 3) cooling forming: until step 2) glass paste that makes after cooled and solidified, continues in mouldBeing cooled to normal temperature can take out the antistatic plate glass obtaining from mould.
Further, in step 3) cooling forming process, also comprise annealing operation, step 3) is obtainedPlate glass is annealed 1～2 hour at 480 DEG C～540 DEG C. Annealing can be eliminated the stress of glass kind, anti-Only stress is concentrated the broken loss causing.
The antistatic plate glass of more than making can carry out the machining in later stage, comprise cutting, grinding,Polishing etc.
Certainly, except above method, can also adopt float glass process, vertical drawing process, horizontal sheet process, rolling process etc.Known manufacture plate glass technique is prepared above-mentioned dull and stereotyped antistatic glass.
Further, the present invention also provides a kind of method of manufacturing antistatic glass vessel, and it comprises following stepRapid:
Step 1) batch mixing: by a kind of in the titanate by inorganic conductive oxide, conduction or both is mixedThe inorganic conductive powder of compound composition mixes with glass dust, makes compound, wherein inorganic conductive powderMass fraction be 24%～50%, the mass fraction of glass dust is 50%～76%;
Step 2) found: the compound that step 1) is made is founded in kiln, glass melting temperature be 1200 DEG C～1600 DEG C, obtain the glass paste of molten state;
Step 3) moulding is cooling: by step 2) glass paste that obtains pours blow molding in mould into,Then about 500 DEG C annealing 1～2 hour, finally cooling, obtain the glassware conducting electricity.
Further, the present invention also provides a kind of manufacture method of antistatic glass frit, and it comprises following stepRapid:
Step 1) batch mixing: by a kind of in the titanate by inorganic conductive oxide, conduction or both is mixedThe inorganic conductive powder of compound composition mixes with glass powder, makes compound, wherein inorganic conductive powderThe mass fraction of body is 24%～50%, and the mass fraction of glass particle is 50%～76%;
Step 2) to found: the compound that step 1) is made dispenses and packs in fire resistant sagger, more molten in kilnSystem, or directly compound is conveyed in glass melter and is founded; Glass melting temperature is 1200 DEG C～1600 DEG C,To the glass paste of molten state;
Step 3) moulding is cooling: by step 2) to obtain glass paste shrend cooling, and be broken into graininessCan obtain antistatic glass frit.
Above antistatic glass frit can be used as glaze raw material, or directly cloth imposes on ceramic body surface, shapeBecome to have the Ceramic Tiles goods of antistatic glazed layer or glassy layer.
In the manufacture method of the above antistatic glass of introducing, antistatic plate glass, antistatic plate glassNeed to adopt a large amount of inorganic conductive powder as raw material, inorganic conductive powder cost is higher, therefore corresponding productProduct cost is also higher, is unfavorable for applying, and introduces the method that another reduces costs here for this reason,In new method, the antistatic glass frit of above-mentioned preparation is manufactured to antistatic glass as raw material.
A preparation method for antistatic glass, it comprises the steps:
Step 1) is manufactured antistatic glass frit: first by the titanate by inorganic conductive oxide, conductionIn a kind of or both the inorganic conductive powder of compositions of mixtures mix with glass dust, make compound,Wherein the mass fraction of inorganic conductive powder is 24%～50%, and the mass fraction of glass dust is 50%～76%; SoAfter the compound making is dispensed and is packed in fire resistant sagger, then found in shuttle kiln, or directly will makeCompound is directly conveyed in glass melter and founds; Glass melting temperature is 1200 DEG C～1600 DEG C, obtains molten stateGlass paste; Finally will obtain glass paste shrend cooling, and be broken into particle, can obtain antistaticGlass frit;
Step 2) to found: the antistatic glass frit that step 1) is obtained mixes with simple glass frit,Dispense on supporting body, then enter klining, firing temperature is 1150 DEG C～1300 DEG C, when clinkering zone insulationBetween be 60～120 minutes;
Step 3) cooling forming: after cooling, supporting body is taken out from kiln, then will be attached to supporting bodyThe antistatic glass on surface takes off.
