CN102515774B - Method for producing transparent glass and overglazed color ceramic sandwich by single firing - Google Patents
Method for producing transparent glass and overglazed color ceramic sandwich by single firing Download PDFInfo
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- CN102515774B CN102515774B CN201110339861.9A CN201110339861A CN102515774B CN 102515774 B CN102515774 B CN 102515774B CN 201110339861 A CN201110339861 A CN 201110339861A CN 102515774 B CN102515774 B CN 102515774B
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Abstract
A method for producing transparent glass and overglazed color ceramic sandwich by single firing in the invention relates to the technical field of building materials. By the adoption of ''a key single firing technology with material selection within the range of predetermined product components'', the method provided by the invention comprises the following steps of: applying ground-coat enamel on a ceramic green compact to prepare an enamel green body, printing gelatine-pad printed fancy glaze to prepare an overglazed color ceramic green body, applying transparent frit dry granules on the overglazed color ceramic green body to prepare overglazed color frit dry granular ceramic green body, spraying methyl cellulose for fixation to prepare a greenware to be sintered, sintering the greenware to be sintered to form a semi-finished product, followed by strickling for thickness determination, rough casting, fine casting, edging, chamfering, air drying, picking and grading to prepare the transparent glass and overglazed color ceramic sandwich finished product. The method is used for the production of transparent glass and overglazed color ceramic sandwiches and is the single firing technology with material selection within the range of predetermined product components.
Description
Technical field
Once-firing transparent glass of the present invention and over-glaze decoration Ceramic Composite plate producing process, relate to building materials technology field; Be particularly related to the building materials technology field of glass-ceramic; Relate in particular to the production method technical field of glass-ceramic building material product; Be specifically related to once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process technical field.
Background technology
In making the process of glass ceramic composite boards, in the production process of transparent glass and over-glaze decoration ceramic clad plate, all be unable to do without frit, ceramic green, ground-coat enamel and these raw materials of printing glaze, be and need in advance frit, ceramic green, ground-coat enamel prepared and printing glaze is modulated out, recycle these raw materials ceramic green is implemented to burn till for the first time, then on over-glaze decoration biscuit, after charity frit dry granular, to burn till for the second time after ground-coat enamel printing glaze, the twice firing production technique of Here it is existing known technology.Specifically, all transparent glasses and over-glaze decoration Ceramic Composite panel products in the market, all adopt twice firing production technique, first through burning till for the first time, prepare the over-glaze decoration biscuit of ceramics through screen printing or rubber roll stamp, and then clear frit dry granular on cloth, burn till for the second time again, over-glaze decoration ceramic body and clear frit are combined with each other, then pass through polished finish, thereby make transparent glass and over-glaze decoration Ceramic Composite panel products.The pattern of this product is motherboard mainly with stone material, adopts cat scanner design, recycling silk screen or glue roller printing, and the technology such as spray ink Printing even, can clear reduced stone texture, and fidelity is high; Add surperficial transparent glass and after polishing, can make product have pattern clearly, abundant color, three-dimensional effect, beautiful gloss, the antifouling plurality of advantages such as easy clean, be subject to over the past two years liking of consumers in general.But owing to adopting twice firing production technique, its total cycle all surpasses four hours above (being that the production cycle is long), therefore causes the production cost of product higher, particularly energy consumption high aspect manifest more outstanding; In recent years, the impact that risen by the costs such as material, artificial, the energy, the profit margin of this product is squeezed.Be summed up, the existing deficiency of this existing known technology, defect and drawback are: the technique of twice firing is loaded down with trivial details, lack of standardization, the cycle long, it is high, time-consuming to consume energy, production efficiency is low, random strong, the unstable product quality of selection.1., the clear frit preparing that the reasonable transparency of composition is good, beginning melting temperature is higher, sintering posterior spiracle is few and do not react with over-glaze decoration pattern color accordingly, the gordian technique of developing " once-firing transparent glass and over-glaze decoration ceramic clad plate " is:; 2., the rational ceramic green of prepared composition; 3., prepare the ground-coat enamel that composition rationally has the feature such as matched with blank, high whiteness, high covering power, matt effect, adaptation mobility, well suspended aspect thermal expansion; 4., determine the vanguard technology of scientific and reasonable, energy-conservation saving of labor, operation brief introduction, once-firing.In view of contriver's expertise be engaged in the rich experiences of industry work and to the excelsior unremitting pursue of cause, the present invention is exactly in conscientiously and fully investigation, understand, analyze, sum up, study on existing known technology and present situation basis, with " selecting the single firing process of material in predetermined prod composition range " gordian technique, " to frit, ceramic green, ground-coat enamel is all selected material and is formed " transparent glass and over-glaze decoration ceramic clad plate ' select material in the total composition range of predetermined prod single firing process " gordian technique in predetermined composition range separately, overcome and solved the deficiency of existing known technology and present situation existence, defect and drawback are succeeded in developing.Make it in selection material scientific basic, adopt once-firing advanced technologies, produce transparent glass and the over-glaze decoration ceramic clad plate product innovation of high-quality.
Summary of the invention
The present invention is with " selecting the single firing process of material in predetermined prod composition range " gordian technique, once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process are provided, after implementing ground-coat enamel be prepared into ground-coat enamel base on ceramic green, printing glaze is prepared into again over-glaze decoration greenwave, on over-glaze decoration greenwave, charity clear frit dry granular is prepared into and sprays methylcellulose gum after over-glaze decoration frit dry granular greenwave and be fixed and be prepared into greenwave to be burnt, greenwave to be burnt is fired the work in-process of formation through scraping thicknessing, rough polishing, essence is thrown, edging, chamfering, air-dry, pick, after classification, be prepared into transparent glass and over-glaze decoration Ceramic Composite board finished product.
