CN105601127A - Coloring method of pyroceram - Google Patents

Coloring method of pyroceram Download PDF

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Publication number
CN105601127A
CN105601127A CN201511017758.7A CN201511017758A CN105601127A CN 105601127 A CN105601127 A CN 105601127A CN 201511017758 A CN201511017758 A CN 201511017758A CN 105601127 A CN105601127 A CN 105601127A
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glass
devitrified glass
warming
cooled
slurry
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CN105601127B (en
Inventor
郭宏伟
艾志远
宋建波
王宇飞
池龙兴
莫祖学
杨晨
唐元元
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/008Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in solid phase, e.g. using pastes, powders
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0036Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00Glasses, glazes or enamels with special properties

Abstract

The invention discloses a coloring method of pyroceram. The coloring method comprises the steps of firstly mixing SiO2, Al2O3, CaO, MgO, Na2O, K2O, TiO2, ZrO2, B2O3, ZnO, Fe2O3 and Sb2O3 in parts by mass, thus forming a batch mixture, and then preparing the pyroceram after founding and water quenching; putting water, glycerinum and Arabic gum into a beaker, stirring and mixing evenly, then adding the mixture into a mixture of AgNO3, Cu2O, FeSO4.7H2O, zinc powder and SiC powder, stirring evenly, ball-milling to obtain coloring ion paste, pouring the paste into a screen process press, putting the pyroceram under a silk screen plate for silk-screen printing, sintering in a segmented way, and then washing away redundant copper salt and silver salt on a surface, thus obtaining the colored pyroceram. The pyroceram prepared by a preparation method is various in color and diversity, has real and natural coloring and visual effects, and is smooth and attractive in surface, the decorative effect of a pyroceram decorative slab is improved, the use scope is enlarged, and the added value of a product is high.

Description

A kind of colorize method of devitrified glass
Technical field
The present invention relates to a kind of manufacture method of devitrified glass, particularly a kind of colorize method of devitrified glass.
Background technology
The key property of the existing glass of devitrified glass, has again ceramic polycrystalline feature, has concentrated glass and potteryThe feature of porcelain, becomes the new material of a class uniqueness. High with its mechanical strength, hardness is large, anti-wear performance good,Corrosion resistance is strong, has good chemical stability and heat endurance, can adapt to rugged environment, in recent yearsObtain in the world development fast.
At present, white and the light crystallizing glass sheet material of devitrified glass use amount maximum. Along with people's lifeThe raising of level, increasing to the demand of colour devitrified glass. And produce colour devitrified glass normally firstPrepare stained glass shrend material, and then crystallization is prepared colour devitrified glass. Also there is a small amount of picture pottery that usedThe technique that porcelain is painted, carries out inkjet printing, the techniques pair such as serigraphy again on the devitrified glass surface processingDevitrified glass carries out painted. These coloring process colors are abundant, but the damage that the surface of devitrified glass is carried outEvil, and painted pigment and matrix devitrified glass adhesion are poor, easily fragmentation, the table after this technique is paintedFace is uneven, follow-up cleaning technology complexity.
