CN106396741A - Ceramic tile with mineral crystal fancy glaze layer and preparation method thereof - Google Patents

Ceramic tile with mineral crystal fancy glaze layer and preparation method thereof Download PDF

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Publication number
CN106396741A
CN106396741A CN201610789135.XA CN201610789135A CN106396741A CN 106396741 A CN106396741 A CN 106396741A CN 201610789135 A CN201610789135 A CN 201610789135A CN 106396741 A CN106396741 A CN 106396741A
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China
Prior art keywords
parts
layer
glaze
mineral crystal
fancy glaze
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CN201610789135.XA
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CN106396741B (en
Inventor
钟礼丰
李德英
喻劲军
吴滨
谭静雯
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GUANGDONG KITO CERAMICS CO Ltd
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GUANGDONG KITO CERAMICS CO Ltd
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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/89Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • 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
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation

Abstract

The invention provides a ceramic tile with a mineral crystal fancy glaze layer and a preparation method thereof. The ceramic tile with the mineral crystal fancy glaze layer comprises a blank layer, a printing layer, a protection fancy glaze layer and the mineral crystal fancy glaze layer from bottom to top. The mineral crystal fancy glaze layer is formed by arranging a mineral crystal fancy glaze. The mineral crystal fancy glaze comprises, by mass, 100 parts of a mineral crystal dry granule, 0-50 parts of a clear glaze, 60-80 parts of printing paste, 0.2 part of carboxymethylcellulose and 25-40 parts of water. The mineral crystal dry granule comprises, by oxide weight, 8 parts of SiO2, 3 parts of Al2O3, 20 parts of B2O3, 9 parts of Fe2O3, 46 parts of MnO and 8 parts of TiO2. The ceramic tile is provided with the mineral crystal fancy glaze layer and can show the rich natural mineral crystal texture effect, and the decoration texture similar to natural stone is obtained.

Description

A kind of Ceramic Tiles with mineral crystal fancy glaze layer and preparation method thereof
Technical field
The present invention relates to architectural pottery production field, more particularly, to a kind of Ceramic Tiles with mineral crystal fancy glaze layer and its Preparation method.
Background technology
Glaze decorating is the common approach of Ceramic Tiles decoration, and having mineral crystal decorated is the emphasis that people research and develop, But prior art obtains crystallize effect glaze and mainly obtains crystallize effect by using substantial amounts of zinc oxide, but uses zinc oxide The single effect of the brilliant flower obtaining, and color also based on greyish white it is impossible to the mineral crystal grain decorating of simulation nature stone material Effect.
Similar effect can be obtained by way of stamp, but relatively dull decorative effect also makes it cannot simulate The rich and changeful grain effect of natural stone material.
Content of the invention
The present invention is directed to the technical problem propose in prior art, and the present invention provides a kind of has mineral crystal fancy glaze layer Ceramic Tiles, it includes from the bottom to top:Green body layer, printed layer, protection fancy glaze layer and mineral crystal fancy glaze layer, described mineral crystal flower Glaze layer is formed by charity mineral crystal fancy glaze, and described mineral crystal fancy glaze is calculated with mass fraction, including following component:Mineral 100 parts of crystal dry granular, clear frit 0-50 part, print cream 60-80 part, 0.2 part of carboxymethyl cellulose, water 25-40 part, described mineral are brilliant The chemical constituent of soma grain is calculated with oxide weight number, including following component:SiO2:8 parts, Al2O3:3 parts, B2O3:20 parts, Fe2O3:9 parts, MnO:46 parts, TiO2:8 parts.
Here clear frit known to clear frit Ceramics production.Contain in the mineral crystal dry granular that the present invention provides Substantial amounts of ferrum, manganese and titanium elements, under different firing conditions and have multiple change under base glaze component, particularly with apply In the mode of glaze and/or printing ornament combination, because its fusing point is relatively low, how can be formed down depression, so also reduce follow-up rubbing down The abrasion to it for the processing.
Preferably, before charity mineral crystal fancy glaze on Ceramic Tiles base substrate, stamp and charity protection are first carried out on base substrate Fancy glaze, protection fancy glaze is known clear frit here.Here clear frit preferably has higher hardness, further illustrates, and preferably adopts Printed with the thickening effect net of 60 mesh.Mineral crystal fancy glaze can be melted with following glaze after high temperature sintering Close, form nested brilliant flower decorative effect.
Preferably, in above-mentioned Ceramic Tiles, between green body layer and printed layer, it is additionally provided with cover coat.
Preferably, in above-mentioned Ceramic Tiles, it is additionally provided between green body layer and printed layer and brightens layer, brightening layer is by charity Brighten glaze formation, brighten glaze and calculated with mass fraction, it includes following component:Clear frit:50 parts, Zirconium orthosilicate.:50 Part, print cream:65 parts, sodium tripolyphosphate:0.3 part, water:35 parts;
The chemical constituent of described clear frit is calculated with oxide weight number, including following component:
Na2O:5 parts, CaO:9 parts, ZnO:8 parts, Al2O3:8 parts, B2O3:2 parts, SiO2:60 parts.