1., with " selecting the single firing process of material in predetermined prod composition range " gordian technique the object reaching by the present invention is:, provide once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process.2., by selecting material in predetermined prod composition range, so that acquisition meets the product that constant high quality requires; Be that product can, in the composition range of design in advance, guarantee quality product.3., by advanced single firing process, realize standardization, mass-producing, standardized production.4., make the selection of product materials in product in composition range, composition range, the production technique of product in composition range, the general idea that organically blends is scientific and reasonable, method is simple, effect stability is reliable.5., can make clear frit dry granular and over-glaze decoration Ceramic Composite board finished product obtain the seldom surface of pore, and mate with over-glaze decoration ceramic body.6., make clear frit dry granular and over-glaze decoration Ceramic Composite board finished product there is the outstanding feature that transparency is good, because of high, the easy Exhaust Gas of its melting temperature, do not react with the pattern of over-glaze decoration ceramic body, thereby keep the clear of these patterns.7., make that ceramic green has enough green strengths (making it to complete smoothly the operation of printing, transportation), the suitable firing temperature mating with transparent glass, the thermal expansivity mating with transparent glass, volatile gases (comprising organic matter) is low as far as possible, free air delivery is little, easy oxidation, the applicable feature such as comparatively fast burn till, the impact of minimizing on transparent glass pore, is conducive to shorten firing period.8., make ground-coat enamel matched with blank on thermal expansivity, there is high whiteness, high covering power, matt effect, suitable degree of mobilization, good suspension ... etc. feature; And match with ceramic base substrate has can print artistry compared with high, good aesthetic beauty and ornamental and stable printed patterns.9., make the composition of transparent glass and over-glaze decoration ceramic clad plate in designed in advance composition range, accomplish every batch of product can quality high-quality, quality unification, constant mass, reliable in quality.10., the advanced technologies of once-firing--science, rationally, simple, standard, cycle be short, it is low to consume energy, saving of work and time, production efficiency are high, the chemical composition that sets product according to realization is selected material and make the steady quality of product, this technique be convenient to implementation and operation and cost is low and be conducive to wide popularization and application.
For achieving the above object, technical scheme provided by the invention is:
A kind of once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process:
1., prepare clear frit dry granular: with fineness degree, be less than 100 object quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, each 80-700 kilogram of boric acid, and select fineness degree be less than in 100 object sodium-chlor, sodium sulfate, fluorite a kind of 100 kilograms as finings; The above is mixed as frit raw material, the frit raw material mixing is sent in cell furnace melt, temperature of fusion is 1520-1600 ℃; To the melt having melted, after shrend, oven dry, fragmentation, screening, acquisition composition range is SiO
250-70%, Al
2o
35-20%, CaO0-10%, MgO 0-10%, K
2o+Na
2o 2-8%, BaO 0-8%, B
2o
3the 20-200 order clear frit dry granular of 0-8%, finings 1-10% and moisture < 0.5% is stand-by;
2., prepare ceramic green: the kaolin that is less than 1 millimeter with granularity, clay, quartzy, potassium felspar sand, albite, each 385-12250 of talcum kilogram through mixing as ceramic green raw material, in described ceramic green raw material, add appropriate water, and equalization adds alkali, water glass, tripoly phosphate sodium STPP is as water reducer, the quantity that adds described water reducer is the 0.3-0.5% of described ceramic green raw material, after ball mill ball milling pulping, carry out the dry powder process of spray dried, moisture after the dry powder process of described spraying is 5.5-6.5%, again through automatic hydraulic press shaped by fluid pressure, and then the dry composition range that makes of drying kiln drying is SiO
266-75%, Al
2o
315-25%, CaO+MgO 0.5-5%, K
2o+Na
2the ceramic green of O 2-8%, water reducer 0-2% and moisture < 0.5% is stand-by,
3., prepare ground-coat enamel: the fineness degree of usining is less than 100 object calcined kaolins, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, each 2-30 of nepheline kilogram through mixing as ground-coat enamel raw material, in described ground-coat enamel raw material, add methylcellulose gum as thickening material and appropriate water, and a kind of as water reducer in the alkali that brings Selection In, water glass, tripoly phosphate sodium STPP, add the quantity of described thickening material and water reducer to be the 0.3-0.5% of described ground-coat enamel raw material, entering ball mill ball milling, to become chemical composition be SiO
240-60%, Al
2o
315-25%, CaO 5-15%, MgO 0-8%, K
2o+Na
2o 2-10%, ZnO 0-8%, ZrO
2it is that the pulpous state ground-coat enamel of the remaining 0.4-0.5% of 10000-hole sieve is stand-by that 3-12%, water reducer and thickening material are 0-2% and fineness;
4., prepare ground-coat enamel base: on dried described ceramic green, application pouring glaze machine is implemented described ground-coat enamel, 65-70 ℃ of base temperature, take and spray water 10 grams and the quantity of implementing described ground-coat enamel under the condition of 300 * 300 pallet unit of measure as 60 ± 1 grams of 300 * 300 pallet unit of measure, be prepared into ground-coat enamel base stand-by;
5., preparation over-glaze decoration greenwave: utilize roller or silk screen, on the surface of described ground-coat enamel base, in the mode of printing, print that modulate, good with the colorful one, printability, various printing glazes, be prepared into the over-glaze decoration greenwave that enriches design and color stand-by;
6., preparation over-glaze decoration frit dry granular greenwave: apply dry-type belt material distributing machine, with 3.5-6Kg/m
2cloth amount by the uniform charity of described clear frit dry granular on described over-glaze decoration greenwave, be prepared into over-glaze decoration frit dry granular greenwave stand-by;
7., prepare greenwave to be burnt: in the mode of spray, on the surface of described over-glaze decoration frit dry granular greenwave, the described clear frit dry granular on described over-glaze decoration greenwave is fixed the methylcellulose gum water spray as stationary liquid, be prepared into greenwave to be burnt stand-by;
8., prepare transparent glass and over-glaze decoration Ceramic Composite boards half-finished product: described in inciting somebody to action, greenwave to be burnt is put into roller kiln, in temperature, be that 1120-1200 ℃, time are under the condition of 60-180 minute, greenwave described to be burnt is fired, be prepared into transparent glass and over-glaze decoration Ceramic Composite boards half-finished product is stand-by;
9., prepare transparent glass and over-glaze decoration Ceramic Composite board finished product: described transparent glass and over-glaze decoration Ceramic Composite boards half-finished product are scraped after thicknessing, rough polishing, smart throwing, edging, chamfering, air-dry, pick, classification, be prepared into transparent glass and over-glaze decoration Ceramic Composite board finished product.
Described once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process:
In described preparing in clear frit dry granular 1., described quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, boric acid, finings consumption separately is all determined in setting in advance the described composition range of clear frit dry granular;
In described preparing in ceramic green 2., described kaolin, clay, quartz, potassium felspar sand, albite, talcum, water reducer consumption separately is all determined in setting in advance the described composition range of ceramic green;
In described preparing in ground-coat enamel 3., described calcined kaolin, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, nepheline, thickening material, water reducer consumption separately are all determined in setting in advance the described composition range of ground-coat enamel.