Li Yaohui (Li Yaohui, Cao builds luxuriant, Xu Bo etc. and vanadium, neodymium are to lithium silicon aluminum micro-crystal glass crystallization and paintedImpact [J]. Rare Metals Materials and engineering, 2009,38 (2): 1128-1132.) etc. people introduce V2O5、Nd2O3To transparent Li2O-Al2O3-SiO2(LAS) devitrified glass carries out paintedly, and analyzes vanadium, neodymium ion to glass crystallizationThe impact of process and tinctorial property. Guo Xingzhong (Guo Xingzhong, Yang Hui, Li Haimiao etc. with fusion process preparation containing paintedAgent Li2O-Al2O3-SiO2The coring of glass and crystallization [J]. silicate journal, 2007,35 (10): 1390-1395.)Contain mixed colorant (Fe Deng people with fusion process preparation2O3+Co2O3+Ni2O3) Li2O-Al2O3-SiO2(LAS)Glass, result shows: mix coloring ion and cause LAS glass to show black in the overlapping absorption of visible-range; ?Adding of toner makes LAS devitrification of glass peak temperature increase by 50~100 DEG C, and the crystallization peak of high Co content glassTemperature will be higher than the glass of high Ni content, but colouring agent does not affect coring and the crystalline phase group of LAS glass substantiallyBecome; Be 610 DEG C containing the suitable nucleation temperature of colouring agent LAS glass, crystallization temperature is 900~930 DEG C. SummerHai Ping (Xia Haiping, Zhang Jianli, Chen Hongbing etc. the absorption spectrum [J] of Colored Transparent Glass Ceramic. Acta Optica,2002,22 (7): 878-881.) etc. people is at Li2O-Al2O3-SiO2In system glass, mix a small amount of Nucleating Agent TiO2、ZrO2、P2O5, then mix rare earth ion and transition metal ions as colouring agent, at high temperature found and obtain coloured silkLook clear glass. Han Ronghui (Han Rong luxuriant growth .CaO-Al2O3-SiO2System color phosphor slag microcrystalline glass composition, knotThe research [D] of structure and performance. Wuhan University of Technology, 2012.) develop cas system color phosphor slag microcrystalline glass,Improve the decorative effect of phosphorus slag devitrified glass. Fixing under the prerequisite that phosphorus slag volume is constant, painted by changingThe painted impact on Structure of Glass Ceramic and performance of agent kind and content system research hybrid ionic. By experimentHigh performance ecru, green, grey phosphorus slag devitrified glass are successfully developed. Yang Lanlan (Yang Lanlan. transitionMetal oxide is to R2O-CaO-SiO2The research [D] of-F system glass ceramics coloring mechanism. Wuhan University of Technology,2011.) the coloring process preparation of simulation material road is applicable to the painted colorant in material road by experiment, and research colorant is at siliconDiffusion velocity in alkali calcium stone white glass liquid, adopts stirring technique to prepare the colour devitrified glass of uniform coloring.This colorant is expected to for canasite devitrified glass Liao road painted. Expect in the painted experiment in road system in simulationStandby colour devitrified glass surface is without striped, and the soft homogeneous of color and luster has and becomes high-grade decoration panel materialPotentiality. In the batch of canasite system glass, add respectively K2Cr2O7And Co2O3Two kinds of colouring agents.Above bibliographical information be all in glass smelting process, add painted after, then adopt method of piling to prepare devitrified glass,This process colour dullness, and can not form colorful pattern, range of application is narrow.
(devitrified glass ceramics of illusion-colour abstract art style crystallization is compound in Guangdong Bode Jinggong Building Materials Co., LtdPlate [Z] .2011. of Guangdong Bode Jinggong Building Materials Co., Ltd) develop can increase crystallization amount and form smeared out boundaryGlass ceramics frit, adopt first the distributing mode of template and the combination of dry powder silk screen, create a kind of patternThere is the new product of illusion-colour abstract art style, and called after " Boulder Seiko jade auspicious cloud series ". Employing is manyBrilliant microcrystalline glass formula and the double action that reduces devitrified glass pellet sizes, increase crystallization interface, and utilizePossess the coloring ion of different self-diffusion coefficients and the mutual scattering and permeating of the devitrified glass of composition, form crystallite glassThe obfuscation on glass different color border, chaotization. Utilize taking template as main, dry powder silk screen cloth and cloth equalEven is auxiliary process, manufactures the