A kind of anti-electrostatic glass and manufacture method thereof
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, relate in particular to glass and production technology thereof, relate more specifically to a kind of anti-electrostatic glass and manufacture method thereof.
Background technology
Static is a kind of objective spontaneous phenomenon, and the mode of generation is multiple, as contact, friction etc.Static, to some responsive instrument and place, may cause fatal harm.Normal work as magnetoresistive effect (electromagnetic interference or electromagnetic compatibility) the meeting interference precision instrument of static generation when discharging, causes the flase operation of automatic equipment; The gathering of electric charge may produce point discharge phenomenon, may burn precision instrument, and the electrical spark of the generation dust that may ignite, causes explosion hazard.Therefore electrostatic protection technology, all receiving very big attention as electronic industry, petroleum industry, weapon industry, textile industry, rubber industry and space flight and military field, makes every effort to seek to reduce the loss that static causes.
Simple glass material has very high resistivity, easily gathers electric charge, and gathering of these electric charges may bring multiple harm described above.There is every year the damnous report of relevant static hazard, be therefore badly in need of a kind of material of construction that can overcome the above problems.
Research shows, when the volume specific resistance of material surpasses 1 * 10
10during Ω m, the ability of material dissipation electric charge obviously weakens; From eliminating the angle of static, consider, the volume specific resistance of material should be higher than 1 * 10
10Ω m.When material surface resistance is 10
4~10
9during Ω, the electric charge of accumulation can discharge as soon as possible, thereby reaches the effect of anti-electrostatic.
Our common simple glass is a kind of isolator under normal conditions, thereby electric charge is easily gathered, accumulation static in surface.People have researched and developed the technique of a lot of production anti-electrostatic glass for this reason, for example, in glass, add conductive ion, at glass surface additional guide electrolemma etc.In glass, add conductive ion mainly for the manufacture of solid electrolyte glass, electrocondution slurry anti-electrostatic glass powder, above main application is lithium ion battery etc.; At glass surface additional guide electrolemma, mainly for the manufacture of anti-electrostatic glass fiber and the glasswork with surface conduction ability, it is mainly used in flat pannel display field, the ITO(tin Indium sesquioxide being for example widely used in flat pannel display) glass.The anti-electrostatic glass cost of above two kinds of mode manufacturings is high, and use range is substantially fixing, and particularly ito glass producing apparatus is expensive, needs plasma sputtering equipment, and the anti-electrostatic glass of manufacturing only has the conducting film that one deck sputter forms on surface.The anti-electrostatic glass that above two kinds of modes make is not all suitable for as building and ornament materials.
In building and ornament materials, glasswork occupies very large ratio.Progress along with production technology and material, except traditional building glass, the product innovations such as glass Mosaic, devitrified glass brick, glass-ceramic clad plate, the brilliant brick of throwing, throwing glazed brick continue to bring out, and are bringing into play more and more important effect in buildings internal and external ornament.If anti-electrostatic glass material, for above product, can be obtained to the building decorative product with electro-magnetic screen function, electrostatic-proof function, avoid static hazard.People constantly research and develop and have the batch production of being applicable to, anti-electrostatic glass for building and goods thereof with low cost for this reason.
Summary of the invention
The object of the invention is to propose a kind of anti-electrostatic glass of cheapness, it has with low cost, the features such as manufacturing process is simple, and can as a kind of basic material, manufacture building and ornament materials by it or using it, can provide comfortable, healthy living space to people.And using this kind of anti-electrostatic glass as material, can also produce for example anti-electrostatic sheet glass, anti-electrostatic glass vessel, anti-electrostatic glass mosaic, anti-electrostatic glass frit, the antistatic product such as the glass micro-crystalline ceramic composition board of anti-electrostatic.
For reaching this object, the present invention is by the following technical solutions: a kind of anti-electrostatic glass, melting is cooling after as raw material blending makes for the inorganic conductive powder that it is is at least 24%~50% by mass fraction and 50%~76% glass powder, a kind of in the titanate that described inorganic conductive powder is inorganic conductive oxide compound, conduction or both mixtures.
Further, in above-mentioned anti-electrostatic glass, inorganic conductive oxide compound is one or more mixing that include but not limited in conductive tin oxide, conductive zinc oxide, conductive titanium oxide, electric conductive oxidation iron.
