CN103663986B - A kind of anti-electrostatic glass and manufacture method thereof - Google Patents
A kind of anti-electrostatic glass and manufacture method thereof Download PDFInfo
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Abstract
The present invention relates to technical field of inorganic nonmetallic materials, particularly relate to glass and production technology thereof, relate more specifically to a kind of anti-electrostatic glass and manufacture method thereof.Anti-electrostatic glass provided by the invention its be at least that to be that the inorganic conductive powder of 24% ~ 50% and the glass powder of 50% ~ 76% cool as melting after raw material blending by mass fraction obtained, described inorganic conductive powder is a kind of in the titanate of inorganic conductive oxide compound, conduction or both mixtures.Compared to the prior art, the anti-electrostatic glass of manufacture of the present invention is cheap, technique is simple, be easy to realization, and the material of construction that can enrich as raw material manufacture with it, such as sheet glass, glass Mosaic, pottery glass frit, there is the glass-ceramic clad plate etc. of anti-electrostatic glass coating, use it as material of construction, can static hazard be avoided.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, particularly relate to glass and production technology thereof, relate more specifically to a kind of anti-electrostatic glass and manufacture method thereof.
Background technology
Electrostatic is a kind of objectively spontaneous phenomenon, and the mode of generation is multiple, as contact, friction etc.Electrostatic, to some sensitive instrumentation and place, may cause fatal harm.Magnetoresistive effect (electromagnetic interference or electromagnetic compatibility) as electrostatic generation when discharging can disturb the normal work of precision instrument, 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 generation may ignite dust, causes explosion hazard.Therefore electrostatic protection technology all receives very big attention in such 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 electrostatic causes.
Ordinary glass material has very high resistivity, easy Accumulating charge, and gathering of these electric charges may bring multiple harm described above.There is associated electrostatic to endanger damnous report every year, 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 is more than 1 × 10
10during Ω m, the ability of material Charge dissipation obviously weakens; Consider from the angle eliminating electrostatic, the volume specific resistance of material should 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, thus reaches the effect of anti-electrostatic.
Our common simple glass is a kind of isolator under normal conditions, thus surface easily Accumulating charge, accumulation electrostatic.People have developed a lot of technique of producing anti-electrostatic glass for this reason, such as, add conductive ion in glass, add conducting film etc. at glass surface.Add conductive ion in glass mainly for the manufacture of solid electrolyte glass, electrocondution slurry anti-electrostatic glass powder, above main application is lithium ion battery etc.; Add conducting film mainly for the manufacture of anti-electrostatic glass fibre and the glasswork with surface conduction ability at glass surface, it is mainly used in flat display field, the ITO(tin Indium sesquioxide be such as widely used in flat pannel display) glass.Anti-electrostatic glass cost manufactured by above two kinds of modes 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 manufactured only has the conducting film that one deck sputtering is formed on surface.The anti-electrostatic glass that above two kinds of modes obtain all is not suitable for as building and ornament materials.
In building and ornament materials, glasswork occupies very large ratio.Along with the progress of production technology and material, except traditional building glass, the product innovation such as glass Mosaic, devitrified glass brick, glass-ceramic clad plate, the brilliant brick of throwing, throwing glazed brick continues to bring out, and plays more and more important effect in buildings internal and external ornament.If anti-electrostatic glass material is used for above product, then can obtains the building decorative product with electro-magnetic screen function, electrostatic-proof function, avoid static hazard.People constantly research and develop to have and are applicable to batch production, anti-electrostatic glass for building with low cost and goods thereof for this reason.
Summary of the invention
The object of the invention is to the anti-electrostatic glass proposing a kind of cheapness, it has with low cost, the features such as manufacturing process is simple, and or a kind of basic material can be it can be used as to manufacture building and ornament materials by it, comfortable, healthy living space can be provided to people.And using this kind of anti-electrostatic glass as material, such as anti-electrostatic sheet glass, anti-electrostatic glassware, anti-electrostatic glass Mosaic, anti-electrostatic glass frit can also be produced, 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, it is at least that to be that the inorganic conductive powder of 24% ~ 50% and the glass powder of 50% ~ 76% cool as melting after raw material blending by mass fraction obtained, and described inorganic conductive powder is a kind of in the titanate of inorganic conductive oxide compound, conduction or both mixtures.