crystallizing glass sheet material of providing unique artistic picture scroll style.CN200610095280.4 (Yang Liang. improve the preparation process of microcrystalline stone of decorative effect: China,CN200610095280.4[P] .2007-6-6.) a kind of preparation process of microcrystalline stone that improves decorative effect is provided,The method, on traditional microlite production technology basis, improves cloth material process, by for decorating lookMicrolite pellet is further pulverized and is made slurry or powder, respectively by means of ceramic wall and floor bricks wet method glazing or dryPowder stamp equipment technology, will decorate in microlite bed material slurry or powder transfer, then crystallization, grinding and polishingCutting, thus can produce the microlite product of aesthetic effect brilliance, products obtained therefrom and traditional microliteCompare and there is lively pattern rich and varied, natural beauty, ideally promote the aesthetic effect of microlite.CN200810116886.0 (Beijing Jingya Stone Technology Co., Ltd.. A kind of system of colored drawing crystallizing glass decoration boardMaking method: China, CN200810116886.0[P] .2008-12-10.) disclose a kind of colored drawing crystallizing glass and decoratedThe manufacture method of plate, described manufacture method comprises the following steps: the preparation of (1) devitrified glass colorant; (2) processPlain color after surface cleaning for crystallizing glass sheet material the devitrified glass colorant of step (1) preparation adopt manual colour painting andMethod for printing screen is made various patterns; (3) drawn colour devitrified glass decorative panel is entered to electric furnace roasting;(4) product after firing is carried out to polishing again. It utilizes high temperature decorating colour, by hand colour painting and serigraphyMethod draws a design on plain color crystallizing glass sheet material. After calcining grinding and polishing, obtain again colour devitrified glass dressDecoratice board. CN201120367213.x (Foshan Shiwan Eagle-Brand Ceramic Co., Ltd. Once burn devitrified glass multipleClose brick: China, CN201120367213.X[P] .2012-5-30.) open one once burns devitrified glass composite brick,On vitrified tile ceramic body, lay successively screen printing glaze layer, silk screen dry powder decorative layer and glass frit layer, instituteState glass frit layer and adopt methyl hydropexis, described silk screen dry powder decorative layer passes through colorant dry powder at screen printing glazeOn layer, make with serigraphy. This product is using vitrified tile as main base substrate, and decorative intermediate layer adopts repeatedly silk screenStamp glazing is enriched pattern decorative layer in conjunction with dry powder serigraphy decorative layer, and it adopts once-firing type, hasLow energy consumption, advantage cheaply. CN02149626.9 (Qiaodong Ceramics Co Ltd, Nanhai Nanhai City. Devitrified glassWall floor tile decoration technology and product: China, CN02149626.9[P] .2004-6-30.) with color pigments by silkReticulated printing, decal paper applique or Freehandhand-drawing mode are decorated devitrified glass burnishing surface, put into decorating firing kiln roasting after being driedFlower, decoration firing temperature is 600~1100 DEG C, and the time is greater than 2 hours, and the feature of product of the present invention is at crystallite glassOn the devitrified glass burnishing surface of glass brick or composite microcrystallite glass brick, be attached with the decorative pattern that enamel firing process is madeLayer. Above document has all adopted the coloring and decorating technology of traditional ceramics, and prepared pattern is abundant, but sinteringTemperature high (being greater than 600 DEG C), and all damaged the original surface of devitrified glass.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of without high temperature sintering,Color is abundant, does not damage the painted devitrified glass of the original surface smoothness of devitrified glass, and preparation technology is simple,Easy to operate, energy consumption is low, saves the energy, is suitable for the preparation method of the painted devitrified glass of producing in enormous quantities,Various, rich true and the natural painted and vision of devitrified glass color making according to preparation method of the present inventionEffect, devitrified glass smooth surface, attractive in appearance, increase the decorative effect of microcrystalline glass decorative plate, expandThe scope of application, added value of product is high.
