CN105601127B - A kind of color method of devitrified glass - Google Patents

A kind of color method of devitrified glass Download PDF

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CN105601127B
CN105601127B CN201511017758.7A CN201511017758A CN105601127B CN 105601127 B CN105601127 B CN 105601127B CN 201511017758 A CN201511017758 A CN 201511017758A CN 105601127 B CN105601127 B CN 105601127B
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glass
devitrified glass
coloring
slurry
warming
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CN105601127A (en
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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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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/008—Treatment 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C10/00—Devitrified 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
    • C03C10/0036—Devitrified 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL 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
    • C03C2204/00—Glasses, glazes or enamels with special properties

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The invention discloses a kind of color method of devitrified glass, first, according to mass fraction by SiO2、Al2O3、CaO、MgO、Na2O、K2O、TiO2、ZrO2、B2O3、ZnO、Fe2O3And Sb2O3It is mixed into batch；Then devitrified glass is prepared after founding water quenching.Water, glycerine, gum arabic are put into beaker and be uniformly mixed again, AgNO is then added into3、Cu2O、FeSO4·7H2Stirred in O, zinc powder, the compound of SiC powder, then ball milling is that coloring ion slurry is made；Slurry is poured into screen process press, and devitrified glass, which is put in wash the mantoquita and silver salt of excess surface off after silk-screen printing under silk screen plate, multi-steps sintering, produces coloring devitrified glass.According to devitrified glass color made from preparation method of the present invention it is various, rich in true and naturally coloring and visual effect, devitrified glass surface is smooth, attractive in appearance, adds the decorative effect of microcrystalline glass decorative plate, expands and use scope, added value of product is high.

Description

A kind of color method of devitrified glass
Technical field
The present invention relates to a kind of manufacture method of devitrified glass, more particularly to a kind of color method of devitrified glass.
Background technology
The basic performance of the existing glass of devitrified glass, the polycrystalline feature with ceramics has concentrated the spy of glass and ceramics Point, as the unique new material of a class.With its high mechanical strength, hardness is big, anti-wear performance is good, corrosion resistance is strong, with good Good chemical stability and heat endurance, adapts to rugged environment, has obtained quick development in the world in recent years.
At present, the maximum white and light crystallizing glass sheet material of devitrified glass usage amount.With people's living standard Improve, the demand to colour devitrified glass is increasing.And produce colour devitrified glass and typically first prepare stained glass water Quench material, then crystallization prepares colour devitrified glass again.Also there is a small amount of technique used as ceramic coloring, in the crystallite processed Glass surface carries out inkjet printing again, and the technique such as silk-screen printing is coloured to devitrified glass.These coloring process various colors, But to the infringement that the surface of devitrified glass is carried out, and the pigment and matrix devitrified glass adhesion of coloring are poor, are easily broken, Surface irregularity after technique coloring, follow-up cleaning technology is complicated.