The present invention also provides the preparation method of the above-mentioned Ceramic Tiles with mineral crystal fancy glaze layer, and it comprises the steps:
Step 1) make adobe from known ceramic body powder punching press;
Step 2) on brightening layer, decalcomania layer is formed using known stamp mode;
Step 3) charity protection fancy glaze in decalcomania layer, form protection fancy glaze layer, described protection fancy glaze is known Clear frit;
Step 4) charity mineral crystal fancy glaze on protection fancy glaze layer, form mineral crystal fancy glaze layer, described mineral crystal Fancy glaze is calculated with mass fraction, including following component:100 parts of mineral crystal dry granular, clear frit 0-50 part, print cream 60-80 part, carboxylic 0.2 part of methylcellulose, water 25-40 part, the chemical constituent of described mineral crystal dry granular is calculated with oxide weight number, including Following component:SiO2:8 parts, Al2O3:3 parts, B2O3:20 parts, Fe2O3:9 parts, MnO:46 parts, TiO2:8 parts;
Step 5) enter kiln and fire;
Step 6) base substrate after burning till is polished and edging process, obtain ceramic brick product.
Preferably, step 1) and step 2) between also include printing and brighten the step that layer is brightened in glaze formation, the increasing of use The component of white glaze material is calculated with mass fraction, including following component:Clear frit:50 parts, Zirconium orthosilicate.:50 parts, print cream:65 parts, Sodium tripolyphosphate:0.3 part, water:35 parts;
The chemical constituent of described clear frit is calculated with oxide weight number, including following component:
Na2O:5 parts, CaO:9 parts, ZnO:8 parts, Al2O3:8 parts, B2O3:2 parts, SiO2:60 parts.
Preferably, in above-mentioned preparation method, printing number of times >=2 time brightening glaze are printed.
Preferably, in above-mentioned preparation method, step 5) firing temperature be 1175~1185 DEG C, firing period is 60~ 70min.
Compared to the prior art, the Ceramic Tiles that the present invention provides have mineral crystal fancy glaze layer, and it can assume abundant sky So grain effect of mineral crystal, obtains the decoration texture of similar lithotome.And be combined with printing technology, more can obtain abundant Nested grain effect.
Brief description
Fig. 1 is the sectional view of the Ceramic Tiles that the embodiment of the present invention 1 provides;
Fig. 2 is the sectional view of the Ceramic Tiles that the embodiment of the present invention 2 provides;
Fig. 3 is the sectional view of the Ceramic Tiles that the embodiment of the present invention 3 provides;
Fig. 4 is the sectional view of the Ceramic Tiles that a preferred embodiment of the invention provides;
Fig. 5 is the sectional view of the Ceramic Tiles that the embodiment of the present invention 4 provides;
Fig. 6 is the sectional view of the Ceramic Tiles that the embodiment of the present invention 5 provides.
Description of reference numerals:1- green body layer;2- cover coat;3- brightens layer;4- decalcomania layer;5- increases pink blossom glaze layer;6- Help color fancy glaze layer;7- protects fancy glaze layer;8- mineral crystal fancy glaze layer.
Specific embodiment
Below by accompanying drawing and some embodiments, this patent to be described.It is to be appreciated that the following drawings is merely illustrative, Do not draw in strict accordance with ratio, under projecting some technical characteristics, have zooming in or out of local.
Embodiment 1
Referring to the drawings 1, the present embodiment provide a kind of there are the Ceramic Tiles brightening layer, it includes from the bottom to top:Green body layer 1, Cover coat 2, brighten layer 3 and decalcomania layer 4, brightening layer 3 is to brighten glaze by silk screen printing to be formed, and brightens the thickness of layer 3 Spend for 0.2-1.2mm.
Its preparation method is as follows:
Step 1) make adobe from known ceramic body powder punching press;
Step 2) billet surface by drench glaze by way of cover-coat enamel known to charity, formed cover coat;
Step 3) printed on cover coat using silk screen printing mode and brighten glaze, formed and brighten layer;
Step 4) on brightening layer, printed layer is formed using known stamp mode;
Step 5) enter kiln and fire;
Step 6) base substrate after burning till is polished and edging process, obtain ceramic brick product.
Wherein, the blank formulation in described step 1 is the body recipe of common glazed ceramic brick, provides an example here The formula of property.For ensureing the flatness of product and ripple glaze deformation, base substrate aluminum content 21% about, whiteness at 35 degree about, It is as follows that its formula presses mass fraction:Yichuan sand:20 parts, Ganzhou low temperature potassium sodium sand:15 parts, mud is washed in Qianshan:16~20 parts, Guangxi White mud:8 parts, 3 parts of the white mud in Ji'an, Guangchang potassium sand:31 parts, Fuzhou City's bentonite:1 part, black talc:2~3 parts.Using wet ball grinding Mode, Ball-milling Time 11~12 hours;After slurry fineness was 250 mesh sieves, tail over as 1.6~2.0 grams;Blank moisture content is 6 ~6.5%, its grain composition:More than 20 mesh 0~1.5%, -20~+40 mesh 30~60%, -20~+60 mesh 72~88%, 100 0~6% below mesh, remaining is -60~+100 mesh.
