CN107686245A - There is the soft throwing glazed tile and preparation method thereof that is not cracked of wavellite effect on surface - Google Patents

There is the soft throwing glazed tile and preparation method thereof that is not cracked of wavellite effect on surface Download PDF

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CN107686245A
CN107686245A CN201710833907.XA CN201710833907A CN107686245A CN 107686245 A CN107686245 A CN 107686245A CN 201710833907 A CN201710833907 A CN 201710833907A CN 107686245 A CN107686245 A CN 107686245A
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silver
crystal grain
colored
cover
coat enamel
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CN201710833907.XA
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CN107686245B (en
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梁桐灿
余国明
欧家瑞
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GUANGDONG HONGHAI CERAMIC INDUSTRIAL DEVELOPMENT Co Ltd
Guangdong Hongwei Ceramic Industry Co Ltd
Guangdong Hongyu New Material Co Ltd
GUANGDONG WINTO CERAMICS CO Ltd
Original Assignee
GUANGDONG HONGHAI CERAMIC INDUSTRIAL DEVELOPMENT Co Ltd
Guangdong Hongwei Ceramic Industry Co Ltd
Guangdong Hongyu New Material Co Ltd
GUANGDONG WINTO CERAMICS CO Ltd
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Priority to CN201710833907.XA priority Critical patent/CN107686245B/en
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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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/86—Glazes; Cold glazes

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

Abstract

The soft throwing glazed tile and preparation method thereof that is not cracked that there is wavellite effect on surface includes frit, cover-coat enamel, silver-colored star crystal grain and silver-colored star crystal grain slurry.The present invention to existing glazed tile production technology on the basis of great change is not made, emphasis forms to the formula of frit, the formula composition of cover-coat enamel, the formula composition of silver-colored star crystal grain and silver-colored star grain slurry, silver-colored star crystallite size it is preferred, glazing, the adjustment and optimization of sizing technique, soft polishing chip and the soft optimization for throwing technique etc., obtained glazed tile product surface is set to form strong contrast with unglazed cover-coat enamel on gloss in spherical and column silver-colored star crystal grain, sent under light-illuminating and a glittering starlight of point is sent such as wavellite, seemingly the silver-colored starfish as children's stories is empty, like a dream, dicoration and artistry with uniqueness；Product is by the result judgement of the fitness test of AH Ha Ketefa base glaze：The number of days not ftractureed at room temperature is unconditional safety, solves the shortcomings that existing glazed tile is cracked after long-term use.

Description

There is the soft throwing glazed tile and preparation method thereof that is not cracked of wavellite effect on surface
Technical field：
The present invention relates to the preparing technical field of glazed tile, and referring in particular to a kind of surface has not being cracked for wavellite effect soft Throw glazed tile and preparation method thereof.
Background technology：
Wavellite is aqueous aluminum phosphate, and, typically in spherical or column, the aggregate of crystal has glass light into radial for it Pool is greasy luster, translucent, and wavellite is typically attached to rock surface or is distributed in the crack of rock, and wavellite is by throwing After light processing, there is powerful contrast in these translucent spherical or column wavellite, on gloss with its rock matrix in lamp Silver-colored starfish such as children's stories is empty under light irradiation, point point is glittering, like a dream, has unique decorative effect, obtains upstart personage Pursue, turn into indispensable decoration in some top grade decorations, but wavellite nature content was originally rare, it only adheres to In the crack of rock surface or rock, therefore very expensive for making the decorative material price of house, if it is extensive from The Wall or floor tile of dynamic metaplasia production, which technically develops this surface, the soft throwing glaze paint brick product that is not cracked of wavellite effect, by general The paving of logical Wall or floor tile, and coordinate the design of indoor light, house will necessarily be made to take on an entirely new look, elegant, held wherein imitative Buddhist is entered in the silver-colored starfish sky in Woild of Faivy Jale, simultaneously because product is not cracked, is durable in use, breaches existing glazed tile warp The drawbacks of cracking occurs after long-term use.
The content of the invention：
It is an object of the invention to overcome disadvantages mentioned above, there is provided there is the soft throwing glaze paint that is not cracked of wavellite effect on a kind of surface Brick and preparation method thereof, on the basis of great change is not made to existing glazed tile production technology, by matching somebody with somebody to frit Fang Zucheng, the formula composition of cover-coat enamel, the formula composition of silver-colored star crystal grain and silver-colored star grain slurry, silver-colored the preferred of star crystallite size, glazing, apply The adjustment of sizing process and optimization, soft polishing chip and the soft optimization for throwing technique, so that obtained glaze paint brick product has natural silver Special-effect after the polished polishing of star stone, under light-illuminating, the silver-colored star crystal grain on surface is after soft throwing with unglazed cover-coat enamel in light Strong contrast is formed on pool, so that silver-colored starfish of the silver-colored star crystal grain appearance such as children's stories is empty, point point is glittering, like a dream, tool There is the decorative effect of uniqueness, and product glaze quality is good, corrosion resistance and resistance to soiling are strong, abrasion resistance is high, pin-free, glaze bubble etc. lacks Fall into；And compatibility test detection of the product through AH Ha Ketefa base glaze, and ftractureed the phase according to AH Ha Kete generation Judgement table judges that testing result the number of days that the product does not ftracture at normal temperatures is unconditional safety, so as to sentence The shortcomings that cracking will not occurring as existing glazed tile after the disconnected product long-term use；The technology possesses stronger pervasive simultaneously Property, it is easy in industry promote.