For achieving the above object, the technical solution used in the present invention is:
A colorize method for devitrified glass, comprises the steps:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 45~60% SiO2, 7~12% Al2O3, 8~15% CaO,3~5% MgO, 4~8% Na2O, 1~4% K2O, 2~5% TiO2, 1~3% ZrO2,1~3%B2O3, 3~6% ZnO, 0~5% Fe2O3, 0.5~1% Sb2O3Putting into batch mixer is mixed to allEvenness is greater than 98%, forms batch;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1450~1500 DEG C, and found 10~20h at 1450~1500 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, carry out segmentation and burn till: last, through 6~8h is cooled to room temperature;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing;
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry:
First water, glycerine, gum arabic are put into beaker according to mass fraction and be uniformly mixed, thenIt is joined to AgNO according to mass ratio3、Cu2O、FeSO4·7H2In the compound of O, zinc powder, SiC powderStir, after stirring, then pour this slurry in ball grinder ball milling and, after 2~5 hours, prepareGo out coloring ion slurry;
Then, prepare painted devitrified glass:
The coloring ion slurry making is poured in screen process press, and devitrified glass prepared by the first step is put inUnder silk screen plate, carry out serigraphy, print thickness is 0.1~50 micron, enters horse not after slurry is natural dryingIn stove, carry out, after multi-steps sintering, being cooled to below 50 DEG C with furnace temperature, after taking out sample and by copper unnecessary surfaceSalt and silver salt are washed off, obtain painted devitrified glass.
Further, described SiO2,Al2O3,CaO,MgO,Na2O,K2O,TiO2,ZrO2,B2O3,ZnO,Fe2O3,Sb2O3Respectively by raw material of industry quartz, aluminium oxide, calcite, dolomite, carbonic acidSodium, potash, titanium dioxide, zirconia, borax, zinc oxide, iron oxide red, antimony powder is introduced, and granularity is greater than80 orders.
Further, described first step step 7) in segmentation burn till into, start to be warming up to by 1~3h from room temperature150 DEG C; Then be warming up to 680 DEG C from 150 DEG C through 2~3h; Then be warming up to through 3~4h from 680 DEG C1080~1120 DEG C, and be incubated 1~3h; Then be cooled to 820 DEG C from 1080~1120 DEG C through 3~4h;Then be cooled to 650 DEG C from 820 DEG C through 1~2h, and be incubated 1~2h.
Further, described devitrified glass is shaped as tabular, curved surface, arc or circle.
Further, described coloring ion diffusion slurry is to be prepared from according to the raw material of following mass ratio:
AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic: zinc powder: SiC powder=0~10:3~15:3~5:5~8:8~15:0~5:0~2:0~2。
Further, described second step multi-steps sintering is, is raised to 300 DEG C with the speed of 3~5 DEG C/min from room temperature,Be incubated 20 minutes; Be warming up to 450~550 DEG C with the speed of 5~10 DEG C/min again, be incubated 10~60 minutes.
The present invention utilizes ion diffusion colorize method painted to devitrified glass, does not damage the surface of devitrified glass.Ion diffusion process is carried out in air, need not under reducing condition, process. Devitrified glass surface after paintedSmooth, increase visual effect and the decorative effect of devitrified glass. Make according to preparation method of the present inventionVarious, rich true and the natural painted and visual effect of devitrified glass color, devitrified glass smooth surface,Attractive in appearance, increase the decorative effect of microcrystalline glass decorative plate, expand the scope of application, added value of product is high.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, completeDescription.
Embodiment 1:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 55% SiO2, 8% Al2O3, 11% CaO, 4%MgO, 6% Na2O, 2% K2O, 3% TiO2, 2% ZrO2, 2% B2O3, 4% ZnO,2.5% Fe2O3, 0.5% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, form batch;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1500 DEG C, and found 10h at 1500 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 1h; Then be warming up to 680 DEG C from 150 DEG C through 2h; Then from 680 DEG C of warpsCross 3h and be warming up to 1080 DEG C, and be incubated 3h; Then be cooled to 820 DEG C from 1080 DEG C through 4h; Then certainly820 DEG C are cooled to 650 DEG C through 2h, and are incubated 2h; Finally, be cooled to room temperature through 8h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic:Zinc powder: the mass ratio of SiC powder=7:10:5:8:15:2:1:1. After stirring, then shouldSlurry is poured ball milling in ball grinder into and after 5 hours, is prepared coloring ion slurry;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 10 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 3 DEG C/min from room temperature, be incubated 20 minutes; Again with 10 DEG C/minSpeed be warming up to 550 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 10 minutes, take out after sample and willUnnecessary mantoquita and the silver salt in surface washed off, obtaining brown devitrified glass.