Cover-coat enamel formula is to ensure product sintering temperature, brick, the common porcelain glazed ceramic brick of effect fancy glaze stereoeffect Conventional cover-coat enamel, as follows by mass fraction:Potassium feldspar:25 parts, quartz:15~30 parts, nepheline:15~25 parts, calcined kaolin: 7 parts, aluminium oxide:10 parts, wollastonite:4 parts, zinc oxide:1 part, Zirconium orthosilicate.:20 parts, CNH00058:10~15 parts, sodium humate: 0.2, carboxymethyl cellulose:0.2 part, sodium tripolyphosphate:0.15 part, by the way of wet ball grinding, ball milling 4~5 hours;Cover-coat enamel Proportion 1.75~1.85g/cm3, the flow velocity 30-35 second, after crossing 325 mesh sieves, tail over as 3~4 grams.Cover-coat enamel covers to base substrate, Reduce the impact to glaze paint for the impurity in base substrate.
Brighten glaze, it is calculated with mass fraction, and it includes following component:Clear frit:50 parts, Zirconium orthosilicate.:50 parts, print Cream:65 parts, sodium tripolyphosphate:0.3 part, water:35 parts;
The chemical constituent of described clear frit is calculated with oxide weight number, including following component:
Na2O:5 parts, CaO:9 parts, ZnO:8 parts, Al2O3:8 parts, B2O3:2 parts, SiO2:60 parts.
Here Zirconium orthosilicate. is to brighten Main Ingredients and Appearance, and it is coordinated with the clear frit of speciality, adjusts it using print cream Printing effect, to reach the effect that base substrate is preferably brightened.Here print cream is the print of commercially available traditional regulation glaze charity effect Cream, its exemplary group is divided into, and calculates according to the mass fraction:Methyl:1.3 parts, ethylene glycol:35 parts, water:35 parts, preservative:0.001 Part.This brightens glaze, and using clear frit and Zirconium orthosilicate. as Main Ingredients and Appearance, wherein clear frit is to firing temperature and sintering effect It is adjusted, Zirconium orthosilicate. is brightened, combined by both, on the premise of production cost is relatively low, so that the base substrate after burning is had Higher whiteness, and can be with effective control blank deformation by way of screen printing.
Embodiment 2
Referring to the drawings 2, a kind of Ceramic Tiles, it includes from the bottom to top:Green body layer 1, cover coat 2, brighten layer 3, decalcomania Layer 4 and increasing pink blossom glaze layer 5.
Here form the increasing pink blossom glaze increasing pink blossom glaze layer 5 with mass fraction calculating, including following component:High boron is calcareous transparent Frit:12 parts, complementary color colorant 0.1-10 part, carboxymethyl cellulose:1.3 parts, ethylene glycol:45 parts, water:40 parts;
The chemical constituent of the calcareous clear frit of described high boron is calculated with oxide weight number, including following component:Na2O: 6 parts, CaO:12 parts, ZnO:7 parts, B2O3:8 parts, Al2O3:3 parts, SiO2:54 parts;
Described complementary color colorant is one or more combination of known pottery glaze stain.
Preparation method, increases the step that charity increases pink blossom glaze on the basis of embodiment 1.
It is to be appreciated that cover coat 2 and brighten layer 3 and can not carry out charity here, the ceramic brick product effect certainly obtaining Corresponding decline.
The charity thickness increasing pink blossom glaze layer is 0.2-0.8mm.
Embodiment 3
Referring to the drawings 3, a kind of Ceramic Tiles, it includes from the bottom to top:Green body layer 1, cover coat 2, brighten layer 3, decalcomania Layer 4 and help color fancy glaze layer 6.
Here formed and help the color fancy glaze that helps of color fancy glaze layer 6 to calculate with mass fraction, including following component:Including such as the following group Point:100 parts of high zinc matter frit, prints 130 parts of cream, 0.3 part of sodium tripolyphosphate, 40 parts of water;
The chemical constituent of described high zinc matter frit is calculated with oxide weight number, including following component:
SiO2:53 parts, ZnO:21 parts, K2O:4 parts, Al2O3:7 parts, MgO:3 parts, CaO:3.5 part.
It is to be appreciated that cover coat 2 and brighten layer 3 and can not carry out charity here, the ceramic brick product effect certainly obtaining Corresponding decline.It is, of course, also possible in decalcomania layer 4 and helping between color fancy glaze layer 6 and also to include increasing pink blossom glaze layer 5, its structure is such as Accompanying drawing 4.
The thickness helping color fancy glaze layer is 0.2-0.8mm.
Embodiment 4
Referring to the drawings 5, in the present embodiment, in one layer of protection fancy glaze of billet surface charity, form protection fancy glaze layer 7, this In protection fancy glaze be known clear frit.
Certainly, need exist for illustrating, protection fancy glaze layer 7 charity is on decalcomania layer 4.
Embodiment 5
Referring to the drawings 6, the present embodiment provides a preferred embodiment of the invention in detail, a kind of Ceramic Tiles, and it is by lower Structure be:Including green body layer 1, cover coat 2, brighten glaze layer 3, decalcomania layer 4, increase pink blossom glaze layer 5, help color fancy glaze layer 6, Protection glaze layer 7 and mineral crystal fancy glaze layer 8.