Further, in above-mentioned anti-electrostatic glass, inorganic conductive oxide compound is one or more mixing included 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 including 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, such as lead glass powder; Common building glass powder refers to the powder that door and window sheet glass used is discarded rear fragmentation and made; Ware glass powder refers to the powder that vial, tank, cup, dish are discarded rear fragmentation and made; The powder that microcrystalline glass powder is made after referring to devitrified glass fragmentation, glass frit powder refers to powder block obtained for the cooling of the glass direct-water-quenching of molten state being broken into powder and making.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 as the raw material 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 is higher than 1400 DEG C.
Above-mentioned anti-electrostatic glass can make anti-electrostatic sheet glass, anti-electrostatic glassware, anti-electrostatic glass Mosaic, anti-electrostatic glass frit.
The present invention also provides a kind of method manufacturing anti-electrostatic glass, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form 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) to found: the compound that step 1) is obtained is founded in kiln, and glass melting temperature is 1200 DEG C ~ 1600 DEG C, obtains the glass paste of molten state;
The shaping cooling of step 3): by step 2) the shaping cooling of glass paste that obtains obtains anti-electrostatic glasswork.
Further, in the above-mentioned methods, the conductive oxide used 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 the above-mentioned methods, the titanate of the conduction used in step 1) includes but not limited to one or more mixing of conducting electricity in barium titanate, conduction lead titanate.
Further, in the above-mentioned methods, the inorganic conductive powder a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures formed in step 1) mixes with glass powder and adopts dry mixed mode to carry out.The mode that certain wet method is mixed is also passable, but needs increase by step by the operation of the compound drying after wet-mixed, can increase energy consumption like this.
Further, in the above-mentioned methods, dry mixed equipment is vibrating ball mill or is dry mixed ball mill, and the mixed time is >=30 minutes.
In the above-mentioned methods, step 2) found before, the compound cloth that can first step 1) be mixed is spread on supporting body, then founds.So, the anti-electrostatic glass made can present different shape with supporting body surface topography, and such as supporting body surface topography is plane, then can make anti-electrostatic sheet glass; Supporting body surface has latticed grid, then can make anti-electrostatic glass Mosaic.
Further, in the above-mentioned methods, the material of supporting body can be the one in refractory materials, ceramic green body, ceramic biscuiting base substrate, hot metal.
Further, in the above-mentioned methods, be provided with adherent layer between supporting body and compound, like this after sintering, anti-electrostatic glass just can be easy to take off from supporting body.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, coating on the carrier, and then dispenses compound.
Further, the present invention also provides a kind of method manufacturing anti-electrostatic sheet glass, and it comprises the steps;
Step 1) batch mixing: the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form 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) to found: the compound that step 1) is obtained evenly dispenses in fireproof die, described mould has the die cavity of depression, cavity surface is smooth and die cavity bottom surface is plane, founds in kiln, glass melting temperature is 1200 DEG C ~ 1600 DEG C, obtains the glass paste of molten state;
Step 3) cooling forming: until step 2) obtained glass paste is in a mold after cooled and solidified, and continuing to be cooled to normal temperature can take out the anti-electrostatic sheet glass obtained from mould.
Further, in step 3) cooling forming process, also comprise annealing operation, sheet glass step 3) obtained is annealed 1 ~ 2 hour at 480 DEG C ~ 540 DEG C.Annealing can eliminate the stress of glass kind, the broken loss preventing from stress from concentrating causing.
The anti-electrostatic sheet glass more than made can carry out the mechanical workout in later stage, comprises cutting, grinding, polishing etc.
Certainly in addition to the above method, the known manufacture sheet glass techniques such as float glass process, vertical drawing process, horizontal sheet process, rolling process can also be adopted to prepare above-mentioned dull and stereotyped anti-electrostatic glass.