Further, in above-mentioned anti-electrostatic glass, the titanate of conduction is one or more mixing that include but not limited to conduct electricity in barium titanate, conduction lead titanate.
Further, in above-mentioned anti-electrostatic glass, glass powder can be one or more combinations in cryogenic glass powder, common building glass powder, ware glass powder, microcrystalline glass powder, glass frit powder.
Cryogenic glass powder refers to the glass powder that melt temperature is lower, for example lead glass powder; Common building glass powder refers to the powder that the discarded rear fragmentation of door and window sheet glass used is made; Ware glass powder refers to the powder that vial, tank, cup, the discarded rear fragmentation of dish are made; Microcrystalline glass powder refers to the powder of making after devitrified glass fragmentation, and glass frit powder refers to the cooling block making of the glass direct-water-quenching of molten state is broken into the powder that powder is made.In addition, glass frit, also usually used as the glaze raw material of Production of Ceramics, mainly plays and makes fusing assistant and improve glaze quality effect, and glass frit also can be used as the raw material of producing glass-ceramic clad plate in addition.
Certainly, above glass powder component also can adopt the form of raw mineral materials to add, but melt temperature will be higher than 1400 ℃.
Above-mentioned anti-electrostatic glass can be made anti-electrostatic sheet glass, anti-electrostatic glass vessel, anti-electrostatic glass mosaic, anti-electrostatic glass frit.
The present invention also provides a kind of method of manufacturing anti-electrostatic glass, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%;
Step 2) found: the compound that step 1) is made is founded in kiln, glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state;
Step 3) moulding is cooling: by step 2) the cooling anti-electrostatic glass goods that obtain of glass paste moulding that obtain.
Further, in aforesaid method, the conductive oxide using in step 1) includes but not limited to one or more mixing in conductive tin oxide, conductive zinc oxide, conductive titanium oxide, electric conductive oxidation iron.
Further, in aforesaid method, the titanate of the conduction of using in step 1) includes but not limited to one or more mixing of conducting electricity in barium titanate, conduction lead titanate.
Further, in aforesaid method, in step 1), the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder and adopts dry mixed mode to carry out.Certainly the mixed mode of wet method is also passable, but need to increase by a step by the dry operation of the compound after wet-mixed, can increase energy consumption like this.
Further, in aforesaid method, dry mixed equipment is vibrating ball mill or is dry mixed ball mill, and the mixed time is >=30 minutes.
In aforesaid method, step 2) before founding, the compound cloth that can first step 1) be mixed is spread on supporting body, then founds.So, the anti-electrostatic glass of making can present different shape with supporting body surface topography, and for example supporting body surface topography is plane, can make anti-electrostatic sheet glass; Supporting body surface has latticed grid, can make anti-electrostatic glass mosaic.
Further, in aforesaid method, the material of supporting body can be a kind of in refractory materials, ceramic green body, ceramic biscuiting base substrate, hot metal.
Further, in aforesaid method, between supporting body and compound, be provided with adherent layer, after sintering, anti-electrostatic glass just can be easy to take off from supporting body like this.The material of adherent layer can be the refractory materialss such as aluminum oxide, mullite, aluminium vanadine, trichroite, silicon carbide, silicon nitride; Particularly, can, by above-mentioned refractory materials ball milling form slurry, be coated on supporting body, and then dispense compound.
Further, the present invention also provides a kind of method of manufacturing anti-electrostatic sheet glass, and it comprises the steps;
Step 1) batch mixing: the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%;
Step 2) found: the compound that step 1) is made evenly dispenses in fireproof die, the die cavity on described mould with depression, the smooth and die cavity bottom surface of cavity surface is plane, in kiln, founds, glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state;
Step 3) cooling forming: until step 2) glass paste making after cooled and solidified, continues to be cooled to normal temperature and the anti-electrostatic sheet glass obtaining can be taken out from mould in mould.
Further, in step 3) cooling forming process, also comprise annealing operation, the sheet glass that step 3) is obtained is annealed 1~2 hour at 480 ℃~540 ℃.Annealing can be eliminated the stress of glass kind, prevents the concentrated broken loss causing of stress.
The anti-electrostatic sheet glass of more than making can carry out the mechanical workout in later stage, comprises cutting, grinding, polishing etc.