Described once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process:
In described preparing in ceramic green 2., described kaolin is selected to be replaced by black mud, makes the loss on ignition < 4.7% of described ceramic green;
In described preparing in ground-coat enamel 3., the flow velocity of described pulpous state ground-coat enamel finished product is grace formula viscosity 16-18 second.
Owing to having adopted technical scheme provided by the present invention; Because the present invention has adopted " selecting the single firing process of material in predetermined prod composition range " gordian technique; Due to the present invention on ceramic green, implement ground-coat enamel and be prepared into ground-coat enamel base after printing glaze be prepared into again over-glaze decoration greenwave, on over-glaze decoration greenwave, charity clear frit dry granular is prepared into and sprays methylcellulose gum after over-glaze decoration frit dry granular greenwave and be fixed and be prepared into greenwave to be burnt, and wait burning work in-process that greenwave fires formation, after scraping thicknessing, rough polishing, smart throwing, edging, chamfering, air-dry, pick, classification, is prepared into transparent glass and over-glaze decoration Ceramic Composite board finished product.The present invention is compared with existing known technology and present situation, and the beneficial effect of acquisition is:
1, the present invention, with " selecting the single firing process of material in predetermined prod composition range " gordian technique, provides once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process.
2, the present invention, by select material within the scope of predetermined prod chemical composition, can obtain and meet the product that constant high quality requires with this; Be that product can, within the scope of the chemical composition of design in advance, guarantee the high quality that product is constant.
3, the present invention, by advanced single firing process, has realized standardization, mass-producing, standardized production.
4, the present invention is by the once-firing production technique of product within the scope of the selection of product materials within the scope of the product within the scope of chemical composition, chemical composition, chemical composition, organically blend as a whole, it organically blends, and whole design is scientific and reasonable, method is simple, effect stability is reliable.
5, the transparent glass pore that the present invention can make finished product seldom, and mates with over-glaze decoration ceramic body.
6, the present invention makes clear frit dry granular have the outstanding feature that transparency is good, because of high, the easy Exhaust Gas of its melting temperature, do not react with the pattern of over-glaze decoration ceramic body, thereby has kept the clear of these patterns.
7, the present invention makes the composition of clear frit dry granular compare with existing known technology, have two significant different, 1., its alumina composition is over 10%, much larger than the clear frit of twice firing that is exactly:; 2., must add a certain amount of finings, the clear frit of twice firing is containing this type of finings.Thereby also just had that existing known technology cannot compare such as high, the easy Exhaust Gas of beginning melting temperature, seldom surface, the transparency of pore good, mate with over-glaze decoration ceramic body, do not react with the pattern of over-glaze decoration ceramic body, can keep the clear beneficial effect that waits of pattern.
8, the present invention make that ceramic green has enough green strengths (making it to complete smoothly the operation of printing, transportation), the suitable firing temperature mating with transparent glass, the thermal expansivity mating with transparent glass, volatile gases (comprising organic matter) is low as far as possible, free air delivery is little, easy oxidation, the applicable features such as (having shortened the production cycle) of comparatively fast burning till, the impact of minimizing on transparent glass pore, is conducive to shorten firing period.
9, the present invention makes ground-coat enamel matched with blank on thermal expansivity, has high whiteness, high covering power, matt effect, suitable degree of mobilization, good suspension ... etc. feature; And match with ceramic base substrate has can print artistry compared with high, good aesthetic beauty and ornamental and stable printed patterns.
10, the present invention makes the chemical composition of transparent glass and over-glaze decoration ceramic clad plate in designed in advance composition range, accomplished every batch of product can quality high-quality, quality unification, constant mass, reliable in quality.
11, the present invention has adopted the vanguard technology of once-firing; Its firing temperature is 1120-1200 ℃, and firing period is 60-180 minute, and the water-intake rate that burns till rear product is 0.04-0.10%.Obtained the beneficial effect that efficient energy-saving, minimizing discharge, protection of the environment, low-carbon (LC) production, low-carbon (LC) are lived.
12, the advanced technologies of once-firing of the present invention--science, rationally, simple, standard, cycle be short, it is low to consume energy, saving of work and time, production efficiency are high, the chemical composition that sets product according to realization is selected material and makes product have firm and constant high quality, this technique is convenient to implementation and operation and cost is low and be conducive to wide popularization and application.
Accompanying drawing explanation
Figure of description is the technological operation step window schematic diagram of the specific embodiment of the invention.