Further, the present invention also provides a kind of method manufacturing anti-electrostatic glassware, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form 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) to found: the compound that step 1) is obtained is founded in kiln, and glass melting temperature is 1200 DEG C ~ 1600 DEG C, obtains the glass paste of molten state;
The shaping cooling of step 3): by step 2) glass paste that obtains pours blow molding in forming mould into, and then about 500 DEG C annealing 1 ~ 2 hour, finally cool, obtain the glassware conducted electricity.
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 that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form 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 obtained is dispensed and loads in fire resistant sagger, then found in kiln, or direct being conveyed in glass melter by compound is founded; Glass melting temperature is 1200 DEG C ~ 1600 DEG C, obtains the glass paste of molten state;
The shaping cooling of step 3): by step 2) obtain glass paste shrend cooling, and be broken into particulate state and can obtain anti-electrostatic glass frit.
Above anti-electrostatic glass frit can 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.
Need to adopt a large amount of inorganic conductive powder as raw material in the manufacture method of the anti-electrostatic glass introduced above, anti-electrostatic sheet glass, anti-electrostatic sheet glass, inorganic conductive powder cost is higher, therefore corresponding product cost is also higher, be unfavorable for applying, here introduce another method reduced costs for this reason, in new method, the anti-electrostatic glass frit of above-mentioned preparation is manufactured anti-electrostatic glass as raw material.
A preparation method for anti-electrostatic glass, it comprises the steps:
Step 1) manufactures anti-electrostatic glass frit: first mixed with glass powder by the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form, make compound, wherein the mass fraction of inorganic conductive powder is 24% ~ 50%, and the mass fraction of glass powder is 50% ~ 76%; Then obtained compound is dispensed and load in fire resistant sagger, then found in shuttle kiln, or direct being directly conveyed in glass melter by obtained compound 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 be broken into particle, anti-electrostatic glass frit can be obtained;
Step 2) to found: anti-electrostatic glass frit step 1) obtained mixes with simple glass frit, dispenses on the carrier, and then enter klining, firing temperature is 1150 DEG C ~ 1300 DEG C, and clinkering zone soaking time is 60 ~ 120 minutes;
Step 3) cooling forming: after cooling, takes out supporting body from kiln, is then taken off by the anti-electrostatic glass being attached to supporting body surface.
Mixed with simple glass frit by the anti-electrostatic glass frit of conduction, it is 1150 DEG C ~ 1300 DEG C with firing temperature in kiln, clinkering zone soaking time is burn till under the calcining system of 60 ~ 120 minutes, the structure of obtained 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 made, make electric charge by its conducting, thus the object of electrostatic discharge can be reached.In order to ensure anti-static effect, in the above-mentioned methods, 3 times of quality≤anti-electrostatic glass clinker quality of simple glass frit.More than 3 times, the conducting bridge formed in anti-electrostatic glass because of anti-electrostatic glass frit is less, and body resistance can more than 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 manufacturing anti-electrostatic glass Mosaic, and it comprises the steps:
Step 1) batch mixing: the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form 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) to found: compound cloth step 1) obtained is sprinkled in the mould be made up of refractory materials or hot metal with latticed grid die cavity, found in kiln again, glass melting temperature is 1200 DEG C ~ 1600 DEG C, and soaking time is 1 ~ 2 hour, obtains the glass paste of molten state;
The shaping cooling of step 3): take out after latticed die for molding cooling until glass paste, obtain anti-electrostatic glass Mosaic finished product.