Embodiment 2:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 56% SiO2, 10% Al2O3, 9% CaO, 3%MgO, 4% Na2O, 3% K2O, 3% TiO2, 1% ZrO2, 3% B2O3, 5% ZnO,2% Fe2O3, 1% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, form batch;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1480 DEG C, and found 12h at 1480 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 2h; Then be warming up to 680 DEG C from 150 DEG C through 2h; Then from 680 DEG C of warpsCross 4h and be warming up to 1100 DEG C, and be incubated 1h; Then be cooled to 820 DEG C from 1100 DEG C through 4h; Then certainly820 DEG C are cooled to 650 DEG C through 1h, and are incubated 1h; Finally, be cooled to room temperature through 8h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic:Zinc powder: the mass ratio of SiC powder=6:12:5:8:12:4:2:2, after stirring, then by this slurryMaterial is poured ball milling in ball grinder into and after 2 hours, is prepared coloring ion slurry;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 20 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 4 DEG C/min from room temperature, be incubated 20 minutes; Again with 8 DEG C/minSpeed be warming up to 510 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 40 minutes, take out after sample and willRed coloration devitrified glass is washed and obtained to unnecessary mantoquita and the silver salt in surface off.
Embodiment 3:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 50% SiO2, 12% Al2O3, 15% CaO, 3%MgO, 8% Na2O, 1% K2O, 2% TiO2, 1% ZrO2, 1% B2O3, 6% ZnO,1% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, form batch;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1460 DEG C, and found 15h at 1460 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 1.5h; Then be warming up to 680 DEG C from 150 DEG C through 2.5h; Then from 680 DEG CBe warming up to 1120 DEG C through 3.5h, and be incubated 1h; Then be cooled to 820 DEG C from 1120 DEG C through 3h; SoBe cooled to 650 DEG C from 820 DEG C through 2h afterwards, and be incubated 2h; Finally, be cooled to room temperature through 8h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic:The mass ratio of zinc powder=4:9:5:7:12:3:1, after stirring, then pours this slurry into ball grinderMiddle ball milling prepares coloring ion slurry after 3 hours;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 30 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 5 DEG C/min from room temperature, be incubated 20 minutes; Again with 10 DEG C/minSpeed be warming up to 450 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 60 minutes, take out after sample and willYellow devitrified glass is washed and obtained to unnecessary mantoquita and the silver salt in surface off.
Embodiment 4:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 45% SiO2, 11.2% Al2O3, 11% CaO, 5%MgO, 8% Na2O, 4% K2O, 5% TiO2, 3% ZrO2, 1% B2O3, 4%ZnO, 2% Fe2O3, 0.8% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, formation is joinedClose material;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1450 DEG C, and found 20h at 1450 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 3h; Then be warming up to 680 DEG C from 150 DEG C through 3h; Then from 680 DEG C of warpsCross 4h and be warming up to 1080 DEG C, and be incubated 3h; Then be cooled to 820 DEG C from 1080 DEG C through 4h; Then certainly820 DEG C are cooled to 650 DEG C through 2h, and are incubated 2h; Finally, be cooled to room temperature through 6h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic:Zinc powder: the mass ratio of SiC powder=6:6:5:7:10:1:1:1, after stirring, then by this slurryMaterial is poured ball milling in ball grinder into and after 3 hours, is prepared coloring ion slurry;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 50 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 5 DEG C/min from room temperature, be incubated 20 minutes; Again with 10 DEG C/minSpeed be warming up to 550 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 60 minutes, take out after sample and willBrown devitrified glass is washed and obtained to unnecessary mantoquita and the silver salt in surface off.