Its preparation technology comprises the steps:
The present invention also provides a kind of production technology of Ceramic Tiles, and it comprises the steps:
Step 1) base raw material through dispensing, ball milling be obtained slurry, then remove ferrum, sieve, old, powder by spraying after sieve, Prepared blank;
Step 2) by press, blank is pressed, prepare base substrate;
Step 3) base substrate is put into dry kiln it is dried;
Step 4) carry out charity cover-coat enamel by the way of drenching glaze;
Step 5) glaze is brightened using silk screen printing brightened;
Step 6) carry out decorating stamp by ink-jet printing apparatus;
Step 7) color that pink blossom glaze compensates needs reinforcement is increased by silk screen printing;
Step 8) help color fancy glaze to help color development by silk screen printing;
Step 9) protect glaze layer that ink-jetting pattern is protected by silk screen printing;
Step 10) pass through silk screen printing mineral crystal fancy glaze;
Step 11) enter kiln and be fired;
Step 12) polishing;
Step 13) edging, quality inspection, packaging obtain final product.
Wherein, the blank formulation in described step 1 is the body recipe of common glazed ceramic brick, provides an example here The formula of property.For ensureing the flatness of product and ripple glaze deformation, base substrate aluminum content 21% about, whiteness at 35 degree about, It is as follows that its formula presses mass fraction:Yichuan sand:20 parts, Ganzhou low temperature potassium sodium sand:15 parts, mud is washed in Qianshan:16~20 parts, Guangxi White mud:8 parts, 3 parts of the white mud in Ji'an, Guangchang potassium sand:31 parts, Fuzhou City's bentonite:1 part, black talc:2~3 parts.Using wet ball grinding Mode, Ball-milling Time 11~12 hours;After slurry fineness was 250 mesh sieves, tail over as 1.6~2.0 grams;Blank moisture content is 6 ~6.5%, its grain composition:More than 20 mesh 0~1.5%, -20~+40 mesh 30~60%, -20~+60 mesh 72~88%, 100 0~6% below mesh, remaining is -60~+100 mesh.
Baking temperature in step 3 is 100~160 DEG C, and arid cycle is 50~70min.Drying is to remove base substrate In unnecessary moisture content, this guarantee product quality, be typically dried process.
Cover-coat enamel formula in step 4 is to ensure product sintering temperature, brick, the common ceramic glaze of effect fancy glaze stereoeffect The conventional cover-coat enamel of surface ceramic tile, as follows by mass fraction:Potassium feldspar:25 parts, quartz:15~30 parts, nepheline:15~25 parts, forge Burn Kaolin:7 parts, aluminium oxide:10 parts, wollastonite:4 parts, zinc oxide:1 part, Zirconium orthosilicate.:20 parts, CNH00058:10~15 parts, Sodium humate:0.2, carboxymethyl cellulose:0.2 part, sodium tripolyphosphate:0.15 part, by the way of wet ball grinding, ball milling 4~5 Hour;Cover-coat enamel proportion 1.75~1.85g/cm3, the flow velocity 30-35 second, after crossing 325 mesh sieves, tail over as 3~4 grams.Cover-coat enamel is to base substrate Covered, reduced the impact to glaze paint for the impurity in base substrate.
Brighten fancy glaze in described step 5,80 mesh full impregnated nets are printed using silk-screen printing technique, print twice brighten fancy glaze, burn After one-tenth, in 60-68 degree, Yin Sandao brightens fancy glaze to finished product whiteness, and in 72-78 degree, Yin Sidao brightens fancy glaze to finished product whiteness, and finished product is white Degree is in 80-83 degree.Brighten fancy glaze as follows by mass fraction:Clear frit:50 parts, Zirconium orthosilicate.:50 parts, print cream:65 parts, trimerization phosphorus Sour sodium:0.3 part, water:35 parts.The glaze slip using after ball milling needs to reach following requirement:325 mesh sieves tail over 0.05-0.1%, than 1.55-1.58 gram/cc of weight.The composition of clear frit is following (calculating of oxide mass number):Na2O:5 parts, CaO:9 Part, ZnO:8,Al2O3:8 parts, B2O3:2 parts, SiO2:60 parts.Print cream is that common fancy glaze print cream (is chosen as Dow in the present embodiment The DS4003 of science and technology), it is counted as point as follows according to the mass fraction:Carboxymethyl cellulose:1.3 parts, ethylene glycol:35 parts, water:35 parts, Preservative:0.001 part.
Brighten mode in view of glaze for glazed tile, can by improve base substrate whiteness and raising cover-coat enamel whiteness reach similar Effect, brightens mode around these three in experimentation and does a lot of work.
The serial example 1 of contrast:Under the experiment condition of fixing step 2,3,4,5,6,7,8,9,10,11,12,13, only to step Base substrate whiteness in rapid 1 is adjusted, and draws following table:
Base substrate finished product whiteness Formulation cost
19-22 degree 140-180 yuan/ton
30-35 degree 280-300 yuan/ton
35-40 degree 320-380 yuan/ton
40-45 degree 420-480 yuan/ton
45-50 degree 520-550 yuan/ton
80 degree Do not reach
Base substrate is the basis of product, and its deformation has a direct impact to follow-up finished product glacing flatness and ripple glaze, by adopting Selected raw material can improve finished product whiteness to a certain extent, but raw material is required too high.Also indivedual enterprises are had to be to reach in industry To preferable base substrate whiteness, to be realized by slow burning (reducing more than half yield), thus can relax to base substrate composition Require, the problems such as without excessively considering the deformation producing due to due to base substrate composition, a large amount of blank raw materials using high whiteness, But because yield is too low, cost input is too big, also do not reach preferable whiteness simultaneously.Adjust the mode of whiteness using body recipe Sexual valence is poor.