(Li Yaohui, Cao builds luxuriant to Li Yaohui, and the such as Xu Bo vanadium, neodymium are to lithium silicon aluminum micro-crystal glass crystallization and influence [J] of coloring Rare Metals Materials and engineering, 2009,38 (2):1128-1132.) et al. introduce V2O5、Nd2O3To transparent Li2O-Al2O3-SiO2 (LAS) devitrified glass is coloured, and analyzes the influence of vanadium, neodymium ion to Crystallizing Process In System and tinctorial property.Guo Xingzhong (Guo The such as Xing Zhong, Yang Hui, Li Haimiao prepare Li containing colouring agent with fusion process2O-Al2O3-SiO2The coring of glass and crystallization [J] silicic acid Salt journal, 2007,35 (10):1390-1395.) et al. (Fe containing mixed colorant is prepared with fusion process2O3+Co2O3+Ni2O3) Li2O-Al2O3-SiO2(LAS) glass, as a result shows:Mixing coloring ion causes LAS glass in visible-range overlapping absorbance Aobvious black；The addition of colouring agent makes LAS devitrifications of glass peak temperature increase by 50~100 DEG C, and the crystallization peak temperature of high Co contents glass Degree is higher than the glass of high Ni contents, but colouring agent has substantially no effect on coring and the crystalline phase composition of LAS glass；Containing colouring agent The suitable nucleation temperature of LAS glass is 610 DEG C, and crystallization temperature is 900~930 DEG C.Xia Haiping (Xia Haiping, Zhang Jianli, Chen Hongbing Deng absorption spectrum [J] Acta Opticas of Colored Transparent Glass Ceramics, 2002,22 (7):878-881.) et al. in Li2O- Al2O3-SiO2A small amount of Nucleating Agent TiO is mixed in system glass2、ZrO2、P2O5, then mix rare earth ion and transition metal ions work For colouring agent, found obtain colour transparent glass at high temperature.Han Ronghui (Han Rong luxuriant growths .CaO-Al2O3-SiO2System color phosphorus slag Research [D] the Wuhan University of Technologys of devitrified glass composition, structure and performance, 2012.) develop the colored phosphorus slag crystallite of cas system Glass, improves the decorative effect of phosphorus slag devitrified glass.On the premise of fixed phosphorus slag volume is constant, by changing colorant assortment The influence to Structure of Glass Ceramic and performance is coloured with content system research hybrid ionic.High-performance have developed by Success in Experiment Ecru, green, grey phosphorus slag devitrified glass.(Yang Lan orchid transition metal oxides are to R by Yang Lanlan2O-CaO-SiO2- F systems Research [D] the Wuhan University of Technologys of system devitrified glass coloring mechanism, 2011.) prepared and fitted by experimental simulation material road coloring process The colorant of material road coloring, and diffusion velocity of the research colorant in canasite white glass liquid are closed, is prepared using stirring technique The colour devitrified glass of uniform coloring.The colorant is expected to be used for the material road coloring of canasite devitrified glass.In simulation material road In the experiment of color, the colour devitrified glass surface of preparation is without striped, and color and luster is soft homogeneous, with as top grade decoration panel material Potentiality.K is separately added into the batch of canasite system glass2Cr2O7And Co2O3Two kinds of colouring agents.Document above report Road is to be added in glass melting process after coloring, then prepares devitrified glass using method of piling, and the process colour is dull, and not Colorful pattern can be formed, application is narrow.
Guangdong Bode Jinggong Building Materials Co., Ltd's (glass-ceramic clad plate [Z] of illusion-colour abstract art style crystallization Guangdong Bode Jinggong Building Materials Co., Ltd .2011.) develop can increase crystallization amount and formed smeared out boundary devitrified glass melt Block, the distributing mode combined first using template and dry powder silk screen, createing a kind of pattern has illusion-colour abstract art style New product, and it is named as " Boulder Seiko jade auspicious cloud series ".Using polycrystalline microcrystalline glass formula and reduction devitrified glass grain Material granularity, the double action at increase crystallization interface, and utilize the coloring ion and the crystallite of composition for possessing different self-diffusion coefficients The mutual scattering and permeating of glass, forms the obfuscation, chaotization on devitrified glass different color border.Utilize based on template, dry powder Silk screen cloth and cloth it is uniform supplemented by process, manufacture provides the crystallizing glass sheet material of unique artistic picture scroll style. (Yang Liang improve the preparation process of microcrystalline stone of decorative effect to CN200610095280.4:China, CN200610095280.4 [P] .2007-6-6. a kind of preparation process of microcrystalline stone of improvement decorative effect) is provided, this method is in traditional microlite production technology On the basis of, cloth material process is improved, slurry or powder will be made for further crush of microlite pellet for decorating color, point Not by means of ceramic wall and floor bricks wet process glazing or dry powder stamp equipment technology, slurry or powder will be shifted in microlite bed material to enter Luggage is adornd, then crystallization, grinding and polishing cutting, so as to produce the microlite