By conduction antistatic glass frit mix with simple glass frit, in kiln to burn till temperatureDegree is 1150 DEG C～1300 DEG C, and clinkering zone temperature retention time is to burn till under the calcining system of 60～120 minutes, instituteThe structure of the antistatic glass making is antistatic glass frit and the mutual consolute of simple glass frit, antistaticGlass frit is equivalent to conducting bridge one by one in the antistatic glass of making, and electric charge can be led by itLogical, thus reach the object of electrostatic discharge. In order to ensure anti-static effect, in said method, simple glass3 times of quality≤antistatic glass frit quality of frit. Exceed 3 times, because antistatic glass frit is anti-The conducting bridge forming in static glass is less, and bulk resistor can exceed 109Ω m, anti-static effect is poor or notPossesses anti-static effect.
Further, the present invention also provides a kind of method of manufacturing antistatic glass mosaic, and it comprises as followsStep:
Step 1) batch mixing: by a kind of in the titanate by inorganic conductive oxide, conduction or both is mixedThe inorganic conductive powder of compound composition mixes with glass dust, makes compound, wherein inorganic conductive powderMass fraction be 24%～50%, the mass fraction of glass dust is 50%～76%;
Step 2) found: the compound cloth that step 1) is made be sprinkled into have latticed grid die cavity by resistance toIn the mould that fire material or high-temperature metal are made, then found in kiln, glass melting temperature be 1200 DEG C～1600 DEG C, temperature retention time is 1～2 hour, obtains the glass paste of molten state;
Step 3) moulding is cooling: take out after latticed die for molding is cooling until glass paste, obtainAntistatic glass mosaic finished product.
Further, prepare the cost of antistatic glass mosaic in order to reduce said method, and increase glassThe decorative effect of mosaic, can adopt and prepare with the following method antistatic glass mosaic:
Step 1) is manufactured antistatic glass frit: first by the titanate by inorganic conductive oxide, conductionIn a kind of or both the inorganic conductive powder of compositions of mixtures mix with glass dust, make compound,Wherein the mass fraction of inorganic conductive powder is 24%～50%, and the mass fraction of glass dust is 50%～76%; SoAfter the compound making is dispensed and is packed in fire resistant sagger, then found in shuttle kiln, or directly will makeCompound is directly conveyed in glass melter and founds; Glass melting temperature is 1200 DEG C～1600 DEG C, obtains molten stateGlass paste; Finally will obtain glass paste shrend cooling, and be broken into particle diameter≤4 object particle,Can obtain antistatic glass frit;
Step 2) found: cloth after the antistatic glass frit that step 1) is made and simple glass frit mixBe sprinkled in the mould of being made by refractory material or high-temperature metal with latticed grid die cavity, then in kilnBurn till, 1150 DEG C～1300 DEG C, clinkering zone temperature retention time is 60～120 minutes;
Step 3) cooling forming: after cooling, mold is taken out from kiln, then by the antistatic formingGlass Mosaic takes out from mould.
By conduction antistatic glass frit mix with simple glass frit, in kiln to burn till temperatureDegree is 1150 DEG C～1300 DEG C, and clinkering zone temperature retention time is to burn till under the calcining system of 60～120 minutes, instituteThe structure of the antistatic glass mosaic making is antistatic glass frit and the mutual consolute of simple glass frit,Antistatic glass frit is equivalent to conducting bridge one by one in the antistatic glass mosaic of making, and makes electric chargeCan pass through its conducting, thereby reach the object of antistatic. In order to ensure anti-static effect, at said methodIn, 3 times of quality≤antistatic glass frit quality of simple glass frit. Exceed 3 times, because of antistaticThe conducting bridge that glass frit forms in antistatic glass mosaic is less, and bulk resistor can exceed 109Ω·m，Anti-static effect is poor does not even possess anti-static effect.