Embodiment
Embodiment one
Below in conjunction with Figure of description, the present invention is described in detail.Shown in Figure of description:
A kind of once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process:
1., prepare clear frit dry granular: with fineness degree, be less than 100 object quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, each 80-700 kilogram of boric acid, and select fineness degree be less than in 100 object sodium-chlor, sodium sulfate, fluorite a kind of 100 kilograms as finings; The above is mixed as frit raw material, the frit raw material mixing is sent in cell furnace melt, temperature of fusion is 1520-1600 ℃; To the melt having melted, after shrend, oven dry, fragmentation, screening, acquisition composition range is SiO
250-70%, Al
2o
35-20%, CaO0-10%, MgO 0-10%, K
2o+Na
2o 2-8%, BaO 0-8%, B
2o
3the 20-200 order clear frit dry granular of 0-8%, finings 1-10% and moisture < 0.5% is stand-by;
2., prepare ceramic green: the kaolin that is less than 1 millimeter with granularity, clay, quartzy, potassium felspar sand, albite, each 385-12250 of talcum kilogram through mixing as ceramic green raw material, in described ceramic green raw material, add appropriate water, and equalization adds alkali, water glass, tripoly phosphate sodium STPP is as water reducer, the quantity that adds described water reducer is the 0.3-0.5% of described ceramic green raw material, after ball mill ball milling pulping, carry out the dry powder process of spray dried, moisture after the dry powder process of described spraying is 5.5-6.5%, again through automatic hydraulic press shaped by fluid pressure, and then the dry composition range that makes of drying kiln drying is SiO
266-75%, Al
2o
315-25%, CaO+MgO 0.5-5%, K
2o+Na
2the ceramic green of O 2-8%, water reducer 0-2% and moisture < 0.5% is stand-by,
3., prepare ground-coat enamel: the fineness degree of usining is less than 100 object calcined kaolins, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, each 2-30 of nepheline kilogram through mixing as ground-coat enamel raw material, in described ground-coat enamel raw material, add methylcellulose gum as thickening material and appropriate water, and a kind of as water reducer in the alkali that brings Selection In, water glass, tripoly phosphate sodium STPP, add the quantity of described thickening material and water reducer to be the 0.3-0.5% of described ground-coat enamel raw material, entering ball mill ball milling, to become chemical composition be SiO
240-60%, Al
2o
315-25%, CaO 5-15%, MgO 0-8%, K
2o+Na
2o 2-10%, ZnO 0-8%, ZrO
2it is that the pulpous state ground-coat enamel of the remaining 0.4-0.5% of 10000-hole sieve is stand-by that 3-12%, water reducer and thickening material are 0-2% and fineness;
4., prepare ground-coat enamel base: on dried described ceramic green, application pouring glaze machine is implemented described ground-coat enamel, 65-70 ℃ of base temperature, take and spray water 10 grams and the quantity of implementing described ground-coat enamel under the condition of 300 * 30O pallet unit of measure as 60 ± 1 grams of 300 * 300 pallet unit of measure, be prepared into ground-coat enamel base stand-by;
5., preparation over-glaze decoration greenwave: utilize roller or silk screen, on the surface of described ground-coat enamel base, in the mode of printing, print that modulate, good with the colorful one, printability, various printing glazes, be prepared into the over-glaze decoration greenwave that enriches design and color stand-by;
6., preparation over-glaze decoration frit dry granular greenwave: apply dry-type belt material distributing machine, with 3.5-6Kg/m
2cloth amount by described clear frit dry granular equably charity on described over-glaze decoration greenwave, be prepared into over-glaze decoration frit dry granular greenwave stand-by;
7., prepare greenwave to be burnt: in the mode of spray, on the surface of described over-glaze decoration frit dry granular greenwave, the described clear frit dry granular on described over-glaze decoration greenwave is fixed the methylcellulose gum water spray as stationary liquid, be prepared into greenwave to be burnt stand-by;
8., prepare transparent glass and over-glaze decoration Ceramic Composite boards half-finished product: described in inciting somebody to action, greenwave to be burnt is put into roller kiln, in temperature, be that 1120-1200 ℃, time are under the condition of 60-180 minute, greenwave described to be burnt is fired, be prepared into transparent glass and over-glaze decoration Ceramic Composite boards half-finished product is stand-by;
9., prepare transparent glass and over-glaze decoration Ceramic Composite board finished product: described transparent glass and over-glaze decoration Ceramic Composite boards half-finished product are scraped after thicknessing, rough polishing, smart throwing, edging, chamfering, air-dry, pick, classification, be prepared into transparent glass and over-glaze decoration Ceramic Composite board finished product.
Described once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process:
In described preparing in clear frit dry granular 1., described quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, boric acid, finings consumption separately is all determined in setting in advance the described composition range of clear frit dry granular;
In described preparing in ceramic green 2., described kaolin, clay, quartz, potassium felspar sand, albite, talcum, water reducer consumption separately is all determined in setting in advance the described composition range of ceramic green;
In described preparing in ground-coat enamel 3., described calcined kaolin, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, nepheline, thickening material, water reducer consumption separately are all determined in setting in advance the described composition range of ground-coat enamel.
Described once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process:
In described preparing in ceramic green 2., described kaolin is selected to be replaced by black mud, makes the loss on ignition < 4.7% of described ceramic green;
In described preparing in ground-coat enamel 3., the flow velocity of described pulpous state ground-coat enamel is grace formula viscosity 16-18 second.
In above-mentioned specific implementation process, that is:
1, in described preparing in clear frit dry granular 1.: described quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, boric acid are implemented with 80,100,120,150,180,200,230,250,270,300,330,360,380,400,420,440,460,480,500,530,580,600,620,660,680,700 kilograms respectively; Described temperature of fusion is implemented with 1520,1530,1540,1550,1560,1570,1580,1590,1600 ℃ respectively; To SiO in described composition range
2with 50,55,60,65,70%, implement respectively Al
2o
3with 5,7,10,12,15,18,20%, implement respectively, CaO implements with 0,1,2,3,4,5,6,7,8,9,10% respectively, and MgO implements with 0,1,2,3,4,5,6,7,8,9,10% respectively, K
2o+Na
2o implements with 2,3,4,5,6,7,8% respectively, and BaO implements with 0,1,2,3,4,5,6,7,8% respectively, B
2o
3with 0,2,3,4,5,6,7,8%, implement respectively, finings is implemented with 1,2,3,4,5,6,7,8,9,10% respectively; Described quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, boric acid, finings consumption is separately adjusted and implemented in the composition range of described acquisition clear frit dry granular finished product; The fineness degree of described clear frit dry granular finished product is implemented with 20,30,40,50,80,100,120,140,160,180,200 orders respectively; All received expected effect.
2, in described preparing in ceramic green 2.: described kaolin, clay, quartz, potassium felspar sand, albite, talcum are implemented with 385,400,500,600,700,800,900,1000,1500,2000,2500,3000,3500,4000,4500,5000,5500,6000,6500,7000,7500,8000,8500,9000,9300,9500,9800,10000,12000,12250 kilograms respectively; Described water reducer is implemented with alkali, water glass, tripoly phosphate sodium STPP combination; The quantity of described water reducer is implemented with 0.3,0.4,0.5% of ceramic green raw material respectively; Moisture after the dry powder process of described spraying is implemented with 5.5,5.6,5.7,5.8,5.9,6.0,6.1,6.2,6.3,6.4,6.5% respectively; To the SiO in the described ceramic green composition making
2with 66,67,68,69,70,71,72,73,74,75%, implement respectively Al
2o
3with 15,16,17,18,19,20,21,22,23,24,25%, implement respectively, CaO+MgO implements with 0.5,0.8,1.0,12,1.5,1.8,2.0,2.5,3.0,3.5,4.0,4.3,4.5,4.7,4.8,5.0% respectively, K
2o+Na
2o implements with 2,3,4,5,6,7,8% respectively, and water reducer is implemented with 0,0.5,0.8,1.0,1.2,1.5,1.8,2.0% respectively; Kaolin in described ceramic green raw material is substituted and implemented by black mud; Described kaolin, clay, quartz, potassium felspar sand, albite, talcum, water reducer consumption separately is all determined and implemented in setting in advance the described composition range of ceramic green; All received expected effect.
