CN102249739A - Preparation method of carbon-golden metallic luster crystalline glaze - Google Patents

Preparation method of carbon-golden metallic luster crystalline glaze Download PDF

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CN102249739A
CN102249739A CN2011101383892A CN201110138389A CN102249739A CN 102249739 A CN102249739 A CN 102249739A CN 2011101383892 A CN2011101383892 A CN 2011101383892A CN 201110138389 A CN201110138389 A CN 201110138389A CN 102249739 A CN102249739 A CN 102249739A
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glaze
parts
speed
crystalline
golden
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CN102249739B (en
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韩晓伟
赵玉虎
孔德双
谷昌军
陈春明
孔令仁
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Jiangsu Gaochun Ceramics Co.,Ltd.
SHANXI GAOTAO PORCELAIN Co.,Ltd.
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JIANGSU GAOCHUN CERAMICS CO Ltd
SHANXI GAOTAO PORCELAIN CO Ltd
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Abstract

The invention relates to a preparation method of a carbon-golden metallic luster crystalline glaze. The carbon-golden metallic luster crystalline glaze comprises the following component in parts by mass: 25-30 parts of MnO2 as crystallizing agent, 0.5-1.5 parts of MoO2, 0.5-1.5 parts of V2O5 as crystallization accelerator, 2-4.5 parts of CuO, 2.5-5 parts of Fe2O3, 3-7 parts of ZnO and 0.5-2.5 parts of NiO as colorants, 30-38 parts of potash feldspar produced in Pingjiang, 5-12 parts of quartz produced in Fengyang, 5-10 parts of talcum powder produced in Wuxi, and 5-12 parts of boron fusion cake produced in Yixing. The prepared glaze slip is applied onto a biscuited green body, and subjected to glaze firing according to the temperature curve in the invention. The carbon-golden metallic luster crystalline glaze has carbon-golden metallic luster, rainbow effect and beautiful appearance of crystals. Besides, the carbon-golden metallic luster crystalline glaze has the advantages of low cost, high glaze hardness, high wear resistance and high corrosion resistance, is a brand new glaze of ceramic art, and can be used for decorating ceramic artware.

Description

The preparation method of the golden metalluster crystalline glaze of a kind of charcoal
Technical field
The present invention relates to the preparation method of the golden metalluster crystalline glaze of a kind of charcoal.
Background technology
The metalluster crystalline glaze is that glaze produces outer appearnce such as color harmony gloss like certain metal and contain the ceramic glaze of xln, is a kind of new ceramics artistic glaze that developed recently gets up.It not only has the aesthetic feeling of the luster effect and the xln of metal, and has characteristics such as the ceramic glaze cost is low, hardness of glaze surface is high, wear resistance is good, corrosion-resistant.Metalluster is because tiny needle-like crystal densification interweaves to due to the strong reflection of light intensity, makes glaze present thick and heavy solid, luxurious gorgeous sensation.The report of relevant metalluster crystalline glaze is many, but does not find the report of the golden metalluster crystalline glaze of charcoal at present as yet.
CN1521145 discloses a kind of construction sanitary ceramic metalluster crystalline glaze, it is with zinc oxide, silicon oxide or titanium oxide are the one-tenth eutectic substance of glaze, with low temperature frit, boric acid is for forming the Vitrea flux raw material of glaze, with cupric oxide, ferric oxide, manganese oxide, metal oxides such as titanium oxide are tinting material, be prepared by common ceramic glaze production technique, impose on the surface of construction sanitary ceramic, by burning till continuously fast of being fit to, adopt short insulation to educate the distinct temperature curve in brilliant cycle, glaze is formed have the glass-ceramic layer of metalluster, the decorative effect of its existing metalluster like this, the physical strength that has devitrified glass again can be widely used in various architectural potteries, the surface decoration of sanitary ceramic ware.