Further, the devitrified glass ceramics that the present invention also provides a kind of manufacture to have antistatic glass layer is compoundThe method of plate, it comprises the steps:
Step 1) is manufactured antistatic glass frit: first by the titanate by inorganic conductive oxide, conductionIn a kind of or both the inorganic conductive powder of compositions of mixtures mix with glass dust, make compound,Wherein the mass fraction of inorganic conductive powder is 24%～50%, and the mass fraction of glass dust is 50%～76%; SoAfter the compound making is dispensed and is packed in fire resistant sagger, then found in shuttle kiln, or directly will makeCompound is directly conveyed in glass melter and founds; Glass melting temperature is 1200 DEG C～1600 DEG C, obtains molten stateGlass paste; Finally will obtain glass paste shrend cooling, and to be broken into particle diameter be≤4 object particles,Can obtain antistatic glass frit;
Step 2) charity frit: on Ceramic Tiles base substrate charity step 1) manufacture antistatic glass frit andThe mixed frit of simple glass frit, wherein the quality of simple glass frit is antistatic glass frit quality0～3 times, then spray bonding agent mixed frit is fixed, and the mixed frit of charity is flattened with roller;
Step 3) enters klining: burn till in roller kilns oxidizing atmosphere, 1200～1250 DEG C of firing temperatures, burnThe one-tenth cycle is 60～120 minutes;
Step 4) rubbing down processing: carry out edging and polishing by going out the cooling goods of kiln, hadThe glass-ceramic clad plate of antistatic glass layer.
Here said simple glass frit refers to the non-conductive glass frit that there is no anti-static effect.
Compared to the prior art, the antistatic glass cheapness of manufacture of the present invention, technique be simple, be easy to realize,And can be with it for example, as the abundant construction material of raw material manufacture, antistatic plate glass, anti-static glassGlass mosaic, antistatic glass frit, the glass-ceramic clad plate that has antistatic glass layer etc.
Detailed description of the invention
Further illustrate technical scheme of the present invention below by concrete preferred embodiment.
The formula table that following table 1 is embodiment.
Table 1
Cryogenic glass powder refers to the glass dust that melt temperature is lower, for example nonex powder; Common building glassPowder refers to the powder that the discarded rear fragmentation of door and window plate glass used is made; Ware glass powder refer to vial,The powder that tank, cup, the discarded rear fragmentation of dish are made; Microcrystalline glass powder refers to the powder of making after devitrified glass fragmentationMaterial, glass frit powder refers to that cooling the glass direct-water-quenching of the molten state block making is broken into powder to be madePowder.
Embodiment 1～10: the plate glass of manufacturing conduction.
Its manufacture method is as follows:
A method of manufacturing antistatic plate glass, it comprises the steps;
Step 1) batch mixing: according to the listed recipe ingredient of table 1, by the titanium by inorganic conductive oxide, conductionThe inorganic conductive powder of a kind of in hydrochlorate or both compositions of mixtures and glass dust are poured in ball mill and are dry mixedBall milling about 30 minutes mixes raw material, makes compound, wherein the mass fraction of inorganic conductive powderBe 24%～50%, the mass fraction of glass dust is 50%～76%.
Step 2) to found: the compound that step 1) is made evenly dispenses in fireproof die, described mouldOn there is the die cavity of depression, the smooth and die cavity bottom surface of cavity surface is plane, in kiln, founds, and foundsTemperature is 1200 DEG C～1600 DEG C, obtains the glass paste of molten state.
In above-mentioned steps 2) in the fireproof die material that uses can selective oxidation aluminium, silicon nitride, tungsten orThe alloys of tungsten etc., are chosen as the fireproof die of aluminium oxide material at this serial embodiment.
For the glass and the mould bonding that prevent from forming after compound melting, be difficult to the demoulding, implement in this seriesIn example, be coated with one deck adherent layer at die surface, adherent layer material is aluminium oxide. Certainly art technology peopleMember should be appreciated that, outside alumina, the refractory materials such as mullite, carborundum, silicon nitride are as adherent layer materialMaterial all can. In this serial embodiment, be that aluminium oxide to be added water and add mass fraction be 3% carboxymethyl fibreAfter tieing up plain ball milling, make slurry, then spread upon on mould.