3, in described preparing in ground-coat enamel 3.: the calcined kaolin in described ground-coat enamel raw material, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, nepheline are implemented with 2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30 kilograms respectively; Described water reducer is implemented with alkali, water glass, tripoly phosphate sodium STPP respectively; The quantity of described thickening material and water reducer is implemented with 0.3,0.4,0.5% of ground-coat enamel raw material respectively; To the SiO in the described ground-coat enamel composition making
2with 40,45,50,55,60%, implement respectively Al
2o
3with 15,18,20,23,25%, implement respectively, CaO implements with 5,8,10,12,15% respectively, and MgO implements with 0,1,2,3,4,5,6,7,8% respectively, K
2o+Na
2o implements with 2,3,4,5,6,7,8,9,10% respectively, and ZnO implements with 0,1,2,3,4,5,6,7,8% respectively, ZrO
2with 3,4,5,6,7,8,9,10,11,12%, implement respectively, water reducer and thickening material are implemented with 0,0.5,0.8,1.0,1.2,1.5,1.8,2% respectively; The described pulpous state ground-coat enamel finish fineness making is moreed than and 0.4,0.5% implemented with 10000-hole sieve respectively; The flow velocity of described pulpous state ground-coat enamel finished product is implemented with grace formula viscosity respectively for 16,17,18 seconds; Described calcined kaolin, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, nepheline, thickening material, water reducer consumption separately are all determined and implemented in setting in advance the described composition range of ground-coat enamel; All received expected effect.
4, in described preparing in transparent glass and over-glaze decoration Ceramic Composite boards half-finished product 8.: greenwave described to be burnt is put into the temperature that roller kiln fire and implement with 1120,1140,1150,1155,1160,1180,1200 ℃ respectively, the time of firing implemented with 60,80,100,120,140,160,180 minutes respectively; All received expected effect.
Embodiment two
By embodiment one, implement, shown in Figure of description, just:
1, in described preparing in clear frit dry granular 1.: be less than 100 object quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, boric acid proportioning raw material with fineness degree, and a kind of as finings in selective chlorination sodium, sodium sulfate, fluorite, weigh 2000 kilograms for every batch, the above is mixed as frit raw material, the frit raw material mixing is sent in cell furnace melt, temperature of fusion is 1520-1600 ℃; To the melt having melted, after shrend, oven dry, fragmentation, screening, acquisition composition range is SiO
25 0-70%, Al
2o
35-20%, CaO 0-10%, MgO 0-10%, K
2o+Na
2o 2-8%, BaO 0-8%, B
2o
3the 20-200 order of 0-8%, finings 1-10% and the clear frit dry granular of moisture < 0.5%.Described in it, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, boric acid, finings consumption separately is all determined and implements in setting in advance the described composition range of clear frit dry granular.Received expected effect.
2, in described preparing in ceramic green 2.: (1), the kaolin that is less than 1 millimeter with granularity, clay, quartzy, potassium felspar sand, albite, every batch of talcum proportioning raw material is weighed 35000 kilograms, through mixing as ceramic green raw material, in described ceramic green raw material, add appropriate water, and equalization adds alkali, water glass, tripoly phosphate sodium STPP is as water reducer, the quantity that adds described water reducer is the 0.3-0.5% of described ceramic green raw material, after ball mill ball milling pulping, carry out the dry powder process of spray dried, moisture after the dry powder process of described spraying is 5.5-6.5%, again through automatic hydraulic press shaped by fluid pressure, and then the dry composition range that makes of drying kiln drying is SiO
266-75%, Al
2o
315-25%, CaO+MgO 0.5-5%, K
2o+Na
2the ceramic green of O 2-8%, water reducer 0-2% and moisture < 0.5%.(2), described kaolin selects to be replaced by black mud.(3), make the loss on ignition < 4.7% of described ceramic green.(4), described kaolin, clay, quartz, potassium felspar sand, albite, talcum, water reducer consumption is separately and in setting in advance the described composition range of ceramic green, determines and implement.Received equally expected effect.
3, in described preparing in ground-coat enamel 3.: (1), with fineness degree, be less than 100 object calcined kaolins, quartzy, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, every batch of nepheline proportioning raw material is weighed 100 kilograms, through mixing as ground-coat enamel raw material, in described ground-coat enamel raw material, add methylcellulose gum as thickening material and appropriate water, and add alkali, water glass, tripoly phosphate sodium STPP is as water reducer, add the quantity of described thickening material and water reducer to be the 0.3-0.5% of described ground-coat enamel raw material, entering ball mill ball milling, to become chemical composition be SiO
240-60%, Al
2o
315-25%, CaO 5-15%, MgO 0-8%, K
2o+Na
2o 2-10%, ZnO 0-8%, ZrO
23-12%, water reducer and thickening material are 0-2% and fineness is the pulpous state ground-coat enamel of the remaining 0.4-0.5% of 10000-hole sieve.(2), the flow velocity of described pulpous state ground-coat enamel is grace formula viscosity 16-18 second.(3), described calcined kaolin, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, nepheline, thickening material, water reducer consumption separately are all determined and are implemented in setting in advance the described composition range of ground-coat enamel.Received equally expected effect.
Embodiment three
By embodiment one, implement, shown in Figure of description, just in described preparing in clear frit dry granular 1.: set in advance the composition of clear frit dry granular by SiO
2be 57.20%, Al
2o
3be 10.62%, CaO is 7.20%, MgO is 5.12%, K
2o+Na
2o is 4.72%, BaO is 4.13%, B
2o
3be 7.26%, finings is 3.75%, set in advance under clear frit dry granular finished product composition, choose corresponding proportion, be less than 100 object quartz, potassium felspar sand, calcite, rhombspar, soda ash, barium carbonate, boric acid, saltpetre, and the finings of appropriate ratio, prepare burden.In mixer, mix 30 minutes, in the tank furnace of 22 square metres, found, glass melting temperature is 1580 ℃, and approximately 24 hours material stock time, the liquation after clarification, through shrend, oven dry, fragmentation, screening, makes 20-200 object clear frit dry granular.Received equally expected effect.