In order to solve the above technical problems, the present invention is achieved through the following technical solutions：
The surface of the present invention has wavellite effect not to be cracked soft throwing glazed tile, and it includes：
Frit：Prepared by following weight percent composition：
SiO265.5%~66.5%, Al2O37.4%~8.4%, CaO 7.8%~8.8%, MgO 1.8%~ 2.2%, K2O 4.8%~5.4%, Na2O 1.6%~2.2%, ZrO24.6%~5.6%, B2O31.8%~2.2%, Li2O 0.4%~1.2%, P2O50.7%~1.1%, all component sums are 100%；
Cover-coat enamel：Prepared by following weight percent composition：
SiO255%~56%, Al2O316%~17%, CaO 4.4%~5%, MgO 2.4%~3%, K2O 2.4%~3%, Na2O 2.1%~2.5%, TiO21.5%~2.5%, ZrO26%~7%, B2O31%~2%, Li2O0.1%~0.3%, P2O50.7%~1.1%, ZnO 1.4%~2%, loss on ignition 1.5%~2.5%, all groups / and be 100%；
Added weight percentage is 0.4%~1% auxiliary material；Wherein described auxiliary material includes carboxymethyl cellulose Element, sodium tripolyphosphate and sodium humate；The glaze volume of the cover-coat enamel is that aqueous glaze slip weighs 760~900g/ ㎡, and described cover-coat enamel is high Temperature is in mat glaze after burning till；
Silver-colored star crystal grain：Prepared by following weight percent composition：
SiO260.2%~61.2%, Al2O33.2%~4.2%, CaO 6.2%~7%, MgO 2.4%~ 3.2%, K2O 3.2%~4%, Na2O 1%~1.8%, TiO21.2%~2%, ZrO25%~6%, B2O34%~ 5%, ZnO 6%~7%, SrO 1%~1.6%, P2O50.6%~1%, all component sums are 100%；
The granularity of described silver-colored star crystal grain is the mesh of 60 mesh~160, and after high temperature is burnt till, silver-colored star crystal grain is in spherical and column bonding On unglazed cover-coat enamel surface, pico- raised, translucent there is greasy luster；
Silver-colored star crystal grain slurry：Prepared by following parts by weight of component：
Silver-colored 30~50 parts of star crystal grain, 10~20 parts of ethylene glycol, 1~2 part of carboxymethyl cellulose, 30~50 parts of water, venting agent 0.2~0.4 part；Described silver-colored star crystal grain slurry sizing amount is that aqueous wet pulp weighs 170~280g/ ㎡.
There is the preparation method of the soft throwing glazed tile that is not cracked of wavellite effect the invention further relates to a kind of surface, it includes：
A, the preparation of frit：
The percentage by weight of the component of frit is：
SiO265.5%~66.5%, Al2O37.4%~8.4%, CaO 7.8%~8.8%, MgO 1.8%~ 2.2%, K2O 4.8%~5.4%, Na2O 1.6%~2.2%, ZrO24.6%~5.6%, B2O31.8%~2.2%, Li2O 0.4%~1.2%, P2O50.7%~1.1%, all component sums are 100%；
Granularity containing said components is respectively less than to the raw material of 150 mesh：Silica flour, feldspar powder, calcium carbonate, alumina powder, talcum Powder, zirconium English powder, potassium carbonate, sodium carbonate, spodumene powder, floats and boric acid, according to said components scope dispensing, mixer Mixing, frit tank furnace are founded, and the temperature range founded is 1500 DEG C~1520 DEG C, and then water quenching is into frit granules, drying Frit；
B, the preparation of cover-coat enamel：
The percentage by weight of the component of cover-coat enamel is：
SiO255%~56%, Al2O316%~17%, CaO 4.4%~5%, MgO 2.4%~3%, K2O 2.4%~3%, Na2O 2.1%~2.5%, TiO21.5%~2.5%, ZrO26%~7%, B2O31%~2%, Li2O0.1%~0.3%, P2O50.7%~1.1%, ZnO 1.4%~2%, loss on ignition 1.5%~2.5%, all groups / and be 100%；
By the weight percent content of the component of above-mentioned cover-coat enamel, choose corresponding proportion above-mentioned steps A be prepared it is molten Block, feldspar powder, silica flour, alumina powder, calcium carbonate, burn talcum, titanium dioxide, zirconium silicate, zinc oxide, apatite, kaolin with And added weight percentage be 0.4%~1% auxiliary material, add appropriate water through ball milling it is in small, broken bits into fineness be 325 mesh Sieve is tailed over for mass percent 0.4%~0.8% and containing the glaze slip that mass percent is 28%~30% moisture, through iron removaling mistake Sieve and produce cover-coat enamel；Additional auxiliary material therein includes carboxymethyl cellulose, sodium tripolyphosphate and sodium humate；
C, the preparation of silver-colored star crystal grain：
The percentage by weight of the component of silver-colored star crystal grain is：
SiO260.2%~61.2%, Al2O33.2%~4.2%, CaO 6.2%~7%, MgO 2.4%~ 3.2%, K2O 3.2%~4%, Na2O 1%~1.8%, TiO21.2%~2%, ZrO25%~6%, B2O34%~ 5%, ZnO 6%~7%, SrO 1%~1.6%, P2O50.6%~1%, all component sums are 100%；