In addition, overflow mould for fear of the glass paste of the molten state forming after compound melting, at clothTime mix the bed of material thickness be 1/2～2/3 of the upper mould chamber degree of depth, in this serial embodiment, select mouldDie cavity be cuboid, its specification is long × wide × dark=500mm × 400mm × 15mm, mixes the cloth of the bed of materialThickness is 7.5mm～10mm.
Step 3) cooling forming: until step 2) glass paste that makes after cooled and solidified, continues in mouldBeing cooled to normal temperature can take out the antistatic plate glass obtaining from mould.
Further, in step 3) cooling forming process, also comprise annealing operation, step 3) is obtainedPlate glass is annealed 1～2 hour at 480 DEG C～540 DEG C. Annealing can be eliminated the stress of glass kind, anti-Only stress is concentrated the broken loss causing.
The antistatic plate glass of more than making can carry out the machining in later stage, comprise cutting, grinding,Polishing etc.
The plate glass that test makes, its sheet resistance is 2.0 × 103～8×105Ohm, bulk resistor is 3.0×103～9.0×105Ω m is good antistatic material.
Embodiment 11
Embodiment 11 provides a kind of manufacture method of antistatic glass vessel, selects joining as sequence number in table 15Prepare raw material and (be construed as here at the formula of listed other of table 1 and be also suitable for, because comparing class all sideSeemingly, only given an illustrative example here).
The method that this embodiment manufactures glassware is as follows:
Step 1) batch mixing: fill a prescription according to sequence number in table 15, will be existed by inorganic conductive powder and glass particleIn vibrating ball-mill, vibration mixes 30 minutes, and raw material is mixed, and makes compound;
Step 2) found: the compound that step 1) is made is founded in kiln, glass melting temperature be 1200 DEG C～1600 DEG C, obtain the glass paste of molten state;
Step 3) moulding is cooling: by step 2) glass paste that obtains pours blow molding in mould into,Then about 500 DEG C annealing 1～2 hour, cooling, obtain the glassware conducting electricity.
The sheet resistance of the antistatic glass vessel that test is manufactured is 8 × 104Ohm, bulk resistor is 9 × 104Ω m. It is a kind of good antistatic product.
Embodiment 12-15
In a kind of method of manufacturing antistatic glass mosaic of this serial embodiment, in option table 1 sequence number be 3,4,7,9 formula, (is construed as at table 1 listed here as the formula of embodiment 12-15 respectivelyOther formula be also suitable for as the formula of manufacturing antistatic glass mosaic).
The method that this serial embodiment manufactures antistatic glass mosaic is as follows:
Step 1) batch mixing: take inorganic conductive powder according to 3,4,7, No. 9 formulas listed in formula tableWith glass particle, and in ball mill, dry ball milling mixes 30 minutes, and raw material is mixed, and makes mixingMaterial;
Step 2) found: the compound cloth that step 1) is made be sprinkled into have latticed grid die cavity by resistance toIn the mould that fire material or high-temperature metal are made, then found in kiln, glass melting temperature be 1200 DEG C～1600 DEG C, temperature retention time is 1～2 hour, obtains the glass paste of molten state;
Step 3) moulding is cooling: take out after latticed die for molding is cooling until glass paste, obtainAntistatic glass mosaic finished product.
Step 2) found adopted mould and can be formed by refractory material manufactures such as aluminium oxide, certainly also canAdopt the resistant to elevated temperatures metal manufacture such as tungsten to form, and antistatic glass in order to prevent that moulding from making after coolingMosaic and mould adhesion are selected at die surface and are coated with one deck adherent layer, adherent layer material in embodiment 15For aluminium oxide. Certainly it should be appreciated by those skilled in the art that outside alumina mullite, carborundum, nitrogenThe refractory materials such as SiClx all can as adherent layer material. In this serial embodiment, be that aluminium oxide is added water alsoAfter the carboxymethyl cellulose ball milling that interpolation mass fraction is 3%, make slurry, then spread upon on mould.
In addition, in order to prevent that the glass paste forming after melting from overflowing, step 2) when cloth compound at mould1/2～2/3 degree of depth that on tool, in latticed grid die cavity, the thickness of the bed of material that forms is cavity depth. ?It is 12mm that this series is executed routine selected depth, and the maximum ulking thickness of compound in grid is 8mm.