Embodiment four
By embodiment one, three, implement, shown in Figure of description, but be with the difference of embodiment three: in described preparing in clear frit dry granular 1., the composition of clear frit dry granular is pressed SiO
2be 54.27%, Al
2o
3be 12.67%, CaO is 6.29%, MgO is 4.92%, K
2o+Na
2o is 4.98%, BaO is 4.56%, B
2o
3be 7.88%, finings is 4.43%.Apply clear frit dry granular described in this and carried out the making of transparent glass and over-glaze decoration ceramic clad plate, and the printing glaze using in making processes is pale yellow, middle Huang and deep yellow color, silk screen or roller pattern are cloud shape pattern, so just produce once-firing transparent glass and over-glaze decoration Ceramic Composite panel products with yellow cloud shape decorative pattern.Received expected effect.
Embodiment five
By embodiment one, three, implement, shown in Figure of description, but be with the difference of embodiment three: in described preparing in clear frit dry granular 1., the composition of clear frit dry granular is pressed SiO
2be 52.28%, Al
2o
3be 13.58%, CaO is 5.44%, MgO is 6.23%, K
2o+Na
2o is 5.68%, BaO is 5.90%, B
2o
3be 8.20%, finings is 2.69%.Apply clear frit dry granular described in this and carried out the making of transparent glass and over-glaze decoration ceramic clad plate, and the printing glaze using in making processes is pale red, middle Huang and dark red color, silk screen or roller pattern are band pattern, so just produce once-firing transparent glass and the over-glaze decoration Ceramic Composite panel products of the red alternate color of Huang of roe figure pattern.Received expected effect.
Embodiment six
By embodiment one, three, implement, shown in Figure of description, but be with the difference of embodiment three: in described preparing in clear frit dry granular 1., the composition of clear frit dry granular is pressed SiO
2be 54.77%, Al
2o
3be 13.44%, CaO is 5.20%, MgO is 3.54%, K
2o+Na
2o is 3.58%, BaO is 7.21%, B
2o
3be 8.41%, finings is 3.85%.Simultaneously, in described preparing in ceramic green 2., ceramic body composition is pressed SiO
2be 66.23%, Al
2o
3be 20.43%, CaO+MgO is 2.88%, K
2o+Na
2o is 5.24%, Fe
2o
3be 0.89%, TiO
2be 0.28%, loss on ignition is 4.05%.Apply described in this clear frit dry granular and described in this ceramic body carried out the making of transparent glass and over-glaze decoration ceramic clad plate, and the printing glaze using in making processes is white, pale yellow and black color, silk screen or roller pattern are net-like pattern, so just produce background color, be black, with once-firing transparent glass and the over-glaze decoration Ceramic Composite panel products of the Portoro decorative pattern of adularescent and yellow line.Received equally expected effect.
Embodiment seven
By embodiment one, implement, shown in Figure of description, just in described preparing in ceramic green 2.: the composition of ceramic green is set as SiO
267.72%, Al
2o
319.82%, CaO+MgO 2.62%, K
2o+Na
2o 5.37%, Fe
2o
30.64%, TiO
20.21%, loss on ignition 3.62%, the composition setting according to ceramic green, choose the black mud that granularity that ceramic green sets composition corresponding proportion is less than 1 millimeter, kaolin, high temperature sand, middle temperature sand, hypothermia grait, potassium sand, talcum is as ceramic green raw material, weigh 35000 kilograms after mixing for every batch, add the tripoly phosphate sodium STPP of ceramic green raw material weight 0.4% and 0.2% soda ash as water reducer, the water that simultaneously adds 0.55 times of ceramic green raw material weight, in ball mill, to become fineness be the mud of 0.5-1% more than 10000-hole sieve to ball milling, again through mist projection granulating, make the powder that water content is 5.5-6.5%.The automatic hydraulic press of recycling 40Mpa molds the ceramic green of 930 * 930mm specification.Use after drying.
In above-mentioned specific implementation process: except implementing by embodiment one, also described tripoly phosphate sodium STPP and soda ash are replaced with respectively to soda ash, water glass, tripoly phosphate sodium STPP as water reducer and implement; The fineness that also ball milling in be set forth in ball mill is become to mud is moreed than and 0.5,0.6,0.7,0.8,0.9,1.0% is implemented with 10000-hole sieve respectively; Also the moisture content of described powder is implemented with 5.5,5.6,5.7,5.8,5.9,6.0,6.1,6.2,6.3,6.4,6.5% respectively; Obtained expected effect.
Embodiment eight
By embodiment one, implement, shown in Figure of description, just in described preparing in ceramic green 2.: the composition of ceramic green is set as SiO
2be 66.23%, Al
2o
3be 20.43%, CaO+MgO is 2.88%, K
2o+Na
2o is 5.24%, Fe
2o
3be 0.89%, TiO
2be 0.28%, loss on ignition is 4.05%; Obtained equally expected effect.
Embodiment nine
By embodiment one, implement, shown in Figure of description, just in described preparing in ground-coat enamel 3.: the composition of ground-coat enamel is set as SiO
254.40%, Al
2o
313.86%, CaO 8.12%, MgO4.67%, K
2o+Na
2o 5.72%, ZnO 3.80%, ZrO
28.52%, TiO
20.24%, Fe
2o
30.06%, loss on ignition 0.61%, the granularity of choosing corresponding proportion is less than 100 object ball clays, calcined kaolin, quartz, potassium felspar sand, calcite, nepheline, zinc oxide, zirconium English powder, burns talcum proportioning raw material as ground-coat enamel raw material, after mixing in corresponding ratio, add appropriate water reducer, thickening material and appropriate water, enter ball mill ball milling and wear into the glaze slip that fineness is the remaining 0.4-0.5% of 10000-hole sieve, glaze slip flow velocity is adjusted into 16-18 second.Obtained equally expected effect.
Embodiment ten
By embodiment one, implement, shown in Figure of description, just in described preparing in ground-coat enamel 3.: the composition of ground-coat enamel is set as SiO
257.66%, Al
2o
312.44%, CaO 6.77%, MgO 5.37%, K
2o+Na
2o 6.02%, ZnO 4.27%, ZrO
26.21%, TiO
20.16%, Fe
2o
30.28%, loss on ignition 0.82%.Printing glaze is shallow coffee, middle coffee and dark coffee color, and silk screen or roller pattern are net-like pattern, so just produce once-firing transparent glass and the over-glaze decoration Ceramic Composite panel products of Emperador shape decorative pattern.Obtained expected effect.
Embodiment 11
By embodiment one, implement, shown in Figure of description, just:
In described preparing in clear frit dry granular, by SiO 1.