Certainly, except above method, can also adopt the known manufacture sheet glass techniques such as float glass process, vertical drawing process, horizontal sheet process, rolling process to prepare above-mentioned dull and stereotyped anti-electrostatic glass.
Further, the present invention also provides a kind of method of manufacturing anti-electrostatic glass vessel, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%;
Step 2) found: the compound that step 1) is made is founded in kiln, glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state;
Step 3) moulding is cooling: by step 2) glass paste that obtains pours blow molding in forming mould into, then about 500 ℃ annealing 1~2 hour, finally cooling, obtains the glassware of conduction.
Further, the present invention also provides a kind of manufacture method of anti-electrostatic glass frit, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass particle is 50%~76%;
Step 2) found: the compound that step 1) is made dispenses and packs in fire resistant sagger, then founds in kiln, or directly compound is conveyed in glass melter and is founded; Glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state;
Step 3) moulding is cooling: by step 2) to obtain glass paste shrend cooling, and be broken into particulate state and can obtain anti-electrostatic glass frit.
Above anti-electrostatic glass frit can be used as glaze raw material, or directly cloth imposes on ceramic body surface, forms the ceramic tile goods with anti-electrostatic glazed layer or glass coating.
Manufacture method at the above anti-electrostatic glass of introducing, anti-electrostatic sheet glass, anti-electrostatic sheet glass need to adopt a large amount of inorganic conductive powder as raw material, inorganic conductive powder cost is higher, therefore corresponding product cost is also higher, be unfavorable for applying, here introduce the method that another reduces costs for this reason, in new method, the anti-electrostatic glass frit of above-mentioned preparation is manufactured to anti-electrostatic glass as raw material.
A preparation method for anti-electrostatic glass, it comprises the steps:
Step 1) is manufactured anti-electrostatic glass frit: first the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%; Then the compound making is dispensed and packed in fire resistant sagger, then found in shuttle kiln, or directly the compound making is directly conveyed in glass melter and is founded; Glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state; Finally will obtain glass paste shrend cooling, and be broken into particle, can obtain anti-electrostatic glass frit;
Step 2) found: the anti-electrostatic glass frit that step 1) is obtained mixes with simple glass frit, dispenses on supporting body, then enter klining, firing temperature is 1150 ℃~1300 ℃, and clinkering zone soaking time is 60~120 minutes;
Step 3) cooling forming: after cooling, supporting body is taken out from kiln, then the anti-electrostatic glass that is attached to supporting body surface is taken off.
Anti-electrostatic glass frit by conduction mixes with simple glass frit, in kiln, take firing temperature as 1150 ℃~1300 ℃, clinkering zone soaking time is to burn till under the calcining system of 60~120 minutes, the structure of prepared anti-electrostatic glass is anti-electrostatic glass frit and the mutual consolute of simple glass frit, anti-electrostatic glass frit is equivalent to conducting bridge one by one in the anti-electrostatic glass of making, make electric charge can pass through its conducting, thereby reach the object of electrostatic discharge.In order to guarantee anti-static effect, in aforesaid method, 3 times of quality≤anti-electrostatic glass frit quality of simple glass frit.Surpass 3 times, less because of the conducting bridge that anti-electrostatic glass frit forms in anti-electrostatic glass, body resistance can surpass 10
9Ω m, anti-static effect is poor or do not possess anti-static effect.
Further, the present invention also provides a kind of method of manufacturing anti-electrostatic glass mosaic, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%;
Step 2) found: the compound cloth that step 1) is made is sprinkled in the mould of being made by refractory materials or hot metal with latticed grid die cavity, in kiln, found again, glass melting temperature is 1200 ℃~1600 ℃, and soaking time is 1~2 hour, obtains the glass paste of molten state;
Step 3) moulding is cooling: until glass paste, after latticed die for molding is cooling, take out, obtain anti-electrostatic glass mosaic finished product.