CN100575310C discloses a kind of method of manufacturing golden yellow mirror surface glaze, this glaze comprises zinc oxide, rhombspar, titanium oxide, calcite, no lead frit, kaolin, silica powder, cupric oxide, manganese oxide, Vanadium Pentoxide in FLAKES, 11 kinds of raw materials of ferric oxide, and wherein cupric oxide and manganese oxide are coloring oxide; During making,, sieve then,, get bright and clean porcelain blank and soak to go into kiln behind the glaze and under 1160～1200 ℃ oxidizing atmosphere, fire and form by the concentration of 45～60 degree Beaume allotment slurry by wet ball grinding, the flicker of gained finished product glaze golden light, sparkling, coloured and dazzling.CN100537487C discloses a kind of making method of placer gold glaze material, after this glaze burns till in 1170～1200 ℃ of oxidizing atmospheres fast, glaze Venus brilliance, flicker under ordinary ray irradiation is luminous, glittering especially, gorgeous luxurious under shining than the high light line, comprise borax, boric acid and sodium, two kinds of carbonate of potassium in the described glaze, also be added with quartzy and albite and a small amount of clay and some tinting materials.During making, earlier borax and carbonate are made frit, extremely pass through 250 mesh sieves with quartz, albite, clay and tinting material ball milling again after frit is pulverized, it is 0.15～0.3mm that the glaze layer is implemented thickness.The influence of calcining system to the glazed metal luster effect reported in " Chinese pottery industry " 2008 (04), adopting kaolin, quartz, feldspar etc. is raw material, with manganese oxide, cupric oxide is that the crystallization agent prepares metal-lustrous glaze, and having inquired into calcining systems such as firing temperature, soaking time influences rule to the glazed metal glossy.The result shows: under current prescription was formed, 1120 ℃ of following glaze firing also were incubated 30 minutes, and the back is at 820 ℃ of following slow coolings to 620 ℃, and glaze has the good metal luster effect.
" Chinese pottery " 2008 (08) reported the influence of the paired glazed metal luster effect of ingredient groups, and adopting kaolin, quartz, feldspar etc. is raw material, and introduces cupric oxide, manganese oxide as the crystallization agent, the preparation metal-lustrous glaze.Inquired into SiO in the prescription 2/ Al 2O 3Ratio, the content of crystallization agent, the content of PbO influence rule to the glazed metal glossy.Experimental result shows: work as SiO 2/ Al 2O 3Than being 10, the content of crystallization agent is 5%, and the content of PbO is 40% o'clock, and under suitable calcining system, glaze has the good metal luster effect.
" Wuhan University of Technology's journal " 2009 (12) reported CuO-MnO 2-V 2O 5-TiO 2Being metal-lustrous glaze and structure thereof, is main raw material with Suzhou soil, BF235-1 frit, by adjusting metal oxide photoghraphic coupler CuO, MnO 2, V 2O 5, TiO 2Addition, adopt different calcining systems prepared simple to operate, control is convenient, is fit to the golden yellow metal-lustrous glaze that burns till fast.Having inquired into calcining system, metal oxide addition, glaze layer thickness influences the glaze glossy.Adopt the modern measuring technology of SEM that the glaze layer is carried out morphology observation, studies show that crystal growth has certain orientation, and all be parallel to the distribution of glaze laminar surface.
Summary of the invention
The objective of the invention is:Aim to provide the preparation method of the golden metalluster crystalline glaze of a kind of charcoal, it not only has the aesthetic feeling of the luster effect and the xln of metal, and have characteristics such as the ceramic glaze cost is low, hardness of glaze surface is high, wear resistance is good, weathering resistance is good, corrosion-resistant, be a kind of brand-new ceramic artistic glaze, can be used for decorative porcelain artwork and tableware for Western-style food.
Technical scheme of the present invention is:The preparation method of the golden metalluster crystalline glaze of charcoal, the source of its glaze and consist of (mass parts): adopt 25～30 MnO 2Be crystallizing agent, 0.5～1.5 MoO 2With 0.5～1.5 V 2O 5Be crystallization promoter, 2～4.5 CuO, 2.5～5 Fe 2O 3, 3～7 ZnO and 0.5～2.5 multiple metal oxides such as NiO be tinting material, other composition is that potassium felspar sand is produced in Pingjiang River of 30～38, Fengyang of 5～12 is produced quartzy, 5～10 Wuxi is produced Yixing of talcum powder and 5～12 and is produced boron frit etc.
Glaze slip preparation: the compositing formula by glaze takes by weighing raw material respectively, and in raw material: ballstone: water equals ratio ball milling in ball mill of 1:1.5:1, tails over and gets final product when being (mass percent) below 0.05 when the glaze slip fineness reaches 250 mesh sieves.