257.20%, Al
2o
310.62%, CaO 7.20%, MgO 5.12%, K
2o+Na
2o 4.72%, BaO 4.13%, B
2o
37.26%, finings 3.75%, choose corresponding proportion, be less than 100 object quartz, potassium felspar sand, calcite, rhombspar, soda ash, barium carbonate, boric acid, saltpetre, the finings of proportioning raw material and appropriate ratio, prepares burden; In mixer, mix 30 minutes, in the tank furnace of 22 square metres, found, glass melting temperature is 1580 ℃, and approximately 24 hours material stock time, the liquation after clarification, through shrend, oven dry, fragmentation, screening, makes 20-200 object clear frit dry granular stand-by;
In described preparing in ceramic green 2., by SiO
267.72%, Al
2o
319.82%, CaO+MgO 2.62%, K
2o+Na
2o 5.37%, Fe
2o
30.64%, TiO
20.21%, loss on ignition 3.62%, the granularity of choosing corresponding proportion is less than the raw materials such as the black mud of 1 millimeter, kaolin, high temperature sand, middle temperature sand, hypothermia grait, potassium sand, talcum, after mixing in corresponding ratio, the water that adds 0.55 times of appropriate water reducer, base substrate toughener and raw material weight, in ball mill, to become fineness be the mud of 0.5-1% more than 10000-hole sieve to ball milling, then through mist projection granulating, make the powder that water content is 5.5-6.5%; The automatic hydraulic press of recycling 40Mpa pressure molds the ceramic green of 930 * 930mm specification; Stand-by after drying;
In described preparing in ground-coat enamel 3., by SiO
254.40%, Al
2o
313.86%, CaO8.12%, MgO4.67%, K
2o+Na
2o 5.72%, ZnO 3.80%, ZrO
28.52%, TiO
20.24%, Fe
2o
30.06%, loss on ignition 0.61%, the granularity of choosing corresponding proportion is less than 100 object ball clays, calcined kaolin, quartz, potassium felspar sand, calcite, nepheline, zinc oxide, zirconium English powder, burns the raw materials such as talcum, after mixing in corresponding ratio, add appropriate water reducer, thickening material and appropriate water, enter ball mill ball milling and wear into the glaze slip that fineness is the remaining 0.4-0.5% of 10000-hole sieve, and glaze slip flow velocity is adjusted into 16-18 second;
By above-mentioned dried ceramic green after purging deashing (green compact temperature is controlled at 65-70 ℃), first spray clear water 10g (300 * 300 pallets are measured), adopt pouring glaze machine to execute the ground-coat enamel preparing above, glaze volume is 60 ± 1 grams (300 * 300 pallets) again; And then utilize roller or silk screen by the printing glaze with shallow orchid, light gray, dark-grey color modulating, be imprinted on the ceramic green surface of having executed ground-coat enamel, so ceramic green surface presents background color for white, with the marbled pattern of shallow blue gray tone lines;
Next, by dry type material distributing machine, printing the clear frit dry granular preparing on the ceramic green surface uniform ground cloth of floral designs, cloth amount is 4.0-4.5Kg/m
2, then to spray stationary liquid and fix, the consumption of stationary liquid is 15-20g (300 * 300 pallets is measured), reenters roller kiln and burns till, and firing period is 150 minutes, and the top temperature of burning till is 1200 ℃ of left and right; Work in-process after burning through scraping the operations such as thicknessing, rough polishing, smart throwing, edging, chamfering, air-dry, pick, packing, finally make the compound once-firing transparent glass of a imitative stone material clear frit dry granular and over-glaze decoration ceramic body and over-glaze decoration Ceramic Composite panel products again.
Embodiment 12
By embodiment one, two, three, four, five, six, seven, eight, nine, ten, 11 implement, shown in Figure of description, just: in embodiment one, two, three, four, five, six, seven, eight, nine, ten, on 11 scale basis, respectively to dwindle 10, 8, 6, 5, 4, 3, 2, 1 times and expand respectively 1, 2, 3, 5, 8, 10, 12, 15, 20, 25, 30, 35, 40, 45, implement for 50 times, make the present invention possess original reason test, laboratory test, small-scale test, expanding test, medium-sized test, large-scale experiment, the solid foundation of Production Type Test, possessed the solid foundation from theory into action, possessed the concrete operability of implementing under theoretical direction, for wide popularization and application has been established solid basis.
The present invention has carried out property examination on probation, and property examination on probation comprises from being tested to the whole process of production, the present invention is by clear frit dry granular, ceramic green, the single test of ground-coat enamel, on single test basis, carry out single test preferred, preferred single test is optimized to combination, after the optimum combination of single test, determine the production technique of once-firing, the production technique of application once-firing, produce " transparent glass and over-glaze decoration ceramic clad plate " product innovation, the present invention is on the research experiment basis of up to a hundred times, determined " once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process ", from in fact effectively having solved to make, meet efficient energy-saving, reduce discharge, protection of the environment, low-carbon (LC) is produced, the series of key techniques problem of " transparent glass and over-glaze decoration ceramic clad plate " product innovation of low-carbon (LC) life." transparent glass and the over-glaze decoration ceramic clad plate " of application the present invention " once-firing transparent glass and over-glaze decoration Ceramic Composite plate producing process " production after testing, its main performance index is as following table:
From table, apply " transparent glass and over-glaze decoration ceramic clad plate " product innovation that the present invention produces, its main performance index has reached or has been better than concerned countries standard.Through examination on probation, obtained expected effect.
These are only preferred embodiment of the present invention, not the present invention is done to any pro forma restriction; The those of ordinary skill of all industry all can be implemented with the above shown in by specification accompanying drawing swimmingly; But the equivalent variations of making differentiation not departing from technical solution of the present invention, is equivalent embodiment of the present invention, all still belongs to technical scheme of the present invention.