Granularity containing said components is respectively less than to the raw material of 150 mesh：Silica flour, feldspar powder, calcium carbonate, talcum powder, potassium carbonate, Borax, titanium dioxide, zirconium English powder, boric acid, zinc oxide, strontium carbonate and apatite, are mixed according to said components scope dispensing, mixer Conjunction, frit tank furnace are founded, and the temperature range founded is 1500 DEG C~1520 DEG C, and then water quenching is into particle, then dries, broken granulating The fine grained spent for 60~160 mesh produces silver-colored star crystal grain；
D, the preparation of silver-colored star crystal grain slurry, is prepared by weight：
By silver-colored 30~50 parts of star crystal grain, 10~20 parts of ethylene glycol, 1~2 part of carboxymethyl cellulose, 30~50 parts of water, venting 0.2~0.4 part of agent, it is mixed evenly and produces silver-colored star crystal grain slurry；
E, the preparation of product and burn till：
On the glazed tile base substrate for normally having applied ground-coat enamel, the cover-coat enamel that above-mentioned steps B is prepared, the glaze volume of cover-coat enamel are first applied For 760~900g/ ㎡, described glaze volume is aqueous glaze slip weight, then by stamp, then applies what above-mentioned steps D was prepared Silver-colored star crystal grain slurry, the sizing amount of silver-colored star crystal grain slurry is 170~280g/ ㎡, and described sizing amount is to starch weight containing water temperature, is then passed through Dry, apply prime cement, enter back into roller kilns glaze firing, maximum sintering temperature scope is 1100 DEG C~1130 DEG C, and firing time scope is 40~80 minutes, then carry out the silver-colored soft throwing of star crystal grain with Elastic abrasive body, Elastic abrasive body can not throw unglazed cover coat during soft throwing, then By waxing or not waxing, then carry out edging and get product.
The finished product is detected using the fitness test of AH Ha Ketefa base glaze, and finished product is slowly added in drying box Heat puts into chilling in 15 DEG C of water and examines flawless in 2 minutes, and repetitive cycling examines equal nothing three times immediately after to 210 DEG C Crackle.
There are the soft throwing glazed tile and preparation method thereof that is not cracked of wavellite effect, the glazed tile production of preparation in the surface of the present invention The silver-colored star crystal grain on product surface burns till rear glomeration by high temperature or column is bonded on unglazed cover-coat enamel surface, pico- raised, semi-transparent It is bright to have greasy luster, then strong contrast is formed with unglazed cover-coat enamel on gloss after being handled by soft throwing, such as natural wavellite After polishing grinding, wavellite crystal forms strong contrast with stone material matrix on gloss, under light-illuminating, these balls Shape or the silver-colored star crystal grain of column send a glittering starlight of point, as the silver-colored starfish in Woild of Faivy Jale is empty, like a dream, noble allusion quotation It is refined, there is unique ornamental artistry, and the product using AH Ha Ketefa glaze fits testing inspection and AH Ha Kete generation cracking phase judgement table testing result is judged, the number of days that the product ftractures at normal temperatures For unconditional safety, therefore solves the shortcomings that cracking occurs in existing glazed tile after long-term use, while the technology has Standby stronger universality, is easy in industry promote.
There is the soft throwing glazed tile and preparation method thereof that is not cracked of wavellite effect on the surface of the present invention, by frit formula The optimization of composition and cover-coat enamel formula composition：
On the one hand ensure that cover-coat enamel has been burnt till in high temperature is in mat glaze, so as to ensure that silver-colored star crystal grain shines after soft throwing in light Penetrate down and strong contrast is formed on gloss with cover-coat enamel, so as to send a glittering starlight of point, such as the silver-colored starfish in Woild of Faivy Jale It is empty；It can weaken the glittering starlight of point point of silver-colored star crystal grain significantly if there is gloss after high temperature is burnt till if cover-coat enamel, or even can not make Silver-colored star crystal grain sends a glittering starlight of point, therefore the Al in cover-coat enamel composition2O3With SiO2Ratio control 1: 3 to 1: 6 it Between, while with the addition of CaO, MgO, TiO favorable to mat glaze in right amount2、ZrO2Deng oxide.