The glaze firing technique that adopts is: beginning is warming up to 100 ± 10 ℃ with 0.8～1.2 ℃/min speed, be warming up to 600 ± 20 ℃ with 1.6～2.2 ℃/min speed then, be warming up to 750 ± 20 ℃ with 1.0～1.4 ℃/min speed then, be incubated 40～60min after being warming up to 950～1000 ℃ with 1.6～2.2 ℃/min speed then, be incubated 100～140min after being warming up to 1230 ± 20 ℃ with 1.6～2.2 ℃/min speed then, be incubated 20～30 min after being cooled to 1130 ± 20 ℃ with 3.0～5.0 ℃/min speed then, be cooled to 850 ± 20 ℃ with 2.0～4.0 ℃/min speed then, be cooled to 600 ± 20 ℃ with 1.5～3.0 ℃/min speed then, naturally cool to room temperature at last, obtain product.
Glazing process is: with soaking glaze or waterfall process glaze slip is imposed on the biscuiting base substrate once, the water-intake rate of biscuiting base substrate should be 1.5～3.5%, and the glaze layer thickness is 0.2～0.4mm, dries.
The crystalline glaze chemical ingredients of making is (mass parts): SiO 2Be 40～50, Al 2O 3Be 3～10, Fe 2O 3Be 2.5～5, CaO is 0.1～0.7, and MgO is 2.5～5, K 2O is 2.5～5, Na 2O is 0.5～1.5, MoO 2Be 0.5～2, B 2O 3Be 0.4～1.0, CuO is 2～2.5, and NiO is 0.5～2.5, and ZuO is 3～7, V 2O 5Be 0.5～1.5, MnO 2Be 25～30, BaO is 0.0.5～0.1, and other component is less than 0.5.
Charcoal 3 requirements that golden metalluster crystalline glaze forms are provided: the one, exist in the glaze melt enough to make glaze at high temperature present hypersaturated state, excessive MnO that its crystal property is good 2The 2nd, an amount of MoO is arranged 2, V 2O 5Be crystallization promoter, CuO, Fe are arranged 2O 3, multiple metal oxides such as ZnO, NiO are tinting material; The 3rd, have to be adapted to the insulation process of cooling that this molten matter nucleus forms and grows up and grow.Therefore 2 relevant critical processes are: the one, and the glaze preparation; The 2nd, glaze firing system, particularly process of cooling control.
Zinc oxide in the raw material, talcum preferably carry out preroasting removing organic impurities, thereby the glaze defective that contracts when reducing glaze firing is improved glaze quality, and calcining temperature is 1200～1300 ℃, and the time is 10～60 min.
The proportion of preferably regulating glaze slip is 1.2～1.4g/cm 3
The glaze formula, glaze slip complete processing, glazing process and the specific calcining system that are uniqueness of the technical scheme of the golden metalluster crystalline glaze preparation of charcoal.
The invention has the beneficial effects as follows:Strong reflection forms golden metalluster of charcoal and rainbow effect to product to light intensity because of the interlacing tiny needle-like crystal of densification, its low cost of manufacture, hardness of glaze surface height, wear resistance are good, corrosion-resistant good, be a kind of brand-new ceramic artistic glaze, can be used for the decorative porcelain artwork.Its another characteristics are that harmful lead of goods and quantity of cadmium release all do not detect (wherein plumbous detecting is limited to 0.2mg/L, and detecting of cadmium is limited to 0.02mg/L), are used as tableware and decorate fool proof.
Description of drawings
Fig. 1 utilizes the finished product photo of 8 inch ceramic discs of the golden metalluster crystalline glaze modification of charcoal for the present invention.
Embodiment
According to the performance index that the golden metalluster crystalline glaze of charcoal will reach, as follows to the embodiment of operational path, material and production method:
At first be stoneware tableware biscuiting base substrates such as preparation square position, bowl, its chemical constitution is (mass parts): SiO 2Be 60 ~ 75, Al 2O 3Be 18 ~ 30, Fe 2O 3Be 1.0 ~ 2.0, CaO is 0.5 ~ 1.5, and MgO is 0.1 ~ 0.4, K 2O is 1.0 ~ 3.0, Na 2O is 0.1 ~ 0.8, and other are 5 ~ 15 years old.The biscuiting temperature of base substrate is 950～1050 ℃, and water-intake rate is 1.5%～3.5%, and base substrate need be polished totally stand-by.