Further, prepare the cost of anti-electrostatic glass Mosaic to reduce aforesaid method, and increase the decorative effect of glass Mosaic, can adopt and prepare anti-electrostatic glass Mosaic with the following method:
Step 1) manufactures anti-electrostatic glass frit: first mixed with glass powder by the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form, make compound, wherein the mass fraction of inorganic conductive powder is 24% ~ 50%, and the mass fraction of glass powder is 50% ~ 76%; Then obtained compound is dispensed and load in fire resistant sagger, then found in shuttle kiln, or direct being directly conveyed in glass melter by obtained compound 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 be broken into particle diameter≤4 object particle, anti-electrostatic glass frit can be obtained;
Step 2) to found: anti-electrostatic glass frit step 1) obtained and the rear cloth of simple glass frit mixing are sprinkled in the mould be made up of refractory materials or hot metal with latticed grid die cavity, again at kiln kiln roasting, 1150 DEG C ~ 1300 DEG C, clinkering zone soaking time is 60 ~ 120 minutes;
Step 3) cooling forming: after cooling, takes out mold from kiln, is then taken out from mould by the anti-electrostatic glass Mosaic of formation.
Mixed with simple glass frit by the anti-electrostatic glass frit of conduction, it is 1150 DEG C ~ 1300 DEG C with firing temperature in kiln, clinkering zone soaking time is burn till under the calcining system of 60 ~ 120 minutes, the structure of obtained 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 made, make electric charge by its conducting, thus the object of anti-electrostatic can be reached.In order to ensure anti-static effect, in the above-mentioned methods, 3 times of quality≤anti-electrostatic glass clinker quality of simple glass frit.More than 3 times, the conducting bridge formed in anti-electrostatic glass Mosaic because of anti-electrostatic glass frit is less, and body resistance can more than 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 coating, and it comprises the steps:
Step 1) manufactures anti-electrostatic glass frit: first mixed with glass powder by the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form, make compound, wherein the mass fraction of inorganic conductive powder is 24% ~ 50%, and the mass fraction of glass powder is 50% ~ 76%; Then obtained compound is dispensed and load in fire resistant sagger, then found in shuttle kiln, or direct being directly conveyed in glass melter by obtained compound 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 anti-electrostatic glass frit;
Step 2) charity frit: the anti-electrostatic glass frit that charity step 1) manufactures 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 clinker quality, then spray caking agent mixed frit is fixed, and with roller, the mixed frit of charity is flattened;
Step 3) enters klining: burn till in roller kiln oxidizing atmosphere, firing temperature 1200 ~ 1250 DEG C, firing period is 60 ~ 120 minutes;
Step 4) rubbing down is processed: the goods going out kiln cooling are carried out edging and polishing, obtains the glass-ceramic clad plate with anti-electrostatic glass coating.
Simple glass frit mentioned here refers to the non-conductive glass frit not having 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 realization, and can 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 etc. of anti-electrostatic glass coating.
Embodiment
Technical scheme of the present invention is further illustrated below by concrete preferred implementation.
Following table 1 is the formula table of embodiment.
Table 1
Cryogenic glass powder refers to the glass powder that melt temperature is lower, such as nonex powder; Common building glass powder refers to the powder that door and window sheet glass used is discarded rear fragmentation and made; Ware glass powder refers to the powder that vial, tank, cup, dish are discarded rear fragmentation and made; The powder that microcrystalline glass powder is made after referring to devitrified glass fragmentation, glass frit powder refers to powder block obtained for the cooling of the glass direct-water-quenching of molten state being broken into powder and making.
Embodiment 1 ~ 10: the sheet glass manufacturing conduction.
Its manufacture method is as follows:
Manufacture a method for anti-electrostatic sheet glass, it comprises the steps;
Step 1) batch mixing: according to recipe ingredient listed by table 1, the inorganic conductive powder a kind of in titanate by inorganic conductive oxide compound, conduction or both mixtures formed and glass powder are poured in ball mill and are dry mixed ball milling and are mixed by raw material for about 30 minutes, 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) to found: the compound that step 1) is obtained evenly dispenses in fireproof die, described mould has the die cavity of depression, cavity surface is smooth and die cavity bottom surface is plane, founds in kiln, glass melting temperature 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 the alloy etc. of selective oxidation aluminium, silicon nitride, tungsten or tungsten, be chosen as the fireproof die of aluminum oxide material at this series embodiment.