On the other hand, it is ensured that cover-coat enamel melt when high temperature is burnt till has suitable viscosity, hardness, is applied so as to ensure that Silver-colored star crystal grain on its face will not incorporate in cover-coat enamel and spherical or column projection is presented, therefore with the addition of in cover-coat enamel composition To melt viscosity and the favorable Al of hardness2O3、SiO2、ZrO2Deng oxide.
Cover-coat enamel will also ensure that melt has suitable ductility in high temperature is burnt till simultaneously, can be incited somebody to action before high temperature burns till end Small pin hole that base substrate leaves when being vented, pit etc. are molten flat, it is ensured that the stain resistance of product, therefore also added in cover-coat enamel composition To the ductility favorable Li of melt2O、K2O、Na2O、P2O5Deng oxide, meanwhile, the burning for also controlling cover-coat enamel is lost Amount, the defects of in order to avoid loss on ignition is excessive, gas emissions are excessive, easy pin-holing, glaze bubble and reduce stain resistance.
In addition, cover-coat enamel melt when high temperature is burnt till will also have strong bonding force, make to apply its face silver-colored star crystal grain tightly Bond together, will not in soft throwing silver star crystal grain because bonding loosely and caused by by the active force of Elastic abrasive body collapse it is de-；Furthermore face Glaze will also have the suitable coefficient of expansion, high glaze layer intensity and low modulus of elasticity, because the modulus of elasticity of glaze is smaller, elasticity is got over Good, the elasticity of glaze is better, on the one hand can compensate stress caused by contact layer between base and glaze, on the other hand can also buffer The effect of mechanical external force.And glaze layer intensity is higher, then the ability for the inside and outside various stress that glaze is born is stronger.Close The suitable coefficient of expansion can ensure the conformability of glaze and base, therefore cover-coat enamel has suitable thermal coefficient of expansion, high glaze layer strong Degree and low modulus of elasticity ensure that product is not in cracking after long-term use.
The optimization of silver-colored star crystal grain formula composition, it on the one hand ensure that silver-colored star crystal grain can closely and face when high temperature is burnt till Glaze bonds together, will not in soft throwing because be bonded loosely and produce collapse it is de-；On the other hand, silver-colored star crystal grain is when high temperature is burnt till, Melt temperature with big surface tension and suitable beginning, so as to present such as natural wavellite crystal in attachment as spherical or column On unglazed cover-coat enamel surface, pico- raised, be translucent shape, and greasy luster is presented in surface, so as to not only ensure that the bullet in soft throwing Property module has only been polished the surface of silver-colored star crystal grain, without hurting unglazed cover-coat enamel surface, after it ensure that the silver-colored soft throwing of star crystal grain Glossiness, it is formed strong contrast on gloss with cover-coat enamel and is sent a glittering starlight of point, therefore in silver-colored star crystal grain Formula composition in the addition of Al favorable to surface tension in right amount2O3、ZrO2、TiO2Deng oxide.Silver-colored star crystal grain grain That spends is preferred, on the one hand ensure that silver-colored star crystal grain can be presented after high temperature is burnt till and unglazed cover-coat enamel table is attached to as spherical or column Face is slightly raised, on the other hand in turn ensure that the Nature Link between crystal grain and crystal grain is close, improves stain resistance.
The optimization for the formula composition that silver-colored star crystal grain is starched, silver-colored star crystal grain slurry is on the one hand ensure that with suitable bonding force and is hanged Buoyancy, it not only ensure that silver-colored star crystal grain will not produce precipitation during sizing because of the Action of Gravity Field of crystal grain；But also ensure The silver-colored star crystal grain applied on cover-coat enamel tightly can be bonded on cover-coat enamel, will not be blown away or be inhaled because the external force such as kiln hood blower fan act on Walk；Also assures that simultaneously will not damage during sizing to ink-jet printed pattern, so that ink-jet printed dim pattern is unclear.
Apply cover-coat enamel amount and apply the preferred of silver-colored star crystal grain slurry amount, on the one hand ensure that cover-coat enamel and ground-coat enamel, silver-colored star crystal grain and cover-coat enamel The stability in intermediate layer, so as to ensure that product occurs without cracking after prolonged use, it on the other hand in turn ensure that silver-colored star crystal grain Spherical or column is presented after high temperature is burnt till, and to be attached to unglazed cover-coat enamel surface slightly raised, without because applying cover-coat enamel amount and Shi Yinxing Crystal grain slurry amount is excessive, so as to cause silver-colored star crystal grain raised completely molten flat not enough even with cover-coat enamel, so as to influence the surface after soft throwing Effect, or because apply cover-coat enamel amount and apply the silver-colored very few cover-coat enamel so as to caused by of star crystal grain slurry amount smoothness not enough, corrugation, and with silver-colored star Loosely, and connection between crystal grain and crystal grain is unnatural and leaves gap etc., exists so as to crystal grain occur for the bonding force of crystal grain Occurs the defects of collapsing de- and reduction product stain resistance during soft throwing.