Further, in order to reduce aforesaid method, prepare the cost of anti-electrostatic glass mosaic, and increase the decorative effect of glass Mosaic, can adopt and prepare with the following method anti-electrostatic glass mosaic:
Step 1) is manufactured anti-electrostatic glass frit: first the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%; Then the compound making is dispensed and packed in fire resistant sagger, then found in shuttle kiln, or directly the compound making is directly conveyed in glass melter and is founded; Glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state; Finally will obtain glass paste shrend cooling, and be broken into particle diameter≤4 object particle, can obtain anti-electrostatic glass frit;
Step 2) found: after the anti-electrostatic glass frit that step 1) is made and simple glass frit mix, cloth is sprinkled in the mould of being made by refractory materials or hot metal with latticed grid die cavity, again at kiln kiln roasting, 1150 ℃~1300 ℃, clinkering zone soaking time is 60~120 minutes;
Step 3) cooling forming: after cooling, mold is taken out from kiln, then the anti-electrostatic glass mosaic of formation is taken out from mould.
Anti-electrostatic glass frit by conduction mixes with simple glass frit, in kiln, take firing temperature as 1150 ℃~1300 ℃, clinkering zone soaking time is to burn till under the calcining system of 60~120 minutes, the structure of prepared anti-electrostatic glass mosaic is anti-electrostatic glass frit and the mutual consolute of simple glass frit, anti-electrostatic glass frit is equivalent to conducting bridge one by one in the anti-electrostatic glass mosaic of making, make electric charge can pass through its conducting, thereby reach the object of anti-electrostatic.In order to guarantee anti-static effect, in aforesaid method, 3 times of quality≤anti-electrostatic glass frit quality of simple glass frit.Surpass 3 times, less because of the conducting bridge that anti-electrostatic glass frit forms in anti-electrostatic glass mosaic, body resistance can surpass 10
9Ω m, anti-static effect is poor does not even possess anti-static effect.
Further, the present invention also provides a kind of manufacture to have the method for the glass-ceramic clad plate of anti-electrostatic glass layer, and it comprises the steps:
Step 1) is manufactured anti-electrostatic glass frit: first the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures is mixed with glass powder, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%; Then the compound making is dispensed and packed in fire resistant sagger, then found in shuttle kiln, or directly the compound making is directly conveyed in glass melter and is founded; Glass melting temperature is 1200 ℃~1600 ℃, 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 anti-electrostatic glass frit;
Step 2) charity frit: the anti-electrostatic glass frit that charity step 1) is manufactured on ceramic tile base substrate and the mixed frit of simple glass frit, wherein the quality of simple glass frit is 0~3 times of anti-electrostatic glass frit quality, then spray caking agent mixed frit is fixed, and with roller, the mixed frit of charity is flattened;
Step 3) enters klining: in roller kiln oxidizing atmosphere, burns till, and 1200~1250 ℃ 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 anti-electrostatic 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 anti-electrostatic glass of manufacture of the present invention is cheap, technique is simple, be easy to realize, and can be with it as the abundant material of construction of raw material manufacture, such as anti-electrostatic sheet glass, anti-electrostatic glass mosaic, anti-electrostatic glass frit, there is the glass-ceramic clad plate of anti-electrostatic glass layer etc.
Embodiment
Below by concrete preferred implementation, further illustrate technical scheme of the present invention.
The formula table that following table 1 is embodiment.
Table 1
Cryogenic glass powder refers to the glass powder that melt temperature is lower, for example nonex powder; Common building glass powder refers to the powder that the discarded rear fragmentation of door and window sheet glass used is made; Ware glass powder refers to the powder that vial, tank, cup, the discarded rear fragmentation of dish are made; Microcrystalline glass powder refers to the powder of making after devitrified glass fragmentation, and glass frit powder refers to the cooling block making of the glass direct-water-quenching of molten state is broken into the powder that powder is made.
Embodiment 1~10: the sheet glass of manufacturing conduction.
Its manufacture method is as follows:
A method of manufacturing anti-electrostatic sheet glass, it comprises the steps;
Step 1) batch mixing: according to the listed recipe ingredient of table 1, the inorganic conductive powder of a kind of in the titanate by inorganic conductive oxide compound, conduction or both compositions of mixtures and glass powder are poured into and in ball mill, is dry mixed ball milling and about 30 minutes, raw material mixed, make compound, wherein the mass fraction of inorganic conductive powder is 24%~50%, and the mass fraction of glass powder is 50%~76%.
Step 2) found: the compound that step 1) is made evenly dispenses in fireproof die, the die cavity on described mould with depression, the smooth and die cavity bottom surface of cavity surface is plane, in kiln, founds, glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state.