Claims (2)
1. once-firing transparent glass and an over-glaze decoration Ceramic Composite plate producing process, is characterized in that:
1., prepare clear frit dry granular: with fineness degree, be less than 100 object quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, barium carbonate, sodium carbonate, salt of wormwood, borax, each 80-700 kilogram of boric acid, and select fineness degree be less than in 100 object sodium-chlor, sodium sulfate, fluorite a kind of 100 kilograms as finings; The above is mixed as frit raw material, the frit raw material mixing is sent in cell furnace melt, temperature of fusion is 1520-1600 ℃; To the melt having melted, after shrend, oven dry, fragmentation, screening, acquisition composition range is SiO
250-70%, Al
2o
35-20%, CaO0-10%, MgO0-10%, K
2o+Na
2o2-8%, BaO0-8%, B
2o
3the 20-200 order clear frit dry granular of 0-8%, finings 1-10% and moisture < 0.5% is stand-by;
2., prepare ceramic green: the kaolin that is less than 1 millimeter with granularity, clay, quartzy, potassium felspar sand, albite, each 385-12250 of talcum kilogram through mixing as ceramic green raw material, in described ceramic green raw material, add appropriate water, and equalization adds alkali, water glass, tripoly phosphate sodium STPP is as water reducer, the quantity that adds described water reducer is the 0.3-0.5% of described ceramic green raw material, after ball mill ball milling pulping, carry out the dry powder process of spray dried, moisture after the dry powder process of described spraying is 5.5-6.5%, again through automatic hydraulic press shaped by fluid pressure, and then the dry composition range that makes of drying kiln drying is SiO
266-75%, Al
2o
315-25%, CaO+MgO0.5-5%, K
2o+Na
2the ceramic green of O2-8%, water reducer 0-2% and moisture < 0.5% is stand-by,
3., prepare ground-coat enamel: the fineness degree of usining is less than 100 object calcined kaolins, quartz, potassium felspar sand, albite, calcite, talcum, rhombspar, zinc oxide, zirconium English powder, each 2-30 of nepheline kilogram through mixing as ground-coat enamel raw material, in described ground-coat enamel raw material, add methylcellulose gum as thickening material and appropriate water, and a kind of as water reducer in the alkali that brings Selection In, water glass, tripoly phosphate sodium STPP, add the quantity of described thickening material and water reducer to be the 0.3-0.5% of described ground-coat enamel raw material, entering ball mill ball milling, to become chemical composition be SiO
240-60%, Al
2o
315-25%, CaO5-15%, MgO0-8%, K
2o+Na
2o2-10%, ZnO0-8%, ZrO
2it is that the pulpous state ground-coat enamel of 10000-hole sieve She 0.4-0.5% is stand-by that 3-12%, water reducer and thickening material are 0-2% and fineness;
4., prepare ground-coat enamel base: on dried described ceramic green, application pouring glaze machine is implemented described ground-coat enamel, 65-70 ℃ of base temperature, take and spray water 10 grams and the quantity of implementing described ground-coat enamel under the condition of 300 * 300 pallet unit of measure as 60 ± 1 grams of 300 * 300 pallet unit of measure, be prepared into ground-coat enamel base stand-by;
5., preparation over-glaze decoration greenwave: utilize roller or silk screen, on the surface of described ground-coat enamel base, in the mode of printing, print that modulate, good with the colorful one, printability, various printing glazes, be prepared into the over-glaze decoration greenwave that enriches design and color stand-by;
6., preparation over-glaze decoration frit dry granular greenwave: apply dry-type belt material distributing machine, with 3.5-6Kg/m
2cloth amount by the uniform charity of described clear frit dry granular on described over-glaze decoration greenwave, be prepared into over-glaze decoration frit dry granular greenwave stand-by;
7., prepare greenwave to be burnt: in the mode of spray, on the surface of described over-glaze decoration frit dry granular greenwave, the described clear frit dry granular on described over-glaze decoration greenwave is fixed the methylcellulose gum water spray as stationary liquid, be prepared into greenwave to be burnt stand-by;
8., prepare transparent glass and over-glaze decoration Ceramic Composite boards half-finished product: described in inciting somebody to action, greenwave to be burnt is put into roller kiln, in temperature, be that 1120-1200 ℃, time are under the condition of 60-180 minute, greenwave described to be burnt is fired, be prepared into transparent glass and over-glaze decoration Ceramic Composite boards half-finished product is stand-by;
9., prepare transparent glass and over-glaze decoration Ceramic Composite board finished product: described transparent glass and over-glaze decoration Ceramic Composite boards half-finished product are scraped after thicknessing, rough polishing, smart throwing, edging, chamfering, air-dry, pick, classification, be prepared into transparent glass and over-glaze decoration Ceramic Composite board finished product.
2. once-firing transparent glass according to claim 1 and over-glaze decoration Ceramic Composite plate producing process, is characterized in that:
In described preparing in ceramic green 2., described kaolin is selected to be replaced by black mud, makes the loss on ignition < 4.7% of described ceramic green;
In described preparing in ground-coat enamel 3., the flow velocity of described pulpous state ground-coat enamel is grace formula viscosity 16-18 second.
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CN115894084B (en) * | 2022-11-10 | 2023-09-19 | 福建省德化非凡陶瓷有限公司 | Texalized high-whiteness porcelain decorated by tortoise back texture and preparation process thereof |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1888351A (en) * | 2006-07-20 | 2007-01-03 | 广东东鹏陶瓷股份有限公司 | Stere-colour decorative transparent nucleated glass ceramic bricks and producing method thereof |
CN101445325A (en) * | 2008-12-25 | 2009-06-03 | 广东博德精工建材有限公司 | Method for producing microcrystalline glass-ceramics composite board with novel microcrystalline phase |
CN101921136A (en) * | 2010-04-13 | 2010-12-22 | 张垠 | Raw material matting glaze |
-
2011
- 2011-11-02 CN CN201110339861.9A patent/CN102515774B/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1888351A (en) * | 2006-07-20 | 2007-01-03 | 广东东鹏陶瓷股份有限公司 | Stere-colour decorative transparent nucleated glass ceramic bricks and producing method thereof |
CN101445325A (en) * | 2008-12-25 | 2009-06-03 | 广东博德精工建材有限公司 | Method for producing microcrystalline glass-ceramics composite board with novel microcrystalline phase |
CN101921136A (en) * | 2010-04-13 | 2010-12-22 | 张垠 | Raw material matting glaze |
Non-Patent Citations (4)
Title |
---|
利用废渣生产微晶玻璃复合板;杨会智 等;《佛山陶瓷》;20100630(第6期);第17-19页 * |
戴长禄.第二代微晶玻璃陶瓷复合砖生产技术.《广东建设报》.2004,第B03版. |
杨会智 等.利用废渣生产微晶玻璃复合板.《佛山陶瓷》.2010,(第6期),第17-19页. |
第二代微晶玻璃陶瓷复合砖生产技术;戴长禄;《广东建设报》;20040406;第B03版 * |
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