It is soft to throw the preferred of technique and abrading block, the surface smoothness of product silver-colored star crystal grain after soft throwing is not only ensure that, and Unglazed cover-coat enamel will not be damaged.
The soft throwing glazed tile and preparation method thereof that is not cracked that there is wavellite effect on the surface of the present invention has the following advantages：
1st, due to optimizing the formula composition of frit, the formula composition of cover-coat enamel, silver-colored star crystal grain and the formula group of silver-colored star grain slurry Into, silver-colored the preferred of star crystallite size, glazing, the adjustment of sizing technique and optimization, soft polishing chip and the soft optimization for throwing technique, so as to Make effect of the product surface of manufacture such as wavellite, under light-illuminating, the silver-colored star crystal grain on surface on gloss with dull surface Glaze forms strong contrast and sends a glittering starlight of point, and the silver-colored starfish such as children's stories is empty, has unique decorative effect.
2nd, product surface flatness, the modulus of rupture, rupture strength, resistance to acids and bases, wearability, radioactivity, the Lead and cadmium Amount reaches the requirement of GB/T4100-2015, GB6566-2010 and HT/T297-2006 standard.
3rd, compatibility test detection of the product through AH Ha Ketefa base glaze, and opened according to AH Ha Kete Split judgement of the phase judgement table to testing result：The number of days that the product does not ftracture at normal temperatures is unconditional safety.
4th, the product uses the production technology of existing glazed tile, makes after the polished polishing of wavellite energy under distinctive illumination An effect for the glittering starlight of point is sent to be able to copy on glaze paint brick product, it is easy to accomplish industrialized scale, while solve again The shortcomings that cracking occurs after existing glazed tile long-term use.
Brief description of the drawings：
Fig. 1 is the process chart for preparing the soft throwing glazed tile that is not cracked that there is wavellite effect on surface of the invention.
Embodiment：
The present invention is described in further detail with reference to embodiment.
Embodiment 1
There is the preparation method of the soft throwing glazed tile that is not cracked of silver-colored star effect on a kind of surface, and it comprises the following steps：
A, frit is prepared：
The chemical composition composition such as table 1 below of frit
The chemical composition table (percentage by weight, %) of table 1, frit
Prepare frit：By the base substrate chemical composition of table 1 choose corresponding proportion granularity be respectively less than 150 mesh silica flour, Feldspar powder, calcium carbonate, alumina powder, talcum powder, zirconium English powder, potassium carbonate, sodium carbonate, spodumene powder, floats, boric acid are former Material, dispensing is carried out, mixes in mixer, founded in frit tank furnace, the temperature range founded is 1500 DEG C~1520 DEG C, so Water quenching is into frit granules, drying frit afterwards；
B, cover-coat enamel is prepared：
The chemical composition of cover-coat enamel such as table 2 below：
The chemical composition table (percentage by weight, %) of table 2, cover-coat enamel
Prepare cover-coat enamel：Frit, the length that the above-mentioned steps A of corresponding proportion is prepared are chosen by the chemical composition of table 2 Stone flour, silica flour, alumina powder, calcium carbonate, burn talcum, titanium dioxide, zirconium silicate, zinc oxide, apatite, kaolin and additional Percentage by weight is 0.4%~1% auxiliary material；It is in small, broken bits into the sieve that fineness is 325 mesh sieves through ball milling to add appropriate water Remaining is mass percent 0.4%~0.8% and containing the glaze slip that mass percent is 28%~30% moisture, sieves and stores through iron removaling It is standby to produce cover-coat enamel；Additional auxiliary material therein includes carboxymethyl cellulose, sodium tripolyphosphate and sodium humate；Described Cover-coat enamel high temperature is in mat glaze after burning till；
C, silver-colored star crystal grain is prepared：
The chemical composition composition such as table 3 below of silver-colored star crystal grain：
The chemical composition table (percentage by weight, %) of table 3, silver-colored star crystal grain
Component SiO2 Al2O3 CaO MgO K2O Na2O TiO2 ZrO2 B2O3 ZnO SrO P2O5
1# 60.2 4.2 6.6 3.2 4 1.4 2 5.5 5 6 1.3 0.6
2# 60.7 3.7 6.2 2.8 3.6 1.8 1.6 6 4.5 7 1.3 0.8
3# 61.2 3.2 7 2.4 3.2 1 1.4 6 5 7 1.6 1
4# 60.8 4 6.8 3 3.8 1.6 1.8 5.8 4 6.5 1 0.9
5# 61 3.9 6.5 3 3.9 1.7 1.2 5 4.8 6.8 1.5 0.7