product that aesthetic effect is remarkable, products obtained therefrom and tradition Microlite compare have rich and varied, natural beauty lively pattern, ideally lifted microlite aesthetic effect. CN200810116886.0 (Beijing Jingya Stone Technology Co., Ltd..A kind of manufacture method of colored drawing crystallizing glass decoration board:In State, CN200810116886.0 [P] .2008-12-10.) disclose a kind of manufacture method of colored drawing crystallizing glass decoration board, institute Manufacture method is stated to comprise the following steps：(1) preparation of devitrified glass colorant；(2) the plain color devitrified glass after surface cleaning The devitrified glass colorant that sheet material is prepared with step (1) makes various patterns using manual colour painting and method for printing screen；(3) it will paint The colour devitrified glass decorative panel made enters electric furnace roasting；(4) product after firing is processed by shot blasting again.It utilizes high temperature Colorant, colour painting and method for printing screen draw a design on plain color crystallizing glass sheet material by hand.Taken again after calcining grinding and polishing Obtain colour devitrified glass dalle.CN201120367213.x (Foshan Shiwan Eagle-Brand Ceramic Co., Ltd.Once burn crystallite glass Glass composite brick:China, CN201120367213.X [P] .2012-5-30.) a kind of open once burning devitrified glass composite brick, Screen printing glaze layer, silk screen dry powder decorative layer and glass frit layer, the glass frit layer are laid on vitrified tile ceramic body successively Using methyl hydropexis, the silk screen dry powder decorative layer is made up of colorant dry powder in screen printing glaze layer of silk-screen printing.Should Product is using vitrified tile as main base substrate, and decorative intermediate layer enriches pattern decorative layer combination dry powder silk using multiple screen printing glazing Wire mark brush finish layer, it uses once-firing type, has the advantages that low energy consumption, low cost.CN02149626.9 (Nanhai City Qiao Dong Ceramic Co., Ltd.Micro Crystal galss wall floor brick decorating process and product:China, CN02149626.9 [P] .2004-6-30.) use Color pigments decorate devitrified glass burnishing surface by silk-screen printing, applique paper applique or Freehandhand-drawing mode, and decorating firing kiln is put into after drying Middle decoration firing, decoration firing temperature is 600~1100 DEG C, and the time is more than 2 hours, and product of the present invention is characterized in devitrified glass brick or multiple The decoration layer that enamel firing process is made is attached with the devitrified glass burnishing surface for closing devitrified glass brick.Document above is employed The coloring and decorating technology of traditional ceramics, prepared pattern enriches, but sintering temperature is high (being more than 600 DEG C), and all compromises micro- The original surface of crystal glass.
The content of the invention
It is an object of the invention to overcome the shortcoming of above-mentioned prior art there is provided one kind without high temperature sintering, color is rich Richness, the coloring devitrified glass of the original surface smoothness of devitrified glass is not damaged, and preparation technology is simple, and easy to operate, energy consumption is low, The energy is saved, suitable for the preparation method of the coloring devitrified glass of production in enormous quantities, according to crystallite made from preparation method of the present invention Glass color is various, rich true and naturally colours and visual effect, and devitrified glass surface is smooth, attractive in appearance, adds crystallite The decorative effect of glass decoration sheet material, expands and uses scope, and added value of product is high.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：
A kind of color method of 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% Sb2O3It is put into batch mixer to mix to the uniformity and is more than 98%, forms batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1450~ In 1500 DEG C of horse-shoe flame furnace, and 10~20h is founded at 1450~1500 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, segmentation is carried out and burns till：Finally, it is cooled to by 6~8h Room temperature；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing；
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：
First water, glycerine, gum arabic are put into beaker according to mass fraction and are uniformly mixed, then by its according to Mass ratio is added to AgNO3、Cu2O、FeSO4·7H2Be stirred in O, zinc powder, the compound of SiC powder, it is to be mixed it is uniform after, After the slurry is poured into ball grinder into ball milling 2~5 hours again, that is, prepare coloring ion slurry；
Then, coloring devitrified glass is prepared：
The coloring ion slurry made is poured into screen process press, devitrified glass prepared by the first step is put in silk screen plate Under, silk-screen printing is carried out, print thickness is 0.1~50 micron, enters to carry out multi-steps sintering in Muffle furnace after after slurry natural drying Afterwards, less than 50 DEG C are cooled to furnace temperature, take out after sample and wash the mantoquita and silver salt of excess surface off, produce coloring crystallite glass Glass.