Embodiment 5:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 60% SiO2, 7% Al2O3, 9% CaO, 4%MgO, 4.4% Na2O, 4% K2O, 3% TiO2, 3% ZrO2, 1% B2O3, 3%ZnO, 1% Fe2O3, 0.6% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, formation is joinedClose material;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1480 DEG C, and found 15h at 1480 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 3h; Then be warming up to 680 DEG C from 150 DEG C through 2h; Then from 680 DEG C of warpsCross 4h and be warming up to 1120 DEG C, and be incubated 2.5h; Then be cooled to 820 DEG C from 1120 DEG C through 4h; ThenBe cooled to 650 DEG C from 820 DEG C through 2h, and be incubated 2h; Finally, be cooled to room temperature through 7h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic:Zinc powder: the mass ratio of SiC powder=2:8:5:8:15:5:2:2, after stirring, then by this slurryMaterial is poured ball milling in ball grinder into and after 4 hours, is prepared coloring ion slurry;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 50 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 5 DEG C/min from room temperature, be incubated 20 minutes; Again with 10 DEG C/minSpeed be warming up to 550 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 60 minutes, take out after sample and willRed coloration devitrified glass is washed and obtained to unnecessary mantoquita and the silver salt in surface off.
Embodiment 6:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 48% SiO2, 11% Al2O3, 8% CaO, 5%MgO, 7% Na2O, 3% K2O, 4% TiO2, 2% ZrO2, 2% B2O3, 4.2%ZnO, 5% Fe2O3, 0.8% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, formation is joinedClose material;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1450 DEG C, and found 10h at 1450 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 1h; Then be warming up to 680 DEG C from 150 DEG C through 2h; Then from 680 DEG C of warpsCross 4h and be warming up to 1080 DEG C, and be incubated 3h; Then be cooled to 820 DEG C from 1080 DEG C through 4h; Then certainly820 DEG C are cooled to 650 DEG C through 2h, and are incubated 1h; Finally, be cooled to room temperature through 8h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic:Zinc powder: the mass ratio of SiC powder=10:3:3:5:15:5:2:2, after stirring, then by this slurryMaterial is poured ball milling in ball grinder into and after 5 hours, is prepared coloring ion slurry;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 50 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 5 DEG C/min from room temperature, be incubated 20 minutes; Again with 10 DEG C/minSpeed be warming up to 510 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 40 minutes, take out after sample and willPainted devitrified glass is washed and obtained to unnecessary mantoquita and the silver salt in surface off.
Embodiment 7:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 48% SiO2, 11% Al2O3, 8% CaO, 5%MgO, 7% Na2O, 3% K2O, 4% TiO2, 2% ZrO2, 2% B2O3, 4.2%ZnO, 5% Fe2O3, 0.8% Sb2O3Put into batch mixer and be mixed to the uniformity and be greater than 98%, formation is joinedClose material;
2) then, the batch mixing is joined and is warming up to equably by inclined blanket type batcherIn the horse-shoe flame furnace of 1450 DEG C, and found 10h at 1450 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, burn till according to following technique: open from room temperatureBegin to be warming up to 150 DEG C by 1h; Then be warming up to 680 DEG C from 150 DEG C through 2h; Then from 680 DEG C of warpsCross 4h and be warming up to 1080 DEG C, and be incubated 3h; Then be cooled to 820 DEG C from 1080 DEG C through 4h; Then certainly820 DEG C are cooled to 650 DEG C through 2h, and are incubated 1h; Finally, be cooled to room temperature through 8h;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing.