In order to the glass that formed after preventing compound melting and die bonds, be difficult to the demoulding, in this series embodiment, be coated with one deck adherent layer at die surface, release layer materials 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 are as release layer materials.In this series embodiment, be that to be added water by aluminum oxide and add mass fraction be make slurry after the carboxymethyl cellulose ball milling of 3%, then spread upon on mould.
In addition, the glass paste of the molten state formed after compound melting overflows mould, the thickness mixing the bed of material when cloth is 1/2 ~ 2/3 of the upper mould chamber degree of depth, in this series embodiment, select the die cavity of mould to be rectangular parallelepiped, its specification is long × wide × dark=500mm × 400mm × 15mm, and the fabric thickness of the mixing bed of material is 7.5mm ~ 10mm.
Step 3) cooling forming: until step 2) obtained glass paste is in a mold after cooled and solidified, and continuing to be cooled to normal temperature can take out the anti-electrostatic sheet glass obtained from mould.
Further, in step 3) cooling forming process, also comprise annealing operation, sheet glass step 3) obtained is annealed 1 ~ 2 hour at 480 DEG C ~ 540 DEG C.Annealing can eliminate the stress of glass kind, the broken loss preventing from stress from concentrating causing.
The anti-electrostatic sheet glass more than made can carry out the mechanical workout in later stage, comprises cutting, grinding, polishing etc.
The sheet glass that test is obtained, 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 glassware, selects the formula as sequence number in table 15 to prepare raw material (other the formula be construed as listed by table 1 is also suitable for, because all comparing class seemingly, only gives an illustrative example here) 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 mix 30 minutes by inorganic conductive powder with glass particle vibration in vibrating ball mill, and be mixed by raw material, make compound;
Step 2) to found: the compound that step 1) is obtained is founded in kiln, and glass melting temperature is 1200 DEG C ~ 1600 DEG C, obtains the glass paste of molten state;
The shaping cooling of step 3): by step 2) glass paste that obtains pours blow molding in forming mould into, and then about 500 DEG C annealing 1 ~ 2 hour, cooling, obtains the glassware conducted electricity.
The surface resistivity of the anti-electrostatic glassware that test manufactures 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 manufacturing anti-electrostatic glass Mosaic of this series embodiment, in option table 1, sequence number is the formula of 3,4,7,9, respectively as the formula (other the formula be construed as here listed by table 1 is also suitable for the formula as manufacturing anti-electrostatic glass Mosaic) of embodiment 12-15.
The method that this series 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, is mixed by raw material, makes compound;
Step 2) to found: compound cloth step 1) obtained is sprinkled in the mould be made up of refractory materials or hot metal with latticed grid die cavity, found in kiln again, glass melting temperature is 1200 DEG C ~ 1600 DEG C, and soaking time is 1 ~ 2 hour, obtains the glass paste of molten state;
The shaping cooling of step 3): take out after latticed die for molding cooling until glass paste, obtain anti-electrostatic glass Mosaic finished product.
Step 2) found adopted mould and can be formed by refractory materials manufactures such as aluminum oxide, certainly the resistant to elevated temperatures metal manufactures such as tungsten also can be adopted to form, and in order to the anti-electrostatic glass Mosaic made after preventing shaping cooling and mould adhesion, select in embodiment 15 and be coated with one deck adherent layer at die surface, release layer materials 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 are as release layer materials.In this series embodiment, be that to be added water by aluminum oxide and add mass fraction be make slurry after the carboxymethyl cellulose ball milling of 3%, then spread upon on mould.
In addition, in order to the glass paste formed after preventing melting overflows, step 2) cloth time compound in mould mesh-type grid die cavity form the bed of material thickness be 1/2 ~ 2/3 degree of depth of cavity depth.Executing routine selected depth in this series is 12mm, and compound maximum ulking thickness is within a grid 8mm.
Certainly, in order to eliminate stress, also annealing operation can be increased.
Test the anti-electrostatic glass Mosaic 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 and manufacture with the following method, pours in the mould that latticed refractory materials or hot metal make, after glass paste cooling via the molten glass slurry made after above-mentioned formula material melting, the demoulding, obtains anti-electrostatic glass Mosaic product.