Further, the SiO2, Al2O3, CaO, MgO, Na2O, K2O, TiO2, ZrO2, B2O3, ZnO, Fe2O3, Sb2O3Respectively By raw material of industry quartz, aluminum oxide, calcite, dolomite, sodium carbonate, potassium carbonate, titanium dioxide, zirconium oxide, borax, oxidation Zinc, iron oxide red, antimony powder is introduced, and granularity is more than 80 mesh.
Further, the first step step 7) in segmentation burn till to begin through 1~3h from room temperature and be warming up to 150 DEG C；So Afterwards 680 DEG C are warming up to from 150 DEG C of 2~3h of process；Then 1080~1120 DEG C are warming up to from 680 DEG C of 3~4h of process, and are incubated 1 ~3h；Then 820 DEG C are cooled to from 1080~1120 DEG C of 3~4h of process；Then 650 DEG C are cooled to from 820 DEG C of 1~2h of process, And it is incubated 1~2h.
Further, the devitrified glass is shaped as tabular, curved surface, arc or circle.
Further, the coloring ion diffusion slurry is prepared from according to the raw material of following mass ratioes：
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, the second step multi-steps sintering is to be raised to 300 DEG C, insulation 20 from room temperature with 3~5 DEG C/min speed Minute；450~550 DEG C are warming up to 5~10 DEG C/min speed again, 10~60 minutes are incubated.
The present invention is coloured using ion diffusion color method to devitrified glass, and the surface of devitrified glass is not damaged.Ion expands Scattered process is carried out in atmosphere, without handling under the reducing conditions.Devitrified glass surface after coloring is smooth, adds micro- The visual effect and decorative effect of crystal glass.It is various, rich true according to devitrified glass color made from preparation method of the present invention Coloured and visual effect with natural, devitrified glass surface is smooth, attractive in appearance, add the decoration effect of microcrystalline glass decorative plate Really, expand and use scope, added value of product is high.
Embodiment
Below in conjunction with the embodiment of the present invention, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
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 Enter to mix in batch mixer to the uniformity and be more than 98%, form batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1500 DEG C Horse-shoe flame furnace in, and found 10h at 1500 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：1h is begun through from room temperature It is warming up to 150 DEG C；Then 680 DEG C are warming up to by 2h from 150 DEG C；Then 1080 DEG C are warming up to by 3h from 680 DEG C, and be incubated 3h；Then 820 DEG C are cooled to by 4h from 1080 DEG C；Then 650 DEG C are cooled to by 2h from 820 DEG C, and are incubated 2h；Finally, Room temperature is cooled to by 8h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein AgNO3： Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder：SiC powder=7：10：5：8：15：2：1：1 mass ratio.Wait to stir Mix it is uniform after, then the slurry poured into ball milling in ball grinder prepare coloring ion slurry after 5 hours；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 10 microns, is entered after after slurry natural drying in Muffle furnace, with 3 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 550 DEG C again with 10 DEG C/min speed, after insulation 10 minutes with Furnace temperature is cooled to less than 50 DEG C, takes out after sample and washes the mantoquita and silver salt of excess surface off, produces 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% Sb2O3It is put into mixed Mixed in material machine to the uniformity and be more than 98%, form batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1480 DEG C Horse-shoe flame furnace in, and found 12h at 1480 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：2h is begun through from room temperature It is warming up to 150 DEG C；Then 680 DEG C are warming up to by 2h from 150 DEG C；Then 1100 DEG C are warming up to by 4h from 680 DEG C, and be incubated 1h；Then 820 DEG C are cooled to by 4h from 1100 DEG C；Then 650 DEG C are cooled to by 1h from 820 DEG C, and are incubated 1h；Finally, Room temperature is cooled to by 8h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein AgNO3： Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder：SiC powder=6：12：5：8：12：4：2：2 mass ratio, waits to stir Mix it is uniform after, then the slurry poured into ball milling in ball grinder prepare coloring ion slurry after 2 hours；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 20 microns, is entered after after slurry natural drying in Muffle furnace, with 4 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 510 DEG C again with 8 DEG C/min speed, after insulation 40 minutes with Furnace temperature, which is cooled to after less than 50 DEG C, taking-up sample and washes the mantoquita and silver salt of excess surface off, produces red coloration devitrified glass.