Prepare silver-colored star crystal grain：The quartz of 150 mesh is respectively less than by the granularity of the chemical composition selection corresponding proportion of table 3 Powder, feldspar powder, calcium carbonate, talcum powder, potassium carbonate, borax, titanium dioxide, zirconium English powder, boric acid, zinc oxide, strontium carbonate, apatite are former Material, dispensing is carried out, mix in mixer, founded in frit tank furnace, the temperature range founded is 1500 DEG C~1520 DEG C, so Water quenching is into particle afterwards, then dries and be broken into the fine grained that granularity is 60~160 mesh and produce silver-colored star crystal grain；Described silver-colored star crystal grain exists High temperature is in that spherical and column is bonded in unglazed cover-coat enamel surface after burning till, and there is greasy luster on pico- raised, translucent, surface；
D, silver-colored star crystal grain slurry is prepared：
The formula constituent table (parts by weight) of table 4, silver-colored star crystal grain slurry
Component Silver-colored star crystal grain Ethylene glycol Carboxymethyl cellulose Water Venting agent
1# 30 20 2 47.6 0.4
2# 40 15 1.5 43.2 0.3
3# 48.8 10 1 40 0.2
4# 50 18 1.7 30 0.3
5# 35 13 1.8 50 0.2
Prepare silver-colored star crystal grain slurry：By the formula composition of the silver medal star crystal grain of table 4 slurry weigh that above-mentioned steps C is prepared by silver-colored star Crystal grain, ethylene glycol, carboxymethyl cellulose, water, venting agent, it is mixed together and stirs that to produce silver-colored star crystal grain slurry standby；Wherein institute The venting agent K3910 of the venting agent stated such as Shandong state porcelain Kang Litai new materials Science and Technology Ltd. production；
E, product is prepared：
The cover-coat enamel that above-mentioned steps B is prepared is applied on the glazed tile base substrate for normally having applied ground-coat enamel, the glaze volume of cover-coat enamel is 760~900g/ ㎡, described glaze volume are aqueous glaze slip weight, need to use silk-screen plate or offset printing roller or spray further according to product design Ink-printed machine carries out printing ornament, then applies the silver-colored star crystal grain slurry that above-mentioned steps D is prepared, and the sizing amount of silver-colored star crystal grain slurry is 170~280g/ ㎡, described sizing amount are aqueous wet pulp weight, then by drying, applying prime cement, enter back into roller kilns glaze firing, most High firing range is 1100 DEG C~1130 DEG C, and firing time scope is 40~80 minutes, then magnificent with such as Nanhai District Foshan City The diamond Elastic abrasive body for containing the production of grinding tool Co., Ltd carries out soft throwing to silver-colored star crystal grain, and Elastic abrasive body can not throw nothing during soft throwing Smooth surface glaze layer, then as needed through waxing or do not wax, then carry out edging and get product.
The present invention by described surface have wavellite effect be not cracked it is soft throwing glazed tile preparation method prepare into Product surface color is abundant, pattern followed rock clear and natural, bright in luster, third dimension is strong, and under light-illuminating, surface is in spherical and post The silver-colored star crystal grain of shape forms strong contrast with unglazed cover-coat enamel on gloss, sends a glittering starlight of point, is such as thrown by surface Natural wavellite after light processing, it is attached to the wavellite crystal of stone surface and formed with stone material matrix on gloss strongly Contrast and send a glittering starlight of point, hold wherein, seemingly enter silver-colored starfish as children's stories it is empty, like a dream, noble allusion quotation It is refined, there is unique dicoration and artistry.And detected by the fitness test of AH Ha Ketefa base glaze, by above-mentioned finished product 120 DEG C are heated slowly in drying box, chilling 2 minutes in 15 DEG C of water is put into immediately, checks for crackle, carried if flawless High 10 DEG C of temperature are heated again, are still put into chilling in water and are checked for crackle, and untill cracking, 10 DEG C of increase every time adds Hot temperature, the temperature to be ftractureed according to glaze paint, its safe-use period can be predicted, make to repeat to try three times at each temperature as far as possible Test.And judge the safe-use period of product by Ha Kete generation cracking phase judgement table.
Finished product indices such as table 5 below after testing：
Table 5：Product quality inspection result
In summary, only presently preferred embodiments of the present invention, any formal limitation not is made to the present invention；It is all The those of ordinary skill of the industry can swimmingly implement the present invention by described above；But all it is familiar with this professional technology people Member without departing from the scope of the present invention, a little change for being made using disclosed above technology contents, repaiies Decorations and the equivalent variations developed, it is the equivalent embodiment of the present invention；Meanwhile all substantial technologicals according to the present invention are real to more than Apply change, modification and the differentiation for any equivalent variations that example is made, still fall within technical scheme protection domain it It is interior.