Certainly,, in order to eliminate stress, also can increase annealing operation.
The antistatic glass mosaic that test has been manufactured, its sheet resistance is 3 × 104～8×105Ohm, bodyResistance is 4.5 × 104～9×105Ω m is a kind of good antistatic material.
Certainly, above antistatic mosaic also can be adopted with the following method and manufacture, molten via above-mentioned formula materialThe molten glass slurry of making after melting is poured in the mould that latticed refractory material or high-temperature metal make,After glass paste is cooling, the demoulding, obtains antistatic glass Mosaic product.
Wherein embodiment 16-20
At this serial embodiment, provide the method for manufacturing antistatic glass frit. In option table 1 sequence number be 3,4,7,9,10 formula, (is construed as at table 1 here as the formula of embodiment 16-20 respectivelyThe formula of listed other is also suitable for as the formula of manufacturing antistatic glass frit). This is class embodiment manufactureMethod is as follows:
Step 1) batch mixing: take inorganic conductive according to 3,4,7,9, No. 10 formulas listed in formula tablePowder mixes approximately 30 minutes with glass particle vibration in vibrating ball-mill, and raw material is mixed, and makes compound;
Step 2) to found: the compound that step 1) is made dispenses and packs in fire resistant sagger, then at shuttle kilnIn found; Glass melting temperature is 1200 DEG C～1600 DEG C, obtains the glass paste of molten state.
Here should illustrate also and compound directly can be inputted in glass melter and founded, obtain the glass of molten stateGlass slurry.
Step 3) moulding is cooling: by step 2) to obtain glass paste shrend cooling, and be broken into graininessCan obtain antistatic glass frit.
In this serial embodiment, founding temperature retention time is 1～2 hour.
In addition, in order to prevent that the glass paste forming after melting from overflowing, step 2) in compound cloth is sprinkled intoWhile packing in saggar, fill up 1/2～2/3 degree of depth of saggar.
Above antistatic glass frit can be used as glaze raw material, or directly cloth imposes on ceramic body surface, shapeBecome to have the Ceramic Tiles goods of antistatic glazed layer or glassy layer.
And in order to obtain more rich decorative effect, can adopt the glass frit particle with different coloursAs raw material, the pottery of manufacturing is like this decorated and is felt stronger with antistatic glass frit, in addition, and for crystallite glassThe needed frit of glass Ceramic Composite panel products can suitably increase the consumption of devitrified glass particle in formula.
Embodiment 21-25
A kind of glass-ceramic clad plate with antistatic glass layer is provided in this serial embodiment,Its manufacture method is as follows:
Step 1): select respectively the pottery antistatic glass frit of embodiment 16-20 manufacturing, brokenBroken, select 4～80 object particles, the pottery antistatic glass that is used as respectively embodiment 21-25 is moltenPiece raw material.
Step 2) charity frit: the pottery antistatic glass that charity step 1) is manufactured on Ceramic Tiles base substrateFrit, charity thickness is 2～8mm, then sprays bonding agent pottery conduction glass frit is fixed, and useRoller flattens the pottery of charity with antistatic glass frit; Wherein the specification of ceramic body be 800mm ×800mm, the ceramic green of embodiment ceramic body that 21-23 uses, embodiment 24,25 uses potteryBase substrate is biscuiting base substrate.
Certainly it will be appreciated by those skilled in the art that biscuit after sintering or the base substrate of glazing and/or stamp all canTo meet instructions for use.
Step 3) enters klining: burn till in roller kilns oxidizing atmosphere, 1200～1250 DEG C of firing temperatures, burnThe one-tenth cycle is 60～120 minutes.
Step 4) rubbing down processing: carry out edging and polishing by going out the cooling goods of kiln, hadThe glass-ceramic clad plate of antistatic glass layer.
In the method providing at this serial embodiment, step 2) in the bonding agent that uses for mass fraction be5% carboxymethyl cellulose aqueous solution.