In above-mentioned steps 2) in the fireproof die material that uses can selective oxidation aluminium, the alloy of silicon nitride, tungsten or tungsten etc., at this serial embodiment, be chosen as the fireproof die of aluminum oxide material.
Glass and mould bonding in order to prevent from forming after compound melting, be difficult to the demoulding, in this serial embodiment, at die surface, is coated with one deck adherent layer, and adherent layer material is aluminum oxide.Certainly it should be appreciated by those skilled in the art that, outside alumina, the refractory materialss such as mullite, silicon carbide, silicon nitride all can as adherent layer material.In this serial embodiment, be that aluminum oxide to be added to water and add mass fraction be to make slurry after 3% carboxymethyl cellulose ball milling, then spread upon on mould.
In addition, glass paste for fear of the molten state forming after compound melting overflows mould, the thickness that mixes the bed of material when cloth is 1/2~2/3 of the upper mould chamber degree of depth, the die cavity of selecting mould in this serial embodiment is rectangular parallelepiped, its specification is long * wide * dark=500mm * 400mm * 15mm, and the fabric thickness that mixes the bed of material is 7.5mm~10mm.
Step 3) cooling forming: until step 2) glass paste making after cooled and solidified, continues to be cooled to normal temperature and the anti-electrostatic sheet glass obtaining can be taken out from mould in mould.
Further, in step 3) cooling forming process, also comprise annealing operation, the sheet glass that step 3) is obtained is annealed 1~2 hour at 480 ℃~540 ℃.Annealing can be eliminated the stress of glass kind, prevents the concentrated broken loss causing of stress.
The anti-electrostatic sheet glass of more than making can carry out the mechanical workout in later stage, comprises cutting, grinding, polishing etc.
The sheet glass that test makes, its surface resistivity is 2.0 * 10
3~8 * 10
5ohm, body resistance is 3.0 * 10
3~9.0 * 10
5Ω m is good antistatic material.
Embodiment 11
Embodiment 11 provides a kind of manufacture method of anti-electrostatic glass vessel, selects and prepares raw material (be construed as at the formula of listed other of table 1 also applicable, because all comparing class seemingly, only given an illustrative example here) here as the formula of sequence number in table 15.
The method that this embodiment manufactures glassware is as follows:
Step 1) batch mixing: according to 5 formulas of sequence number in table 1, will be mixed 30 minutes with glass particle vibration in vibrating ball mill by inorganic conductive powder, raw material is mixed, and make compound;
Step 2) found: the compound that step 1) is made is founded in kiln, glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state;
Step 3) moulding is cooling: by step 2) glass paste that obtains pours blow molding in forming mould into, then about 500 ℃ annealing 1~2 hour, cooling, obtains the glassware of conduction.
The surface resistivity of the anti-electrostatic glass vessel that test is manufactured is 8 * 10
4ohm, body resistance is 9 * 10
4Ω m.It is a kind of good antistatic product.
Embodiment 12-15
In a kind of method of manufacturing anti-electrostatic glass mosaic of this serial embodiment, in option table 1, sequence number is 3,4,7,9 formula, respectively as the formula of embodiment 12-15 (being construed as here at the formula of listed other of the table 1 also applicable formula as manufacturing anti-electrostatic glass mosaic).
The method that this serial embodiment manufactures anti-electrostatic glass mosaic is as follows:
Step 1) batch mixing: take inorganic conductive powder and glass particle according to 3,4,7, No. 9 formulas listed in formula table, and dry ball milling mixes 30 minutes in ball mill, and raw material is mixed, and makes compound;
Step 2) found: the compound cloth that step 1) is made is sprinkled in the mould of being made by refractory materials or hot metal with latticed grid die cavity, in kiln, found again, glass melting temperature is 1200 ℃~1600 ℃, and soaking time is 1~2 hour, obtains the glass paste of molten state;
Step 3) moulding is cooling: until glass paste, after latticed die for molding is cooling, take out, obtain anti-electrostatic glass mosaic finished product.