The serial example 2 of contrast:Under the experiment condition of fixing step 1,2,3,5,6,7,8,9,10,11,12,13, only to step Cover-coat enamel formula in rapid 4 is adjusted, simultaneously remaining component in fixing step 4, only the Zirconium orthosilicate. to impact whiteness most critical Number be adjusted, draw following table:
Because the coefficient of expansion of Zirconium orthosilicate. is less, if excessive add the deformation that can have a strong impact on product in cover-coat enamel so that producing Product increasingly encircle with the increase adding Zirconium orthosilicate. amount, product.Simultaneously in cover-coat enamel after addition is a certain amount of, the impact to whiteness is got over Come weaker, and the glaze volume of cover-coat enamel is relatively thick, so this scheme is also with high costs in the case of not reaching preferable whiteness, But comparatively brightened using cover-coat enamel plus Zirconium orthosilicate. and either will be better than for the lifting of whiteness still becomes present aspect Increase the input of base substrate whiteness and the effect of generation.
The serial example 3 of contrast:Under the experiment condition of fixing step 1,2,3,4,6,7,8,9,10,11,12,13, only to step Rapid 5 brighten glaze is adjusted, and draws following table:
By the research of three of the above mode, we can draw, brightens fancy glaze layer come improving product by silk screen printing The technical scheme of whiteness, to consider from the whitening effect that can reach, production stability, product quality and integrated cost hence it is evident that Better than the technical scheme lifting whiteness in terms of base substrate and cover-coat enamel.Preferable whiteness can be reached moreover it is possible to ensure the deformation of product Deng in product in, external quality, and Optimum cost.This also exactly the present invention program advantage be located, by change tradition Improve base substrate whiteness using drenching glaze mode, glaze layer is thicker and is difficult to adjust, the scheme that the present invention provides, there is provided a kind of suitable Silk screen printing brighten glaze, it is used for ceramic tile production, can be reached different white by way of printing the different numbers of plies Degree effect, makes process window more wide in range, is issued to best effect in the minimum situation of cost.
Increasing pink blossom glaze in step 7, using silk-screen printing technique, prints the set floral pattern consistent with ink-jetting pattern texture (depending on meshcount is according to the required depth heightening the color and clear patterns degree, mesh number scope in 80-250 mesh, in this product Use 160 mesh effect nets.Bigger using meshcount, pattern definition is higher, but the amplitude that can heighten the color is less; And use silk screen mesh number less, then the definition of pattern and fine and smooth degree are lower, but the effect that heightens the color can be higher) so that The color that InkJet printing processes do not reach can be compensated by increasing powder craft, thus reaching more abundant, face true to nature Color effect.In product development and production process, can according to product need adjust silk-screen patterns and colorant proportioning, thus reaching To the various patterns wanted and color.It is as follows that increasing pink blossom glaze presses mass fraction:The calcareous clear frit of high boron:12 parts, Jin Zong:3.3 Part, reddish brown:0.6 part, parcel is red:3 parts, parcel is yellow:0.6 part, carboxymethyl cellulose:1.3 parts, ethylene glycol:45 parts, water:40 parts. Here the calcareous frit of high boron is calculated with oxide mass number:Na2O:6 parts, CaO:12 parts, ZnO:7 parts, B2O3:8 parts, Al2O3:3 Part, SiO2:54 parts.Need exist for illustrating, Jin Zong, reddish brown, parcel is red and parcel Huang is the inorganic pigment of glaze, its select and Proportioning, to need the color increasing powder as reference, is mated according to actual toning experience.Ink-jet can be realized using increasing pink blossom glaze The unapproachable gray scale of stamp.
Help color fancy glaze in step 8,140 mesh full impregnated nets are printed using silk-screen printing technique, for ensureing fancy glaze uniform fold, no Can cause because of the thickness difference helping color fancy glaze helps aberration different thus producing two tone colour, and the full impregnated net using print twice 140 mesh to enter Row is complementary.Help color fancy glaze as follows by mass fraction:High zinc matter frit:100 parts, DS4003 (the print cream of Dow):130 parts, trimerization: 0.3 part, water:40 parts.325 mesh sieves tail over as 0.1-0.2%, and proportion is 1.32-1.35 gram/cc.High zinc matter frit with Chemical oxide mass fraction calculates:SiO2:53 parts, ZnO:21 parts, K2O:4 parts, Al2O3:7 parts, MgO:3 parts, CaO:3.5 part.
Under the experiment condition of fixing step 1,2,3,4,5,6,7,9,10,11,12,13, only step 8 is adjusted, Show that print helps color fancy glaze and not printing to help color fancy glaze to contrast:Coloring intensity lifting more than 10%, so can save the ink of costliness And colorant, advantageously reduce production cost.