Claims (3)

1. there is the soft throwing glazed tile that is not cracked of wavellite effect on surface, it is characterised in that：
Frit：Prepared by following weight percent composition：
SiO265.5%~66.5%, Al2O37.4%~8.4%, CaO 7.8%~8.8%, MgO 1.8%~2.2%, K2O 4.8%~5.4%, Na2O 1.6%~2.2%, ZrO24.6%~5.6%, B2O31.8%~2.2%, Li2O 0.4%~1.2%, P2O50.7%~1.1%, all component sums are 100%；
Cover-coat enamel：Prepared by following weight percent composition：
SiO255%~56%, Al2O316%~17%, CaO 4.4%~5%, MgO 2.4%~3%, K2O 2.4%~ 3%, Na2O 2.1%~2.5%, TiO21.5%~2.5%, ZrO26%~7%, B2O31%~2%, Li2O 0.1% ~0.3%, P2O50.7%~1.1%, ZnO 1.4%~2%, loss on ignition 1.5%~2.5%, all component sums are 100%；
Added weight percentage is 0.4%~1% auxiliary material；
Described auxiliary material includes carboxymethyl cellulose, sodium tripolyphosphate and sodium humate；
The glaze volume of the cover-coat enamel is that aqueous glaze slip weighs 760~900g/ ㎡, described cover-coat enamel high temperature burn till after be in mat glaze；
Silver-colored star crystal grain：Prepared by following weight percent composition：
SiO260.2%~61.2%, Al2O33.2%~4.2%, CaO 6.2%~7%, MgO 2.4%~3.2%, K2O 3.2%~4%, Na2O 1%~1.8%, TiO21.2%~2%, ZrO25%~6%, B2O34%~5%, ZnO 6% ~7%, SrO 1%~1.6%, P2O50.6%~1%, all component sums are 100%；
The granularity of described silver-colored star crystal grain is the mesh of 60 mesh~160, and after high temperature is burnt till, silver-colored star crystal grain is bonded in nothing in spherical and column Smooth surface glaze surface, pico- raised, translucent there is greasy luster；
Silver-colored star crystal grain slurry：Prepared by following parts by weight of component：
Silver-colored 30~50 parts of star crystal grain, 10~20 parts of ethylene glycol, 1~2 part of carboxymethyl cellulose, 30~50 parts of water, venting agent 0.2~ 0.4 part；
Described silver-colored star crystal grain slurry sizing amount is that aqueous wet pulp weighs 170~280g/ ㎡.
2. there is the preparation method of the soft throwing glazed tile that is not cracked of wavellite effect on a kind of surface, it is characterised in that：
It comprises the following steps：
A, the preparation of frit：
The percentage by weight of the component of frit is：
SiO265.5%~66.5%, Al2O37.4%~8.4%, CaO 7.8%~8.8%, MgO 1.8%~2.2%, K2O 4.8%~5.4%, Na2O 1.6%~2.2%, ZrO24.6%~5.6%, B2O31.8%~2.2%, Li2O 0.4%~1.2%, P2O50.7%~1.1%, all component sums are 100%；
Granularity containing said components is respectively less than to the raw material of 150 mesh：Silica flour, feldspar powder, calcium carbonate, alumina powder, talcum powder, zirconium Ying Fen, potassium carbonate, sodium carbonate, spodumene powder, floats and boric acid, mixed according to said components scope dispensing, mixer, Frit tank furnace is founded, and the temperature range founded is 1500 DEG C~1520 DEG C, and then water quenching is into frit granules, drying frit；
B, the preparation of cover-coat enamel：
The percentage by weight of the component of cover-coat enamel is：
SiO255%~56%, Al2O316%~17%, CaO 4.4%~5%, MgO 2.4%~3%, K2O 2.4%~ 3%, Na2O 2.1%~2.5%, TiO21.5%~2.5%, ZrO26%~7%, B2O31%~2%, Li2O 0.1% ~0.3%, P2O50.7%~1.1%, ZnO 1.4%~2%, loss on ignition 1.5%~2.5%, all component sums are 100%；
By the weight percent content of the component of above-mentioned cover-coat enamel, frit, length that the above-mentioned steps A of corresponding proportion is prepared are chosen Stone flour, silica flour, alumina powder, calcium carbonate, burn talcum, titanium dioxide, zirconium silicate, zinc oxide, apatite, kaolin and additional Percentage by weight is 0.4%~1% auxiliary material, and it is in small, broken bits into the sieve that fineness is 325 mesh sieves through ball milling to add appropriate water Remaining is mass percent 0.4%~0.8% and containing the glaze slip that mass percent is 28%~30% moisture, sieves and produces through iron removaling Cover-coat enamel；Additional auxiliary material therein includes carboxymethyl cellulose, sodium tripolyphosphate and sodium humate；
C, the preparation of silver-colored star crystal grain：
The percentage by weight of the component of silver-colored star crystal grain is：
SiO260.2%~61.2%, Al2O33.2%~4.2%, CaO 6.2%~7%, MgO 2.4%~3.2%, K2O 3.2%~4%, Na2O 1%~1.8%, TiO21.2%~2%, ZrO25%~6%, B2O34%~5%, ZnO 6% ~7%, SrO 1%~1.6%, P2O50.6%~1%, all component sums are 100%；
Granularity containing said components is respectively less than to the raw material of 150 mesh：Silica flour, feldspar powder, calcium carbonate, talcum powder, potassium carbonate, boron Sand, titanium dioxide, zirconium English powder, boric acid, zinc oxide, strontium carbonate and apatite, are mixed according to said components scope dispensing, mixer Conjunction, frit tank furnace are founded, and the temperature range founded is 1500 DEG C~1520 DEG C, and then water quenching is into particle, then dries, broken granulating Spend for the fine grained of 60~160 mesh, produce silver-colored star crystal grain；
D, the preparation of silver-colored star crystal grain slurry, is prepared by weight：
By silver-colored 30~50 parts of star crystal grain, 10~20 parts of ethylene glycol, 1~2 part of carboxymethyl cellulose, 30~50 parts of water, venting agent 0.2 ~0.4 part, it is mixed evenly and produces silver-colored star crystal grain slurry；
E, the preparation of product and burn till：
On the glazed tile base substrate for normally having applied ground-coat enamel, the cover-coat enamel that above-mentioned steps B is prepared first is applied, the glaze volume of cover-coat enamel is 760~900g/ ㎡, described glaze volume are aqueous glaze slip weight, then by stamp, then apply the silver that above-mentioned steps D is prepared Star crystal grain is starched, and the sizing amount of silver-colored star crystal grain slurry is 170~280g/ ㎡, and described sizing amount is aqueous wet pulp weight, is then passed through Dry, apply prime cement, enter back into roller kilns glaze firing, maximum sintering temperature scope is 1100 DEG C~1130 DEG C, and firing time scope is 40~80 minutes, then carry out the silver-colored soft throwing of star crystal grain with Elastic abrasive body, Elastic abrasive body can not throw unglazed cover coat during soft throwing, then By waxing or not waxing, then carry out edging and get product.