Step 2) founding adopted mould can be formed by refractory materials manufactures such as aluminum oxide, certainly also can adopt the resistant to elevated temperatures metal manufactures such as tungsten to form, and anti-electrostatic glass mosaic and mould adhesion in order to prevent that moulding from making after cooling, in embodiment 15, select at die surface and be coated with one deck adherent layer, adherent layer material is aluminum oxide.Certainly it should be appreciated by those skilled in the art that, outside alumina, the refractory materialss such as mullite, silicon carbide, silicon nitride all can as adherent layer material.In this serial embodiment, be that aluminum oxide to be added to water and add mass fraction be to make slurry after 3% carboxymethyl cellulose ball milling, then spread upon on mould.
In addition, in order to prevent that the glass paste forming after melting from overflowing, step 2) compound 1/2~2/3 degree of depth that in latticed grid die cavity, the thickness of the bed of material that forms is cavity depth on mould during cloth.In this series, executing routine selected depth is 12mm, and the maximum ulking thickness of compound in grid is 8mm.
Certainly, in order to eliminate stress, also can increase annealing operation.
The anti-electrostatic glass mosaic that test has been manufactured, its surface resistivity is 3 * 10
4~8 * 10
5ohm, body resistance is 4.5 * 10
4~9 * 10
5Ω m is a kind of good antistatic material.
Certainly, above anti-electrostatic mosaic also can be adopted with the following method and to manufacture, and via the molten glass slurry of making after above-mentioned formula material melting, pours in the mould that latticed refractory materials or hot metal make, after glass paste is cooling, the demoulding, obtains anti-electrostatic glass Mosaic product.
Embodiment 16-20 wherein
At this serial embodiment, provide the method for manufacturing anti-electrostatic glass frit.In option table 1, sequence number is 3,4,7,9,10 formula, respectively as the formula of embodiment 16-20 (being construed as here at the formula of listed other of the table 1 also applicable formula as manufacturing anti-electrostatic glass frit).This is that class embodiment manufacture method is as follows:
Step 1) batch mixing: take inorganic conductive powder according to 3,4,7,9, No. 10 formulas listed in formula table and mix approximately 30 minutes with glass particle vibration in vibrating ball mill, raw material is mixed, make compound;
Step 2) found: the compound that step 1) is made dispenses and packs in fire resistant sagger, then founds in shuttle kiln; Glass melting temperature is 1200 ℃~1600 ℃, 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 paste of molten state.
Step 3) moulding is cooling: by step 2) to obtain glass paste shrend cooling, and be broken into particulate state and can obtain anti-electrostatic glass frit.
In this serial embodiment, founding soaking 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 into while packing in saggar, 1/2~2/3 degree of depth of filling up saggar.
Above anti-electrostatic glass frit can be used as glaze raw material, or directly cloth imposes on ceramic body surface, forms the ceramic tile goods with anti-electrostatic glazed layer or glass coating.
And in order to obtain more rich decorative effect, can adopt the glass frit particle with different colours as raw material, the pottery of manufacturing is like this decorated and is felt stronger with anti-electrostatic glass frit, in addition, for the needed frit of glass-ceramic clad plate product, can in formula, suitably increase the consumption of devitrified glass particle.
Embodiment 21-25
A kind of glass-ceramic clad plate with anti-electrostatic glass layer is provided in this serial embodiment, and its manufacture method is as follows:
Step 1): select respectively the anti-electrostatic glass frit for pottery of embodiment 16-20 manufacturing, by its fragmentation, select 4~80 object particles, be used as respectively the anti-electrostatic glass frit raw material for pottery of embodiment 21-25.
Step 2) charity frit: anti-electrostatic glass frit for the pottery that charity step 1) is manufactured on ceramic tile base substrate, charity thickness is 2~8mm, then spray caking agent pottery conduction is fixed with glass frit, and with roller, the pottery of charity is flattened with anti-electrostatic glass frit; Wherein the specification of ceramic body is 800mm * 800mm, the ceramic green of embodiment ceramic body that 21-23 is used, embodiment 24,25 the ceramic body that uses be 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 can meet service requirements.
Step 3) enters klining: in roller kiln oxidizing atmosphere, burns till, and 1200~1250 ℃ 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 anti-electrostatic glass layer.
In the method providing at this serial embodiment, step 2) carboxymethyl cellulose aqueous solution that in, the caking agent that uses is 5% for mass fraction.