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% Sb2O3It is put into batch mixer and mixes It is more than 98% to the uniformity, forms batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1460 DEG C Horse-shoe flame furnace in, and found 15h at 1460 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：Begun through from room temperature 1.5h is warming up to 150 DEG C；Then 680 DEG C are warming up to by 2.5h from 150 DEG C；Then 1120 are warming up to by 3.5h from 680 DEG C DEG C, and it is incubated 1h；Then 820 DEG C are cooled to by 3h from 1120 DEG C；Then 650 DEG C are cooled to by 2h from 820 DEG C, and be incubated 2h；Finally, it is cooled to room temperature by 8h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein AgNO3： Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder=4：9：5：7：12：3：1 mass ratio, it is to be mixed it is uniform after, The slurry is poured into ball milling in ball grinder again and prepares coloring ion slurry after 3 hours；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 30 microns, is entered after after slurry natural drying in Muffle furnace, with 5 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 450 DEG C again with 10 DEG C/min speed, after insulation 60 minutes with Furnace temperature, which is cooled to after less than 50 DEG C, taking-up sample and washes the mantoquita and silver salt of excess surface off, produces yellow microcrystalline glass.
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% Sb2O3It is put into Mixed in batch mixer to the uniformity and be more than 98%, form batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1450 DEG C Horse-shoe flame furnace in, and found 20h at 1450 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：3h is begun through from room temperature It is warming up to 150 DEG C；Then 680 DEG C are warming up to by 3h from 150 DEG C；Then 1080 DEG C are warming up to by 4h from 680 DEG C, and be incubated 3h；Then 820 DEG C are cooled to by 4h from 1080 DEG C；Then 650 DEG C are cooled to by 2h from 820 DEG C, and are incubated 2h；Finally, Room temperature is cooled to by 6h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein AgNO3： Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder：SiC powder=6：6：5：7：10：1：1：1 mass ratio, waits to stir Mix it is uniform after, then the slurry poured into ball milling in ball grinder prepare coloring ion slurry after 3 hours；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 50 microns, is entered after after slurry natural drying in Muffle furnace, with 5 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 550 DEG C again with 10 DEG C/min speed, after insulation 60 minutes with Furnace temperature, which is cooled to after less than 50 DEG C, taking-up sample and washes the mantoquita and silver salt of excess surface off, produces brown devitrified glass.
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% Sb2O3It is put into Mixed in batch mixer to the uniformity and be more than 98%, form batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1480 DEG C Horse-shoe flame furnace in, and found 15h at 1480 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：3h is begun through from room temperature It is warming up to 150 DEG C；Then 680 DEG C are warming up to by 2h from 150 DEG C；Then 1120 DEG C are warming up to by 4h from 680 DEG C, and be incubated 2.5h；Then 820 DEG C are cooled to by 4h from 1120 DEG C；Then 650 DEG C are cooled to by 2h from 820 DEG C, and are incubated 2h；Most Afterwards, it is cooled to room temperature by 7h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein AgNO3： Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder：SiC powder=2：8：5：8：15：5：2：2 mass ratio, waits to stir Mix it is uniform after, then the slurry poured into ball milling in ball grinder prepare coloring ion slurry after 4 hours；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 50 microns, is entered after after slurry natural drying in Muffle furnace, with 5 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 550 DEG C again with 10 DEG C/min speed, after insulation 60 minutes with Furnace temperature, which is cooled to after less than 50 DEG C, taking-up sample and washes the mantoquita and silver salt of excess surface off, produces red coloration devitrified glass.