Wherein embodiment 16-20
At this series embodiment, provide the method manufacturing anti-electrostatic glass frit.In option table 1, sequence number is the formula of 3,4,7,9,10, respectively as the formula (other the formula be construed as here listed by table 1 is also suitable for the formula as manufacturing anti-electrostatic glass frit) of embodiment 16-20.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 about 30 minutes with glass particle vibration in vibrating ball mill, raw material is mixed, makes compound;
Step 2) found: the compound that step 1) is obtained is dispensed and loads in fire resistant sagger, then found in shuttle kiln; Glass melting temperature is 1200 DEG C ~ 1600 DEG C, obtains the glass paste of molten state.
Here should illustrate also compound directly can be inputted in glass melter and found, obtain the glass paste of molten state.
The shaping cooling of step 3): by step 2) obtain glass paste shrend cooling, and be broken into particulate state and can obtain anti-electrostatic glass frit.
In this series embodiment, found soaking time is 1 ~ 2 hour.
In addition, in order to the glass paste formed after preventing melting overflows, step 2) in compound cloth is sprinkled into when loading in saggar, fill up 1/2 ~ 2/3 degree of depth of saggar.
Above anti-electrostatic glass frit can 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, the glass frit particle with different colours can be adopted as raw material, the pottery anti-electrostatic glass frit decoration sense of such manufacture is stronger, in addition, for the frit required for glass-ceramic clad plate product, in formula, suitably can increase the consumption of devitrified glass particle.
Embodiment 21-25
In this series embodiment, provide a kind of glass-ceramic clad plate with anti-electrostatic glass coating, its manufacture method is as follows:
Step 1): select the pottery anti-electrostatic glass frit manufactured by embodiment 16-20 respectively, it is broken, select 4 ~ 80 object particles, be used as the pottery anti-electrostatic glass frit raw material of embodiment 21-25 respectively.
Step 2) charity frit: the pottery anti-electrostatic glass frit that charity step 1) manufactures on ceramic tile base substrate, charity thickness is 2 ~ 8mm, then spray caking agent pottery conduction glass frit is fixed, and with roller, the pottery of charity anti-electrostatic glass frit is flattened; Wherein the specification of ceramic body be 800mm × 800mm, embodiment 21-23 use the ceramic green of ceramic body, embodiment 24,25 use ceramic body for biscuiting base substrate.
Certainly it will be appreciated by those skilled in the art that the base substrate of the biscuit after sintering or glazing and/or stamp can meet service requirements.
Step 3) enters klining: burn till in roller kiln oxidizing atmosphere, firing temperature 1200 ~ 1250 DEG C, firing period is 60 ~ 120 minutes.
Step 4) rubbing down is processed: the goods going out kiln cooling are carried out edging and polishing, obtains the glass-ceramic clad plate with anti-electrostatic glass coating.
In the method that this series embodiment provides, step 2) in use caking agent for mass fraction be the carboxymethyl cellulose aqueous solution of 5%.
Manufactured finished product is the glass-ceramic clad plate that surface has one deck anti-electrostatic glass coating, and the surface resistivity of testing its anti-electrostatic glass coating 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, producing except the pottery anti-electrostatic glass frit manufactured by the employing embodiment 16-20 such as described in embodiment 21-25 has except the glass-ceramic clad plate of anti-electrostatic glass coating, can also adopt as embodiment 26 the method manufacture that provides there is the glass-ceramic clad plate of anti-electrostatic glass coating, its manufacture method is as follows:
Step 1) batch mixing: adopt the formula as sequence number in table 1 10 to be mixed with glass particle by inorganic conductive powder, make compound;
Step 2) cloth: the specification after stamp be 800mm × 800mm ceramic body as carrier, the even compound that manufactures of charity step 1) in its surface, the ulking thickness of compound is 2 ~ 8mm;
Step 3) enters klining: burn till in roller kiln oxidizing atmosphere, firing temperature 1200 ~ 1250 DEG C, firing period is 60 ~ 120 minutes;
Step 4) rubbing down is processed: the goods going out kiln cooling are carried out edging and polishing, obtains the method for the glass-ceramic clad plate with anti-electrostatic glass coating.