Protection glaze layer in described step 9, prints 80 mesh full impregnated nets using silk-screen printing technique or carries veined effect net, Textured effect net would generally be nested flower with the inkjet printing pattern of the step 6 of as described before, and according to protection glaze thickness Thin needs select print 1-3 road silk screen fancy glaze, for ensureing the needs of later stage cold working polishing, generally select using print 3 road silk screens Fancy glaze, by print clear frit or complete throw glaze and other effects glaze so that ink-jetting pattern be difficult to be worn during routine use or Be conducive to this series of products is carried out with the cold work in later stage.It is as follows that protection glaze fancy glaze presses mass fraction:DJY801-G2 is (big The low-temperature transparent protection glaze of border science and technology):70 parts, DJY801-121 (the temperature resistant transparent protection glaze of big border science and technology):30 parts, DS4003 (the print cream of Dow):47 parts, sodium tripolyphosphate:0.3 part, water:25 parts.250 mesh sieves tail over 0.7-1.0%, proportion 1.60-1.63 Gram/cc.This protection glaze layer can also be other clear frits or entirely throw glaze.DJY801-G2 composition presses the matter of oxide Amount number is calculated as follows:SiO2:67 parts, Al2O3:14 parts, CaO:12 parts, B2O3:5 parts.DJY801-121 composition presses oxidation material Amount number is calculated as follows:SiO2:51 parts, Al2O3:15,K2O part:2,Na2O:5 parts, MgO:3.2 part, CaO:10 parts, B2O3:8 parts.
Mineral crystal fancy glaze in step 10, prints 60 mesh effect nets, this effect net pattern texture using silk-screen printing technique It is mutually matched (set flower) with the inkjet printing pattern of as described before step 6, in the place printing to mineral crystal fancy glaze, mineral crystal Fancy glaze can be merged with following fancy glaze, and (high temperature viscosity of mineral crystal fancy glaze is relatively low, and metal oxide content is higher and molten Also ratio is relatively low to melt temperature, can melt and arrange following glaze layer during burning till) so that this local pattern sink (under Sunken effect can ensure that the pattern of mineral crystal, effect will not be disposed when product is carried out with cold working polishing), produce simultaneously Raw mineral crystal effect.It is as follows that mineral crystal fancy glaze formula presses mass fraction:100 parts of mineral crystal dry granular, clear frit 0-50 part (needing to change according to calcining system), print cream (the print cream of Dow) 60-80 (change adjustment usage amount according to formula and reach need The fancy glaze proportion wanted) part, 0.2 part of carboxymethyl cellulose, water 25-40 part, the particle diameter of mineral crystal dry granular:80~120 mesh account for 70 ~80%, remainder is by 120 mesh, fancy glaze proportion 1.6~1.7g/cm3, after crossing 320 mesh sieves, tail over as 0.1 gram.Mineral crystal Fancy glaze thickeies effect net by 60 mesh together and is printed.Mineral crystal dry granular is as follows with chemical oxide composition:SiO2:8 parts, Al2O3:3 parts, B2O3:20 parts, Fe2O3:9 parts, MnO:46 parts, TiO2:8 parts.
Clear frit is calculated with oxide component, and its chemical constituent is as follows:SiO2:55 parts, Al2O3:14 parts, K2O:2 parts, Na2O:6 parts, MgO:2 parts, CaO:10 parts, B2O3:8 parts.
Firing temperature in step 11 is 1175~1185 DEG C, and firing period is 60~70min.
Polishing edging is the common process of Production of Ceramics, and correspondence carries out selecting here.
Embodiment 6
In the present embodiment, give this product with negative ion health function.
Anion is a kind of negatively charged gas ion of in the air.Various gas componants in air are not exclusively to divide Submode exists, and a portion is existed with the free state of ion.Wherein electronegative molecule or microgranule (be commonly called as bearing from Son) human body synthesis and vitamin storage can not only be facilitated, the physiological activity of strengthening and human activin, to human body and other biological Vital movement has highly important impact, and therefore it is otherwise known as " air vitamin ".
In the prior art, be typically employed in composition of raw materials and add a certain proportion of tourmaline powder, using when temperature and When pressure changes, electric heating difference and voltage difference can be caused between tourmaline crystal, this electrostatic potential difference can be up to 1.0 × 106EV, this energy be enough to make air ionize, and is converted into negative aeroion.But the main component because of tourmaline powder is The aluminum that is characterized with boracic, sodium, ferrum, the silicate material of lithium circulus, a large amount of introducings in base substrate can cause blank deformation, And introduce in glaze, also the characteristic of glaze can be produced with certain impact, especially for marzacotto, thus while there being correlation Functional product occurs, but overall performance not up to optimum.
Pin in this regard, the present embodiment provide corresponding solution, because tourmaline powder need and air contact could produce right The effect answered.Therefore, in the present embodiment, the component of mineral crystal fancy glaze is improved, introduce tourmaline powder wherein With improvement component, it is allowed to both there is abundant brilliant flower decorative effect, with more negative ion health function.
Concrete scheme is as follows:
It is as follows that the present embodiment provides mineral crystal fancy glaze formula to press mass fraction:100 parts of mineral crystal dry granular, tourmaline powder 1-3 part, light rare earth oxide 0.01-0.05 part, 20 parts of clear frit (corresponding firing temperature is suitably selected), print cream (the print cream of Dow) 60-80 (the fancy glaze proportion that adjustment usage amount reaches needs is changed according to formula) part, carboxymethyl cellulose 0.2 part, water 25-40 part, the particle diameter of mineral crystal dry granular:80~120 mesh account for 70~80%, and remainder is by 120 mesh, fancy glaze ratio Weigh 1.6~1.7g/cm3, after crossing 320 mesh sieves, tail over as 0.1 gram.Mineral crystal fancy glaze thickeies effect net by 60 mesh together and enters Row printing.
The use number of clear frit can be 0-50 part, and it uses root in order to adjust firing temperature and effect, marzacotto Suitably adjusted according to firing temperature and service condition.