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 Enter to mix in batch mixer to the uniformity and be more than 98%, form batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1450 DEG C Horse-shoe flame furnace in, and found 10h at 1450 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：1h is begun through from room temperature It is warming up to 150 DEG C；Then 680 DEG C are warming up to by 2h from 150 DEG C；Then 1080 DEG C are warming up to by 4h from 680 DEG C, and be incubated 3h；Then 820 DEG C are cooled to by 4h from 1080 DEG C；Then 650 DEG C are cooled to by 2h from 820 DEG C, and are incubated 1h；Finally, Room temperature is cooled to by 8h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein AgNO3： Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder：SiC powder=10：3：3：5：15：5：2：2 mass ratio, waits to stir Mix it is uniform after, then the slurry poured into ball milling in ball grinder prepare coloring ion slurry after 5 hours；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 50 microns, is entered after after slurry natural drying in Muffle furnace, with 5 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 510 DEG C again with 10 DEG C/min speed, after insulation 40 minutes with Furnace temperature, which is cooled to after less than 50 DEG C, taking-up sample and washes the mantoquita and silver salt of excess surface off, produces coloring devitrified glass.
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 Enter to mix in batch mixer to the uniformity and be more than 98%, form batch；
2) then, well mixed batch is homogeneously added into by inclined blanket type batcher and has been warming up to 1450 DEG C Horse-shoe flame furnace in, and found 10h at 1450 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal to pass through orifice ring, stream Enter in the pond below feeder channel；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, stone Thickness 5cm；
7) then, sample is pushed into kiln together with mould, burnt till according to following technique：1h is begun through from room temperature It is warming up to 150 DEG C；Then 680 DEG C are warming up to by 2h from 150 DEG C；Then 1080 DEG C are warming up to by 4h from 680 DEG C, and be incubated 3h；Then 820 DEG C are cooled to by 4h from 1080 DEG C；Then 650 DEG C are cooled to by 2h from 820 DEG C, and are incubated 1h；Finally, Room temperature is cooled to by 8h；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing.
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：Water, glycerine, gum arabic are first put into stirring mixing in beaker equal It is even, it is then added into AgNO3、Cu2O、FeSO4·7H2It is stirred in O, zinc powder, the compound of SiC powder, wherein Cu2O： FeSO4·7H2O：Water：Glycerine：SiC powder=15：4：5：8：2 mass ratio, it is to be mixed it is uniform after, then the slurry poured into ball milling Ball milling prepares coloring ion slurry after 5 hours in tank；
Then, coloring devitrified glass is prepared：The slurry made is poured into screen process press, the devitrified glass of preparation is put In under silk screen plate, carrying out silk-screen printing, print thickness is 50 microns, is entered after after slurry natural drying in Muffle furnace, with 5 DEG C/min Speed be raised to 300 DEG C from room temperature, be incubated 20 minutes；Be warming up to 510 DEG C again with 10 DEG C/min speed, after insulation 40 minutes with Furnace temperature, which is cooled to after less than 50 DEG C, taking-up sample and washes the mantoquita and silver salt of excess surface off, produces coloring devitrified glass.
The present invention is coloured using ion diffusion color method to devitrified glass, and the surface of devitrified glass is not damaged.After coloring Devitrified glass surface it is smooth, with shock resistance, corrosion-resistant, smooth and beautiful appearance, insulation, it is heat-resisting the features such as, add simultaneously The visual effect and decorative effect of devitrified glass.Devitrified glass color prepared by the inventive method is various, rich true and natural Coloring and visual effect, and easy to operate, preparation technology is simple, and energy consumption is low, saves the energy, suitable for large-batch industrial life Production, good decorating effect, added value of product is high.
Although it is understood that the present invention is disclosed as above with preferred embodiment, but above-described embodiment and being not used to Limit the present invention.For any those skilled in the art, without departing from the scope of the technical proposal of the invention, The technology contents that may be by the disclosure above make many possible variations and modification to technical solution of the present invention, or are revised as The equivalent embodiment of equivalent variations.Therefore, every content without departing from technical solution of the present invention, the technical spirit according to the present invention To any simple modifications, equivalents, and modifications made for any of the above embodiments, the model of technical solution of the present invention protection is still fallen within In enclosing.