3. there are the preparation method of the soft throwing glazed tile that is not cracked of wavellite effect, its feature in surface according to claim 2 It is：
A is used according to the finished product made from the preparation method of soft throwing glazed tile that is not cracked that there is wavellite effect on described surface The fitness test detection of H Ha Ketefa base glaze, finished product is heated slowly in drying box 210 DEG C, put into immediately after Into 15 DEG C of water, chilling examines flawless in 2 minutes, and repetitive cycling examines equal flawless three times.
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CN109824270A (en) * 2019-04-02 2019-05-31 佛山市禅城区科捷陶瓷原料有限公司 A kind of decorative brick of diamond flash effect, colored dry granular and preparation method thereof
CN110963792A (en) * 2019-12-19 2020-04-07 广东宏陶陶瓷有限公司 Porcelain polished brick of 80-degree whiteness and color ratio mutton tallow and preparation method thereof
CN111204978A (en) * 2020-01-23 2020-05-29 福建省德化县尚品陶瓷有限公司 Ceramic glaze with non-cracking glaze surface and glazing method thereof
CN111533454A (en) * 2020-05-24 2020-08-14 福建省德化县灿东陶瓷有限公司 Glaze material with metal luster for ceramics and glazing process thereof
CN111777433A (en) * 2020-07-08 2020-10-16 佛山市东鹏陶瓷有限公司 Preparation method of anti-oxidation ceramic glazed tile and prepared anti-oxidation ceramic glazed tile
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CN106277793A (en) * 2016-08-15 2017-01-04 广东宏宇新型材料有限公司 The glaze of a kind of high temperature gold colored glaze face brick, brick and preparation method thereof
CN106673438A (en) * 2016-12-28 2017-05-17 广东宏陶陶瓷有限公司 Magic star stone glazed brick with surface aventurine effect and preparation method thereof

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CN104529553A (en) * 2014-12-08 2015-04-22 广东宏陶陶瓷有限公司 Glazed tile manufactured by using ceramic waste and having broken diamond sand flashing starlight on surface, and preparation method thereof
CN106277793A (en) * 2016-08-15 2017-01-04 广东宏宇新型材料有限公司 The glaze of a kind of high temperature gold colored glaze face brick, brick and preparation method thereof
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CN108585496A (en) * 2018-07-20 2018-09-28 福建省德化县御泉工艺有限公司 Purplish blue glaze, the preparation method of purplish blue glaze and the method for preparing purplish blue glaze ceramic with it
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CN109824270A (en) * 2019-04-02 2019-05-31 佛山市禅城区科捷陶瓷原料有限公司 A kind of decorative brick of diamond flash effect, colored dry granular and preparation method thereof
CN110963792A (en) * 2019-12-19 2020-04-07 广东宏陶陶瓷有限公司 Porcelain polished brick of 80-degree whiteness and color ratio mutton tallow and preparation method thereof
CN111204978A (en) * 2020-01-23 2020-05-29 福建省德化县尚品陶瓷有限公司 Ceramic glaze with non-cracking glaze surface and glazing method thereof
CN111533454A (en) * 2020-05-24 2020-08-14 福建省德化县灿东陶瓷有限公司 Glaze material with metal luster for ceramics and glazing process thereof
CN111777433A (en) * 2020-07-08 2020-10-16 佛山市东鹏陶瓷有限公司 Preparation method of anti-oxidation ceramic glazed tile and prepared anti-oxidation ceramic glazed tile
CN112777933A (en) * 2021-03-23 2021-05-11 广东宏威陶瓷实业有限公司 Preparation process of cryolite ceramic tile and cryolite ceramic tile

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