The finished product of manufacturing is the surperficial glass-ceramic clad plate with one deck anti-electrostatic glass layer, and the surface resistivity of testing its anti-electrostatic glass layer is 3 * 10
4~8 * 10
5ohm, body resistance is 4.5 * 10
4~9 * 10
5Ω 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 produced and is had the glass-ceramic clad plate of anti-electrostatic glass layer with anti-electrostatic glass frit, can also adopt the method manufacture being provided as embodiment 26 to have the glass-ceramic clad plate of anti-electrostatic glass layer, its manufacture method is as follows:
Step 1) batch mixing: adopt and inorganic conductive powder to be mixed with glass particle as the formula of sequence number in table 1 10, make compound;
Step 2) cloth: the specification after stamp be 800mm * 800mm ceramic body as carrier, the compound that evenly charity step 1) is manufactured in its surface, the ulking thickness of compound is 2~8mm;
Step 3) enters klining: in roller kiln oxidizing atmosphere, burns till, and 1200~1250 ℃ 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 method for the glass-ceramic clad plate of anti-electrostatic 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 anti-electrostatic glass layer of as above method manufacture, and the surface resistivity that records anti-electrostatic glass layer is 5 * 10
4ohm, body resistance is 8 * 10
4ohm.It is a kind of good antistatic material.
Embodiment 27
This embodiment provides a kind of glass-ceramic clad plate that anti-electrostatic has anti-electrostatic glass layer that has, its manufacture method is substantially the same manner as Example 21, difference is in step 2) in, the frit of institute's charity is the prepared anti-electrostatic glass frit of embodiment 16 and the mixed frit of glass frit, and wherein the quality of the mixed frit of simple glass frit is 3 times of anti-electrostatic glass frit.
Test adopts the glass-ceramic clad plate with anti-electrostatic glass layer of as above method manufacture, and the surface resistivity that records anti-electrostatic glass layer is 9 * 10
8ohm, body resistance is 9.5 * 10
8ohm.Between antistatic material, required the threshold value of performance.
Embodiment 28
In this enforcement, provide another to manufacture the method for anti-electrostatic glass, it comprises the steps:
Step 1) is manufactured anti-electrostatic glass frit: first by mixing No. 10 formulas in table 1, take raw material, by raw material ball milling 30 minutes in dry method ball mill, make compound, then directly the compound making is directly conveyed in glass melter and is founded; Glass melting temperature is 1200 ℃~1600 ℃, obtains the glass paste of molten state; Finally will obtain glass paste shrend cooling, and be broken into particle diameter≤4 object particle, can obtain anti-electrostatic glass frit;
Step 2) found: the anti-electrostatic glass frit that step 1) is obtained with simple glass frit in mass ratio for the ratio of 1:1 mixes, dispense on ceramic tile green compact, then enter klining, firing temperature is 1150 ℃~1300 ℃, and clinkering zone soaking time is 60~120 minutes;
Step 3) cooling forming: after cooling, supporting body is taken out from kiln, then the anti-electrostatic glass that is attached to ceramic tile green compact surface is taken off.
Test its electric property, surface resistivity is 5 * 10
6ohm, body resistance is 4.5 * 10
6Ω m is a kind of good antistatic material.
In this embodiment, anti-electrostatic glass is more difficult separated with the ceramic tile as its supporting body, can the adherent layer that one deck has refractory materials to form be set by ceramic tile base substrate.
Embodiment 29
The present embodiment provides a kind of manufacture method of relatively inexpensive anti-electrostatic glass mosaic, and it comprises the steps:
Step 1) is prepared anti-electrostatic glass frit according to the mode of the middle step 1 of embodiment 28;
Step 2) found: the anti-electrostatic glass frit that step 1) is made and simple glass frit in mass ratio for 1:2 mix after cloth be sprinkled into and have in the mould that the hot metal tungsten of latticed grid die cavity makes, again at kiln kiln roasting, 1150 ℃~1300 ℃, clinkering zone soaking time is 60~120 minutes;
Step 3) cooling forming: after cooling, mold is taken out from kiln, then the anti-electrostatic glass mosaic of formation is taken out from mould.
Test its electric property, surface resistivity is 6 * 10
7ohm, body resistance is 8 * 10
7Ω m.It is a kind of good antistatic material.
Know-why of the present invention has below been described in conjunction with specific embodiments.These are described is in order to explain principle of the present invention, and can not be interpreted as by any way limiting the scope of the invention.Explanation based on herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, within these modes all will fall into protection scope of the present invention.