The finished product of manufacturing is the glass-ceramic clad plate that surface has one deck antistatic glass layer, testThe sheet resistance of its antistatic glass layer is 3 × 104～8×105Ohm, bulk resistor is 4.5 × 104～9×105Ω m. It is a kind of good antistatic material.
Embodiment 26
Certainly, except the pottery of the employing embodiment 16-20 manufacturing described in embodiment 21-25 is used anti-Static glass frit produce has outside the glass-ceramic clad plate of antistatic glass layer, can also adopt asThe method manufacture that embodiment 26 provides has the glass-ceramic clad plate of antistatic glass layer, its manufactureMethod is as follows:
Step 1) batch mixing: adopt if the formula of sequence number in table 1 10 is by mixed to inorganic conductive powder and glass particleClose evenly, make compound;
Step 2) cloth: the specification after stamp be 800mm × 800mm ceramic body as carrier,The compound that the upper even charity step 1) in its surface is manufactured, the ulking thickness of compound is 2～8mm;
Step 3) enters klining: burn till in roller kilns oxidizing atmosphere, 1200～1250 DEG C of firing temperatures, burnThe one-tenth cycle is 60～120 minutes;
Step 4) rubbing down processing: carry out edging and polishing by going out the cooling goods of kiln, hadThe method of the glass-ceramic clad plate of antistatic glass layer.
Here in step 1), compounding process preferred embodiment can be with reference to the description in embodiment 1-20.
Test adopts the glass-ceramic clad plate with antistatic glass layer of as above method manufacture, recordsThe sheet resistance of antistatic glass layer is 5 × 104Ohm, bulk resistor is 8 × 104Ohm. A kind of goodAntistatic material.
Embodiment 27
This embodiment provides a kind of glass-ceramic clad plate that has antistatic and have antistatic glass layer,Its manufacture method is substantially the same manner as Example 21, and difference is in step 2) in, the frit of institute's charity isThe antistatic glass frit that embodiment 16 is prepared and the mixed frit of glass frit, wherein simple glass fritThe quality of mixed frit be 3 times of antistatic glass frit.
Test adopts the glass-ceramic clad plate with antistatic glass layer of as above method manufacture, recordsThe sheet resistance of antistatic glass layer is 9 × 108Ohm, bulk resistor is 9.5 × 108Ohm. Between anti-Electrostatic material requires the critical value of performance.
Embodiment 28
Provide another to manufacture the method for antistatic glass in this enforcement, it comprises the steps:
Step 1) is manufactured antistatic glass frit: first take raw material by mixing No. 10 formulas in table 1,By raw material ball milling 30 minutes in dry method ball mill, make compound, then directly by straight the compound makingConnect to be conveyed in glass melter and found; Glass melting temperature is 1200 DEG C～1600 DEG C, obtains the glass paste of molten stateMaterial; Finally will obtain glass paste shrend cooling, and be broken into particle diameter≤4 object particle, can be preventedStatic glass frit;
Step 2) to found: the antistatic glass frit that step 1) is obtained and simple glass frit are in mass ratioFor the ratio of 1:1 mixes, dispense on Ceramic Tiles green compact, then enter klining, firing temperature is1150 DEG C～1300 DEG C, clinkering zone temperature retention time is 60～120 minutes;
Step 3) cooling forming: after cooling, supporting body is taken out from kiln, then will be attached to Ceramic TilesThe antistatic glass on green compact surface takes off.
Test its electric property, sheet resistance is 5 × 106Ohm, bulk resistor is 4.5 × 106Ω m is onePlant good antistatic material.
In this embodiment, antistatic glass is more difficult to be separated with the Ceramic Tiles as its supporting body, can pass throughCeramic Tiles base substrate arranges the adherent layer that one deck has refractory material to form.
Embodiment 29
The present embodiment provides a kind of manufacture method of relatively inexpensive antistatic glass mosaic, and it comprises as followsStep:
Step 1) is prepared antistatic glass frit according to the mode of the middle step 1 of embodiment 28;
Step 2) to found: the antistatic glass frit that step 1) is made and simple glass frit are in mass ratioFor 1:2 mix after cloth be sprinkled into and have in the mould that the high-temperature metal tungsten of latticed grid die cavity makes, then at kilnKiln roasting, 1150 DEG C～1300 DEG C, clinkering zone temperature retention time is 60～120 minutes;
Step 3) cooling forming: after cooling, mold is taken out from kiln, then by the antistatic formingGlass Mosaic takes out from mould.