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry: first water, glycerine, gum arabic are put into beaker and stirredMix and mix, then joined AgNO3、Cu2O、FeSO4·7H2O, zinc powder, SiC powder mixedClose in material and stir, wherein Cu2O:FeSO4·7H2O: water: glycerine: SiC powder=15:4:5:8:2Mass ratio, after stirring, then pour this slurry in ball grinder ball milling and preparing after 5 hoursLook ion slurry;
Then, prepare painted devitrified glass: the slurry making is poured in screen process press, micro-by what prepareCrystal glass is put under silk screen plate, carries out serigraphy, and print thickness is 50 microns, after slurry is natural dryingEnter in Muffle furnace, be raised to 300 DEG C with the speed of 5 DEG C/min from room temperature, be incubated 20 minutes; Again with 10 DEG C/minSpeed be warming up to 510 DEG C, be incubated and be cooled to below 50 DEG C with furnace temperature after 40 minutes, take out after sample and willPainted devitrified glass is washed and obtained to unnecessary mantoquita and the silver salt in surface off.
The present invention utilizes ion diffusion colorize method painted to devitrified glass, does not damage the surface of devitrified glass.Devitrified glass smooth surface after painted is smooth, has shock resistance, corrosion-resistant, smooth and beautiful appearance, insulation, resistance toThe features such as heat have increased visual effect and the decorative effect of devitrified glass simultaneously. Prepared by the inventive method micro-Various, rich true and the natural painted and visual effect of crystal glass color, and easy to operate, preparation technologySimply, energy consumption is low, saves the energy, is suitable for mass industrialized production, good decorating effect, added value of productHigh.
Be understandable that, although the present invention discloses as above with preferred embodiment, but above-described embodiment alsoNon-in order to limit the present invention. For any those of ordinary skill in the art, do not departing from skill of the present inventionIn art scheme scope situation, can utilize the technology contents of above-mentioned announcement that technical solution of the present invention is made and being permittedMany possible variation and modifications, or be revised as the equivalent embodiment of equivalent variations. Therefore, every the disengaging originallyThe content of invention technical scheme, anyly simply repaiies made for any of the above embodiments according to technical spirit of the present inventionChange, equivalent variations and modification, all still belong in the scope of technical solution of the present invention protection.

Claims (6)

1. a colorize method for devitrified glass, is characterized in that, comprises the steps:
The first step: the preparation of crystallite glass substrate
1) first, according to mass fraction by 45~60% SiO2, 7~12% Al2O3, 8~15% CaO,3~5% MgO, 4~8% Na2O, 1~4% K2O, 2~5% TiO2, 1~3% ZrO2,1~3%B2O3, 3~6% ZnO, 0~5% Fe2O3, 0.5~1% Sb2O3Putting into batch mixer is mixed to allEvenness is greater than 98%, forms batch;
2) then, the batch mixing is joined to the horse that has been warming up to 1450~1500 DEG C equablyIn hoof flame kiln, and found 10~20h at 1450~1500 DEG C, obtain glass metal;
3) then, glass metal, by supply channel, is cooled to 1200 DEG C gradually;
4) then,, in the time that glass metal flows to revolving sleeve place, pass through by glass metal by the height of controlling revolving sleeveOrifice ring, flows in the pond of feeder channel below;
5) then, the glass disintegrating slag in tank is pulled out, air-dry;
6) then, glass disintegrating slag is evenly joined in the mullite mould that inner surface is affixed with ceramic fiber paper,Layer thickness 5cm;
7) then, sample is pushed in kiln together with mould, carry out segmentation and burn till: last, through 6~8h is cooled to room temperature;
8) last, specimen surface had both been obtained to devitrified glass through sanding and polishing;
Second step: the preparation of painted enamel
First, prepare coloring ion diffusion slurry:
First water, glycerine, gum arabic are put into beaker according to mass fraction and be uniformly mixed, thenIt is joined to AgNO according to mass ratio3、Cu2O、FeSO4·7H2In the compound of O, zinc powder, SiC powderStir, after stirring, then pour this slurry in ball grinder ball milling and, after 2~5 hours, prepareGo out coloring ion slurry;
Then, prepare painted devitrified glass:
The coloring ion slurry making is poured in screen process press, and devitrified glass prepared by the first step is put inUnder silk screen plate, carry out serigraphy, print thickness is 10~50 microns, enters horse not after slurry is natural dryingIn stove, carry out, after multi-steps sintering, being cooled to below 50 DEG C with furnace temperature, after taking out sample and by copper unnecessary surfaceSalt and silver salt are washed off, obtain painted devitrified glass.