The selection and the glaze slip that are raw material are then made.The source of glaze and composition (mass parts) are: adopt 25～30 MnO 2Be crystallizing agent, 0.5～1.5 MoO 2With 0.5～1.5 V 2O 5Be crystallization promoter, 2～4.5 CuO, 2.5～5 Fe 2O 3, 3～7 ZnO and 0.5～2.5 multiple metal oxides such as NiO be tinting material, other composition is that potassium felspar sand is produced in Pingjiang River of 30～38, Fengyang of 5～12 is produced quartzy, 5～10 Wuxi is produced Yixing of talcum powder and 5～12 and is produced boron frit etc.Glaze slip preparation technology: take by weighing raw material respectively by prescription, and in raw material: ballstone: water equals ratio ball milling in ball mill of 1:1.5:1, tail over and get final product when being (mass percent) below 0.05 when the glaze slip fineness reaches 250 mesh sieves, the proportion of regulating glaze slip is 1.2～1.4g/cm 3
The MnO of major control 25 of the present invention or 30 parts 2Crystallizing agent, and distinguish 0.5 or 1.5 part MoO 2, 0.5 or 1.5 part V 2O 5, condition under good effect is all arranged; A wider range of metallochrome: as adopt 2,3 or 4.5 parts CuO; Add 2.5,3 or 5 parts Fe 2O 3Add 3,5 or 7 parts ZnO; The NiO metal oxide that adds 0.5,1 or 2.5 part is the effect that tinting material all has charcoal non-ferrous metal gloss crystalline glaze of the present invention.It is not too high that other composition requires on the accurate counterweight of component comparatively speaking.
Glazing process on tableware biscuiting base substrate is: with soaking glaze or waterfall process glaze slip is imposed on the biscuiting base substrate once, the water-intake rate of biscuiting base substrate should be 1.5～3.5%, and the glaze layer thickness is 0.2～0.4mm, dries.
The glaze firing system is: beginning is warming up to 100 ℃ with 0.8～1.2 ℃/min speed, be warming up to 600 ℃ with 1.6～2.2 ℃/min speed then, be warming up to 750 ℃ with 1.0～1.4 ℃/min speed then, be incubated 40～60min after being warming up to 950～1000 ℃ with 1.6～2.2 ℃/min speed then, be incubated 100～140min after being warming up to 1230 ℃ with 1.6～2.2 ℃/min speed then, be incubated 20～30 min after being cooled to 1130 ℃ with 3.0～5.0 ℃/min speed then, be cooled to 850 ℃ with 2.0～4.0 ℃/min speed then, be cooled to 600 ℃ with 1.5～3.0 ℃/min speed then, above temperature control point allows controlled deviation in 10～20 ℃ scope.Naturally cool to room temperature at last, obtain product.Carrying out product performance at last detects.
Embodiment:According to above-mentioned the golden metalluster crystalline glaze of charcoal embodiment has been made each 100 in 8 inch square positions, 220ml coffee cup and 8 inch bowls, its salient features is as follows:
1, the product glaze is smooth soft, has the golden metalluster of charcoal, rainbow effect and crystallization aesthetic feeling, and color and luster is evenly beautiful, the MoO of adding 2And V 2O 5Crystallization promoter can promote the generation of xln, makes the structure of metalluster crystalline glaze fine and close more.
2, the crystalline glaze chemical ingredients of making is (mass parts): SiO 2Be 40～50, Al 2O 3Be 3～10, Fe 2O 3Be 2.5～5, CaO is 0.1～0.7, and MgO is 2.5～5, K 2O is 2.5～5, Na 2O is 0.5～1.5, MoO 2Be 0.5～2, B 2O 3Be 0.4～1.0, CuO is 2～2.5, and NiO is 0.5～2.5, and ZuO is 3～7, V 2O 5Be 0.5～1.5, MnO 2Be 25～30, BaO is 0.0.5～0.1, and other component is less than 0.5.
3, Heat stability is good does not ftracture at 1 glaze layer of 20～200 ℃ of heat exchanges.
4, lead release is lower than the 0.2mg/L(detection limit), quantity of cadmium release is lower than the 0.02mg/L(detection limit).