This programme adds a small amount of tourmaline powder and micro light rare earth oxide in mineral crystal fancy glaze, so that Its electrostatic potential difference lifting, can be issued to higher anion releasing effect in less consumption.
The process being provided using such as embodiment 3, prepared Ceramic Tiles, under 25 degrees Celsius, relative humidity 60% Under the conditions of test, anion-generating capacity be 1800-2000/cm3.Because producing anion needs in the larger ring of relative humidity Border, therefore such brick is suitable for using in the larger space of the humidity such as bathroom.
Certainly, tourmaline can also be replaced using rare ice stone, opal or QICAISHI here.Because generation provided above The material of anion has considerable influence to the firing temperature of base substrate and blank deformation, and in the present invention, the mineral being used are brilliant Body fancy glaze contains substantial amounts of metallic element, and the glaze that it can arrange below in sintering forms depression, so both can report barrier The anion effect layer being formed will not be skimmed when follow-up rubbing down is processed, and meanwhile, this being applied in combination also makes Ceramic Tiles produce The anti-pollution characteristic of product and finished product deformation all control in less scope, essentially identical with un-added effect.
And adopt traditional the tradition anion powder such as tourmaline is used as added material, add in conventional glaze, The addition reaching the negative ion concentration of the present invention is needed to need to increase 1.5-2 times.So anion powder burns till to glaze Effect has considerable influence, and then affects anti-pollution characteristic and the deformation of finished product.
Embodiment 7
In the present embodiment, give this product antibacterial functions, in traditional handicraft, product surface material introduces antibacterial Agent is conventional selection.The antibacterial such as example common silver, copper, zinc.But because product needed passes through high temperature sintering, this can be to product Antibacterial effect produce deleterious effect, in this regard, people select using above antibacterial phosphate.But be given with prior art Scheme from the point of view of, all cannot solve the problems, such as the deformation of products after there is good antibacterial effect very well.
Pin, in this regard, the present invention introduces a certain amount of antibacterial components in above mineral crystal fancy glaze, is spent using mineral crystal The a large amount of metallic elements containing in glaze, glaze can melt at a lower temperature, concave downward, it is to avoid follow-up rubbing down is to antibacterial The destruction of layer, the metallic element simultaneously containing in mineral crystal fancy glaze is also so that the antibacterial effect of its antibacterial is enhanced.
It is as follows that the present embodiment provides mineral crystal fancy glaze formula to press mass fraction:100 parts of mineral crystal dry granular, antibacterial 1.5 parts, 10 parts of clear frit (corresponding firing temperature suitably selected), print cream (the print cream of Dow) 60-80 (according to formula Change adjustment usage amount is reaching the fancy glaze proportion of needs) part, 0.2 part of carboxymethyl cellulose, water 25-40 part, mineral crystal does The particle diameter of grain:80~120 mesh account for 70~80%, and remainder is by 120 mesh, fancy glaze proportion 1.6~1.7g/cm3, cross 320 mesh sieves Afterwards, tail over as 0.1 gram.
Antibacterial is the mixture of silver phosphate and zirconium phosphate, and the mass percent of silver phosphate is 85-95%, balance of phosphoric acid Zirconium.In high temperature sintering, silver phosphate and zirconium phosphate are combined, and silver ion will go in the layer structure of zirconium phosphate, part Bedded zirconium phosphate crystal defect is repaired, part replaces zirconium ion, thus defining the mixed crystal knot of silver phosphate and zirconium phosphate Structure, has low cost, the feature of durable antibacterial effect, and it has no adverse effects to the colour generation of color development metal-oxide.
Embodiment 8
In the present embodiment, essentially identical with embodiment 7 preparation technology, institute's difference is that antibacterial is chosen as aoxidizing Silver, the number that it accounts in mineral crystal fancy glaze is 5 parts.After configuring in proportion, by this mineral crystal with antibacterial effect Fancy glaze charity is carrying out the billet surface of printing ornament, tests its effect after sintering, has preferable killing effect to antibacterial, but Its colour generation has a small amount of deviation with default.
Embodiment 9
In the present embodiment, essentially identical with embodiment 7 preparation technology, institute's difference is that antibacterial is chosen as aoxidizing Copper, the number that it accounts in mineral crystal fancy glaze is 1.5 parts.After configuring in proportion, by this mineral crystalline substance with antibacterial effect Body fancy glaze charity, in the billet surface carrying out printing ornament, is tested its effect, and it is compared with embodiment 5 after sintering, colour generation Partially deep, antibacterial effect is slightly poor.
Embodiment 10
In the present embodiment, essentially identical with embodiment 7 preparation technology, institute's difference is that antibacterial is chosen as phosphoric acid Silver, and it is not added with zirconium phosphate.After configuring in proportion, this mineral crystal fancy glaze charity with antibacterial effect is being carried out stamp The billet surface of decoration, tests its effect, and it is compared with embodiment 5 after sintering, colour generation slightly deviation, the holding of antibacterial effect Continuous property is slightly poor.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art. Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general Principle is applied in other embodiment without through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability , according to the announcement of the present invention, the improvement made without departing from scope and modification all should be the present invention's for field technique personnel Within protection domain.