2. the colorize method of devitrified glass according to claim 1, is characterized in that: described SiO2,Al2O3,CaO,MgO,Na2O,K2O,TiO2,ZrO2,B2O3,ZnO,Fe2O3,Sb2O3PointNot by raw material of industry quartz, aluminium oxide, calcite, dolomite, sodium carbonate, potash, titanium dioxide,Zirconia, borax, zinc oxide, iron oxide red, antimony powder is introduced, and granularity is greater than 80 orders.
3. the colorize method of devitrified glass according to claim 1, is characterized in that: the described first stepStep 7) in segmentation burn till into, start to be warming up to 150 DEG C by 1~3h from room temperature; Then from 150 DEG C of warpsCross 2~3h and be warming up to 680 DEG C; Then be warming up to 1080~1120 DEG C from 680 DEG C through 3~4h, and insulation1~3h; Then be cooled to 820 DEG C from 1080~1120 DEG C through 3~4h; Then from 820 DEG C through 1~2h is cooled to 650 DEG C, and is incubated 1~2h.
4. the colorize method of devitrified glass according to claim 1, is characterized in that: described crystallite glassGlass is shaped as tabular, curved surface, arc or circle.
5. the colorize method of devitrified glass according to claim 1, is characterized in that: described painted fromSon diffusion slurry is to be prepared from according to the raw material of following mass ratio:
AgNO3:Cu2O:FeSO4·7H2O: water: glycerine: gum arabic: zinc powder: SiC powder=0~10:3~15:3~5:5~8:8~15:0~5:0~2:0~2。
6. the colorize method of devitrified glass according to claim 1, is characterized in that: described second stepMulti-steps sintering is, is raised to 300 DEG C with the speed of 3~5 DEG C/min from room temperature, is incubated 20 minutes; Again with 5~The speed of 10 DEG C/min is warming up to 450~550 DEG C, is incubated 10~60 minutes.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162428A (en) * 2017-05-31 2017-09-15 江苏精盾节能科技有限公司 A kind of devitrified glass and preparation method thereof
CN108083636A (en) * 2017-11-17 2018-05-29 宁波凯乐工艺品有限公司 A kind of imitated Yuhuatai colorful pebble
CN109678362A (en) * 2019-03-07 2019-04-26 科立视材料科技有限公司 A kind of ion diffusion colorant and its application

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US4056643A (en) * 1973-12-08 1977-11-01 Nippon Sheet Glass Co., Ltd. Method for decorative coloring of glass
US4253861A (en) * 1980-01-21 1981-03-03 General Electric Company Method of copper staining a glass article
CN101279819A (en) * 2008-04-30 2008-10-08 陕西科技大学 Preparation of red glass
CN101560065A (en) * 2009-05-14 2009-10-21 陕西科技大学 Preparation method for colored ice-patterned glass

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4056643A (en) * 1973-12-08 1977-11-01 Nippon Sheet Glass Co., Ltd. Method for decorative coloring of glass
US4253861A (en) * 1980-01-21 1981-03-03 General Electric Company Method of copper staining a glass article
CN101279819A (en) * 2008-04-30 2008-10-08 陕西科技大学 Preparation of red glass
CN101560065A (en) * 2009-05-14 2009-10-21 陕西科技大学 Preparation method for colored ice-patterned glass

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162428A (en) * 2017-05-31 2017-09-15 江苏精盾节能科技有限公司 A kind of devitrified glass and preparation method thereof
CN108083636A (en) * 2017-11-17 2018-05-29 宁波凯乐工艺品有限公司 A kind of imitated Yuhuatai colorful pebble
CN109678362A (en) * 2019-03-07 2019-04-26 科立视材料科技有限公司 A kind of ion diffusion colorant and its application

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