Claims (6)

1. a kind of color method of devitrified glass, it is characterised in that comprise 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% Sb2O3It is put into batch mixer to mix to the uniformity and is more than 98%, forms batch；
2) then, well mixed batch is homogeneously added into and has been warming up to 1450~1500 DEG C of horse-shoe flame furnace In, and 10~20h is founded at 1450~1500 DEG C, obtain glass metal；
3) glass metal gradually then, is cooled to 1200 DEG C by supply channel；
4) then, when glass metal is flowed at revolving sleeve, by controlling the height of revolving sleeve to allow glass metal by orifice ring, flow into and supply In pond below hopper；
5) then, the glass disintegrating slag in tank is pulled out, air-dried；
6) glass disintegrating slag then, is even added into inner surface to be affixed with the mullite mould of ceramic fiber paper, layer thickness 5cm；
7) then, sample is pushed into kiln together with mould, segmentation is carried out and burns till：Finally, it is cooled to room by 6~8h Temperature；
8) specimen surface both finally, is obtained into devitrified glass by sanding and polishing；
Second step：Colour the preparation of enamel
First, coloring ion diffusion slurry is prepared：
First water, glycerine, gum arabic are put into beaker according to mass fraction and be uniformly mixed, then by it according to quality Than being added to AgNO3、Cu2O、FeSO4·7H2Be stirred in O, zinc powder, the compound of SiC powder, it is to be mixed it is uniform after, then will The slurry pours into ball milling in ball grinder and after 2~5 hours, that is, prepares coloring ion slurry；
Then, coloring devitrified glass is prepared：
The coloring ion slurry made is poured into screen process press, devitrified glass prepared by the first step is put under silk screen plate, Silk-screen printing is carried out, print thickness is 10~50 microns, enters after slurry is spontaneously dried in Muffle furnace and carries out after multi-steps sintering, with Furnace temperature is cooled to less than 50 DEG C, takes out after sample and washes the mantoquita and silver salt of excess surface off, produces coloring devitrified glass.
2. the color method of devitrified glass according to claim 1, it is characterised in that：The SiO2, Al2O3, CaO, MgO, Na2O, K2O, TiO2, ZrO2, B2O3, ZnO, Fe2O3, Sb2O3Respectively by raw material of industry quartz, aluminum oxide, calcite, white clouds Stone, sodium carbonate, potassium carbonate, titanium dioxide, zirconium oxide, borax, zinc oxide, iron oxide red, antimony powder is introduced, and granularity is more than 80 mesh.
3. the color method of devitrified glass according to claim 1, it is characterised in that：The first step step 7) middle segmentation Burn till to begin through 1~3h from room temperature and be warming up to 150 DEG C；Then 680 DEG C are warming up to from 150 DEG C of 2~3h of process；Then certainly 680 DEG C of 3~4h of process are warming up to 1080~1120 DEG C, and are incubated 1~3h；Then from 1080~1120 DEG C of 3~4h of process coolings To 820 DEG C；Then 650 DEG C are cooled to from 820 DEG C of 1~2h of process, and are incubated 1~2h.
4. the color method of devitrified glass according to claim 1, it is characterised in that：The devitrified glass is shaped as flat board Shape, curved surface, arc or circle.
5. the color method of devitrified glass according to claim 1, it is characterised in that：The coloring ion spreads slurry Raw material according to following mass ratioes is prepared from：
AgNO3：Cu2O：FeSO4·7H2O：Water：Glycerine：Gum arabic：Zinc powder：SiC powder=2~10：3~15：3~5：5~ 8：8~15：0~5：0~2：0~2.
6. the color method of devitrified glass according to claim 1, it is characterised in that：The second step multi-steps sintering is, 300 DEG C are raised to from room temperature with 3~5 DEG C/min speed, 20 minutes are incubated；450 are warming up to 5~10 DEG C/min speed again~ 550 DEG C, it is incubated 10~60 minutes.
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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
CN108083636B (en) * 2017-11-17 2020-10-30 泉州台商投资区钰宝商贸有限公司 Imitation Yuhua stone
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CN109678362B (en) * 2019-03-07 2022-04-22 科立视材料科技有限公司 Ion diffusion coloring agent and application thereof
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