Here in step 1), compounding process preferred embodiment can with reference to the description in embodiment 1-20.
Test adopts the glass-ceramic clad plate with anti-electrostatic glass coating of as above method manufacture, and the surface resistivity recording anti-electrostatic glass coating 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 and has the glass-ceramic clad plate that anti-electrostatic has anti-electrostatic glass coating, its manufacture method is substantially the same manner as Example 21, difference is in step 2) in, the anti-electrostatic glass frit of frit prepared by embodiment 16 of institute's charity and the mixed frit of glass frit, 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 coating of as above method manufacture, and the surface resistivity recording anti-electrostatic glass coating is 9 × 10
8ohm, body resistance is 9.5 × 10
8ohm.The threshold value of performance has been required between antistatic material.
Embodiment 28
There is provided another to manufacture the method for anti-electrostatic glass in this enforcement, it comprises the steps:
Step 1) manufactures anti-electrostatic glass frit: first take raw material by mixing No. 10 formulas in table 1, and by raw material ball milling 30 minutes in dry method ball mill, make compound, then direct being directly conveyed in glass melter by obtained compound 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 be broken into particle diameter≤4 object particle, anti-electrostatic glass frit can be obtained;
Step 2) to found: anti-electrostatic glass frit step 1) obtained and simple glass frit are in mass ratio for the ratio of 1:1 mixes, dispense on ceramic tile green compact, then enter klining, firing temperature is 1150 DEG C ~ 1300 DEG C, and clinkering zone soaking time is 60 ~ 120 minutes;
Step 3) cooling forming: after cooling, takes out supporting body from kiln, is then taken off by the anti-electrostatic glass being attached to ceramic tile green surface.
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 to be separated with the ceramic tile as its supporting body, can arrange the adherent layer that one deck has refractory materials to form 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) prepares anti-electrostatic glass frit according to the mode of step 1 in embodiment 28;
Step 2) to found: anti-electrostatic glass frit step 1) obtained and simple glass frit are in mass ratio for cloth after 1:2 mixing is sprinkled in the mould that the hot metal tungsten with latticed grid die cavity makes, again at kiln kiln roasting, 1150 DEG C ~ 1300 DEG C, clinkering zone soaking time is 60 ~ 120 minutes;
Step 3) cooling forming: after cooling, takes out mold from kiln, is then taken out from mould by the anti-electrostatic glass Mosaic of formation.
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.
Below know-why of the present invention is described in conjunction with specific embodiments.These describe just in order to explain principle of the present invention, and can not be interpreted as limiting the scope of the invention by any way.Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, and these modes all will fall within protection scope of the present invention.
Claims (1)
1. a preparation method for anti-electrostatic glass, it comprises the steps:
Step 1) manufactures anti-electrostatic glass frit: first mixed with glass powder by the inorganic conductive powder that a kind of in the titanate by inorganic conductive oxide compound, conduction or both mixtures form, make compound, wherein the mass fraction of inorganic conductive powder is 24% ~ 50%, and the mass fraction of glass powder is 50% ~ 76%; Then obtained compound is dispensed and load in fire resistant sagger, then found in shuttle kiln, or direct being directly conveyed in glass melter by obtained compound 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 be broken into particle, anti-electrostatic glass frit can be obtained;
Step 2) found: the anti-electrostatic glass frit that step 1) is obtained and the quality of simple glass frit in anti-electrostatic glass frit: the ratio that simple glass clinker quality is more than or equal to 1:3 mixes, dispense on the carrier, then klining is entered, firing temperature is 1150 DEG C ~ 1300 DEG C, and clinkering zone soaking time is 60 ~ 120 minutes;
Step 3) cooling forming: after cooling, takes out supporting body from kiln, is then taken off by the anti-electrostatic glass being attached to supporting body surface.
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