Test its electric property, sheet resistance is 6 × 107Ohm, bulk resistor is 8 × 107Ω m. A kind ofGood antistatic material.
Know-why of the present invention has below been described in conjunction with specific embodiments. These are described just in order to explain thisThe principle of invention, and can not be interpreted as by any way limiting the scope of the invention. Based on hereinExplain, those skilled in the art does not need to pay performing creative labour can associate other tool of the present inventionBody embodiment, within these modes all will fall into protection scope of the present invention.
Claims (4)
1. a manufacture method with the glass-ceramic clad plate of antistatic glass layer, it comprises the steps:
Step 1) is manufactured antistatic glass frit: first the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide, conduction or both compositions of mixtures is mixed with glass dust, make compound, wherein the mass fraction of inorganic conductive powder is 24%～50%, and the mass fraction of glass dust is 50%～76%; Then the compound making is dispensed and packed in fire resistant sagger, then found in shuttle kiln, maybe the compound making is directly conveyed in glass melter and is founded; Glass melting temperature is 1200 DEG C～1600 DEG C, obtains the glass paste of molten state; Finally will obtain glass paste shrend cooling, and to be broken into particle diameter be≤4 object particles, can obtain antistatic glass frit;
Step 2) charity frit: the antistatic glass frit that charity step 1) is manufactured on Ceramic Tiles base substrate and the mixed frit of simple glass frit, 3 times of the quality≤described antistatic glass frit quality of described simple glass frit, then spray bonding agent mixed frit is fixed, and the mixed frit of charity is flattened with roller;
Step 3) enters klining: burns till in roller kilns oxidizing atmosphere, and 1200～1250 DEG C of firing temperatures, firing period is 60～120 minutes;
Step 4) rubbing down processing: carry out edging and polishing by going out the cooling goods of kiln, obtain having the glass-ceramic clad plate of antistatic glass layer.
2. the method for claim 1, is characterized in that, described inorganic conductive oxide is one or more mixing in conductive tin oxide, conductive zinc oxide, conductive titanium oxide, electric conductive oxidation iron.
3. the method for claim 1, is characterized in that, the titanate of described conduction is one or more mixing in conduction barium titanate, conduction lead titanates.
4. the method for claim 1, is characterized in that step 2) in the bonding agent that the uses carboxymethyl cellulose aqueous solution that is 5% for mass fraction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104291864A (en) * | 2014-09-23 | 2015-01-21 | 佛山市禾才科技服务有限公司 | Preparation method of glass ceramic composite board |
| CN104291875B (en) * | 2014-09-23 | 2016-01-20 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104261881B (en) * | 2014-09-23 | 2016-02-24 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104261883B (en) * | 2014-09-23 | 2016-02-24 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104291877B (en) * | 2014-09-23 | 2016-03-23 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104261895B (en) * | 2014-09-23 | 2016-02-24 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104261892B (en) * | 2014-09-23 | 2016-02-24 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104291874B (en) * | 2014-09-23 | 2016-08-24 | 佛山市禾才科技服务有限公司 | A kind of glass-ceramic clad plate production technology |
| CN104291881B (en) * | 2014-09-23 | 2016-03-23 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104230386B (en) * | 2014-09-23 | 2016-08-24 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN104261891B (en) * | 2014-09-23 | 2016-02-24 | 佛山市禾才科技服务有限公司 | A kind of preparation method of once-firing crystallite glass composite plate |
| CN112897885B (en) * | 2021-03-26 | 2022-05-10 | 连云港神汇硅材料科技有限公司 | High-purity silica glass ceramic material and preparation method thereof |
| CN114956550B (en) * | 2022-07-05 | 2024-01-05 | 四川虹科创新科技有限公司 | High-strength antistatic glass and preparation method thereof |
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