Claims (4)

1. the preparation method of the golden metalluster crystalline glaze of charcoal is characterized in that the source of glaze and consists of (mass parts): adopts 25～30 parts MnO 2Be crystallizing agent, 0.5～1.5 part MoO 2V with 0.5～1.5 part 2O 5Be crystallization promoter, 2～4.5 parts CuO, 2.5～5 parts Fe 2O 3, 3～7 parts ZnO and many kinds of metal oxides of NiO of 0.5～2.5 part are tinting material, other composition is that potassium felspar sand is produced in 30～38 parts the Pingjiang River, Fengyang of 5～12 parts is produced quartzy, 5～10 parts Wuxi is produced Yixing of talcum powder and 5～12 parts and is produced the boron frit;
Glaze slip preparation: the compositing formula by glaze takes by weighing raw material respectively, and in raw material: ballstone: water equals ratio ball milling in ball mill of 1:1.5:1, tails over and gets final product when being (mass percent) below 0.05 when the glaze slip fineness reaches 250 mesh sieves;
Glaze slip imposes on the glaze firing technique that adopt the back on the biscuiting base substrate: beginning is warming up to 100 ± 10 ℃ with 0.8～1.2 ℃/min speed, be warming up to 600 ± 20 ℃ with 1.6～2.2 ℃/min speed then, be warming up to 750 ± 20 ℃ with 1.0～1.4 ℃/min speed then, be incubated 40～60min after being warming up to 950～1000 ℃ with 1.6～2.2 ℃/min speed then, be incubated 100～140min after being warming up to 1230 ± 20 ℃ with 1.6～2.2 ℃/min speed then, be incubated 20～30 min after being cooled to 1130 ± 20 ℃ with 3.0～5.0 ℃/min speed then, be cooled to 850 ± 20 ℃ with 2.0～4.0 ℃/min speed then, be cooled to 600 ± 20 ℃ with 1.5～3.0 ℃/min speed then; Naturally cool to room temperature at last, obtain product.
2. the preparation method of the golden metalluster crystalline glaze of charcoal according to claim 1 is characterized in that the crystalline glaze chemical ingredients of making is (mass parts): SiO 2Be 40～50, Al 2O 3Be 3～10, Fe 2O 3Be 2.5～5, CaO is 0.1～0.7, and MgO is 2.5～5, K 2O is 2.5～5, Na 2O is 0.5～1.5, MoO 2Be 0.5～2, B 2O 3Be 0.4～1.0, CuO is 2～2.5, and NiO is 0.5～2.5, and ZuO is 3～7, V 2O 5Be 0.5～1.5, MnO 2Be 25～30, BaO is 0.0.5～0.1, and other component is less than 0.5.
3. the preparation method of the golden metalluster crystalline glaze of charcoal according to claim 1 is characterized in that zinc oxide, the talcum in the raw material carries out preroasting to remove organic impurities, and pre-calcination temperature is 1200～1300 ℃, and the time is 10～60 min.
4. the preparation method of the golden metalluster crystalline glaze of charcoal according to claim 1, the proportion that it is characterized in that regulating glaze slip is 1.2～1.4g/cm 3, glazing process is: with soaking glaze or waterfall process glaze slip is imposed on the biscuiting base substrate once, the water-intake rate of biscuiting base substrate should be 1.5～3.5%, and the glaze layer thickness is 0.2～0.4mm, dries.
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CN102659453A (en) * 2012-04-01 2012-09-12 江苏拜富科技有限公司 Crystal glaze and its preparation method and use method
CN103332965A (en) * 2013-07-02 2013-10-02 泉州欧米克生态建材科技有限公司 Golden yellow crystallized dry-granular glaze and using method thereof
CN104211444A (en) * 2014-09-03 2014-12-17 江苏省宜兴彩陶工艺厂 Preparation method of furnace transmutation sorghum red-flower glaze
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CN104496560A (en) * 2014-12-06 2015-04-08 李婷 Method for preparing golden-yellow-needle-shaped crystal ceramic artwork
CN105016779A (en) * 2014-03-24 2015-11-04 李甲栈 Crystalline glaze ceramic glaze
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CN101066894A (en) * 2007-06-14 2007-11-07 醴陵玉茶瓷业有限公司 Medium and high temperature sintered coarse crystalline Fe-Ti glaze and its prepn process
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CN102659453A (en) * 2012-04-01 2012-09-12 江苏拜富科技有限公司 Crystal glaze and its preparation method and use method
CN102659453B (en) * 2012-04-01 2014-09-17 江苏拜富科技有限公司 Crystal glaze and its preparation method and use method
CN103332965A (en) * 2013-07-02 2013-10-02 泉州欧米克生态建材科技有限公司 Golden yellow crystallized dry-granular glaze and using method thereof
CN103332965B (en) * 2013-07-02 2015-01-21 泉州欧米克生态建材科技有限公司 Golden yellow crystallized dry-granular glaze and using method thereof
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CN105016779A (en) * 2014-03-24 2015-11-04 李甲栈 Crystalline glaze ceramic glaze
CN104211444A (en) * 2014-09-03 2014-12-17 江苏省宜兴彩陶工艺厂 Preparation method of furnace transmutation sorghum red-flower glaze
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