Claims (6)

1. a kind of Ceramic Tiles with mineral crystal fancy glaze layer, it includes from the bottom to top:Green body layer, printed layer, protection fancy glaze layer With mineral crystal fancy glaze layer, described mineral crystal fancy glaze layer formed by charity mineral crystal fancy glaze, described mineral crystal fancy glaze Calculated with mass fraction, including following component:100 parts of mineral crystal dry granular, clear frit 0-50 part, print cream 60-80 part, carboxymethyl 0.2 part of cellulose, water 25-40 part, the chemical constituent of described mineral crystal dry granular is calculated with oxide weight number, including as follows Component:SiO2:8 parts, Al2O3:3 parts, B2O3:20 parts, Fe2O3:9 parts, MnO:46 parts, TiO2:8 parts.
2. as claimed in claim 1 a kind of Ceramic Tiles with mineral crystal fancy glaze layer it is characterised in that described green body layer and It is provided with cover coat between printed layer.
3. as claimed in claim 1 a kind of Ceramic Tiles with mineral crystal fancy glaze layer it is characterised in that described green body layer and It is additionally provided between printed layer and brightens layer, the described layer that brightens is to brighten glaze by charity to be formed, and the described glaze that brightens is with quality Number calculates, and it includes following component:Clear frit:50 parts, Zirconium orthosilicate.:50 parts, print cream:65 parts, sodium tripolyphosphate:0.3 part, Water:35 parts;
The chemical constituent of described clear frit is calculated with oxide weight number, including following component:
Na2O:5 parts, CaO:9 parts, ZnO:8 parts, Al2O3:8 parts, B2O3:2 parts, SiO2:60 parts.
4. a kind of preparation method of the Ceramic Tiles with mineral crystal fancy glaze layer, it comprises the steps:
Step 1) make adobe from known ceramic body powder punching press;
Step 2) on brightening layer, decalcomania layer is formed using known stamp mode;
Step 3) charity protection fancy glaze in decalcomania layer, form protection fancy glaze layer, described protection fancy glaze is known transparent Glaze;
Step 4) charity mineral crystal fancy glaze on protection fancy glaze layer, form mineral crystal fancy glaze layer, described mineral crystal fancy glaze Calculated with mass fraction, including following component:100 parts of mineral crystal dry granular, clear frit 0-50 part, print cream 60-80 part, carboxymethyl 0.2 part of cellulose, water 25-40 part, the chemical constituent of described mineral crystal dry granular is calculated with oxide weight number, including as follows Component:SiO2:8 parts, Al2O3:3 parts, B2O3:20 parts, Fe2O3:9 parts, MnO:46 parts, TiO2:8 parts;
Step 5) enter kiln and fire;
Step 6) base substrate after burning till is polished and edging process, obtain ceramic brick product.
5. as claimed in claim 4 a kind of preparation method with the Ceramic Tiles helping color fancy glaze layer it is characterised in that described step Rapid 1) and step 2) between include print brighten glaze formation brighten layer step, the described component brightening glaze is with mass fraction Calculate, including following component:Clear frit:50 parts, Zirconium orthosilicate.:50 parts, print cream:65 parts, sodium tripolyphosphate:0.3 part, water:35 Part;
The chemical constituent of described clear frit is calculated with oxide weight number, including following component:
Na2O:5 parts, CaO:9 parts, ZnO:8 parts, Al2O3:8 parts, B2O3:2 parts, SiO2:60 parts.
6. as claimed in claim 5 a kind of preparation method with the Ceramic Tiles helping color fancy glaze layer it is characterised in that described print System brightens printing number of times >=2 time of glaze.
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CN109851398A (en) * 2019-02-27 2019-06-07 佛山石湾鹰牌陶瓷有限公司 A kind of intelligent jet printing technique of the big plate of ceramics
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CN110845227A (en) * 2019-11-27 2020-02-28 蒙娜丽莎集团股份有限公司 Positioning crystal-patterned light-transmitting ceramic tile and preparation method thereof
CN112374920A (en) * 2021-01-12 2021-02-19 佛山市章氏兄弟建材有限公司 Glazed three-dimensional gold-plated combined polished glazed brick and preparation method thereof
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Publication number Priority date Publication date Assignee Title
WO2019015237A1 (en) * 2017-07-21 2019-01-24 广东金意陶陶瓷集团有限公司 Anti-slip wear-resistant glaze, anti-slip wear-resistant easy-clean ceramic tile, and preparation method therefor
US10475264B2 (en) 2017-08-14 2019-11-12 Q & K International Group Limited Application method of Bluetooth low-energy electronic lock based on built-in offline pairing passwords, interactive unlocking method of a Bluetooth electronic lock and electronic lock system
CN109851398A (en) * 2019-02-27 2019-06-07 佛山石湾鹰牌陶瓷有限公司 A kind of intelligent jet printing technique of the big plate of ceramics
CN109851398B (en) * 2019-02-27 2021-11-05 佛山石湾鹰牌陶瓷有限公司 Intelligent jet printing process for ceramic large plate
CN110845227A (en) * 2019-11-27 2020-02-28 蒙娜丽莎集团股份有限公司 Positioning crystal-patterned light-transmitting ceramic tile and preparation method thereof
CN110845227B (en) * 2019-11-27 2021-11-16 蒙娜丽莎集团股份有限公司 Positioning crystal-patterned light-transmitting ceramic tile and preparation method thereof
CN112374920A (en) * 2021-01-12 2021-02-19 佛山市章氏兄弟建材有限公司 Glazed three-dimensional gold-plated combined polished glazed brick and preparation method thereof

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