CN104163570B - A kind of bronze frit for porcelain enamel and preparation method thereof - Google Patents
A kind of bronze frit for porcelain enamel and preparation method thereof Download PDFInfo
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- CN104163570B CN104163570B CN201410424294.0A CN201410424294A CN104163570B CN 104163570 B CN104163570 B CN 104163570B CN 201410424294 A CN201410424294 A CN 201410424294A CN 104163570 B CN104163570 B CN 104163570B
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Abstract
The invention discloses a kind of bronze frit for porcelain enamel, it comprises borax decahydrate 4-6%, albite 12-14%, calcirm-fluoride 2-3%, brium carbonate 6-8%, calcium carbonate 4-7%, nickel monoxide 1-2%, zinc oxide 0.5-2%, lead orthoplumbate 12-15%, potash 2-5%, lithium carbonate 5-8%, sodium nitrate 32-35%, zircon sand 5-7%, molybdenum trioxide 0.5-1% and aluminium oxide 0.5%. The invention also discloses the preparation method of described bronze frit for porcelain enamel, and utilize bronze enamelware of described bronze frit for porcelain enamel making and preparation method thereof. The invention solves the problems such as the burst porcelain, crackle, burning shrinkage of traditional copper enamelware.
Description
Technical field
The invention belongs to copper enamel and make field, be specifically related to a kind of its preparation method of bronze frit for porcelain enamel and utilize this bronzeThe bronze enamelware that frit for porcelain enamel is made.
Background technology
Vitreous enamel is a kind of porcelain or vitrified inorganic thin film that is sintered at metal surface, and its Main Function is to underlying metalProtection and the outward appearance of beautifying metal product. Enamelware has the mechanical strength of metal and the stability of glass concurrently, widelyBe applied in daily life, as tableware, kitchen tools, wallboard, the art work and chemical field. Enamel in the marketGlaze is applicable to mild steel, and on the base materials such as cast iron, stainless steel and aluminium, cloisonne enamel glaze is applicable to red copper and few partBrass, gold, silver etc., extremely rare for the developmental research of bronze frit for porcelain enamel, the technical problem facing be mainly byIn the linear expansion coefficient of common frit for porcelain enamel higher or lower than bronze linear expansion coefficient 17 × 10-6/ DEG C, for example, ordinary steelThe linear expansion coefficient about 10～13 × 10 of plate frit for porcelain enamel-6/ DEG C, lower than the linear expansion coefficient 17 × 10 of copper-6/ DEG C, byIn the too large generation internal stress of coefficient of expansion gap, cause common frit for porcelain enamel and the bronze base material cannot strong bonded.
Summary of the invention
The present invention overcomes the problems referred to above that prior art exists, and innovation has proposed a kind of new for the bronze on bell metal base materialFrit for porcelain enamel and utilize this bronze frit for porcelain enamel to make the bronze enamelware obtaining. The present invention's bronze frit for porcelain enamel can be answeredFor for example bronze base material of part copper alloy base material, brass, on fine copper, with copper alloy base material strong bonded, thereby meets makingThe technological requirement of high-quality copper enamel product, has avoided the problems such as the burst porcelain in conventional art, crackle, burning shrinkage.
The present invention proposes a kind of bronze frit for porcelain enamel, it mass percent that comprises following component and each constituent content is: ten waterBorax 4-6%, albite 12-14%, calcirm-fluoride 2-3%, brium carbonate 6-8%, calcium carbonate 4-7%, nickel monoxide 1-2%, oxidationZinc 0.5-2%, lead orthoplumbate 12-15%, potash 2-5%, lithium carbonate 5-8%, sodium nitrate 32-35%, zircon sand 5-7%,Molybdenum trioxide 0.5-1%, aluminium oxide 0.5%.
The present invention's bronze frit for porcelain enamel, preferably, it mass percent that comprises following component and each constituent content is: ten water boronSand 4.08%; Albite 13.21%; Calcirm-fluoride 2.50%; Brium carbonate 7.50%; Calcium carbonate 5.26%; Nickel monoxide 1.35%;Zinc oxide 0.88%; Lead orthoplumbate 13.98%; Potash 3.99%; Lithium carbonate 6.86%; Sodium nitrate 33.26%; Zircon sand5.95%; Molybdenum trioxide 0.68%; And, aluminium oxide 0.5%.
The linear expansion coefficient of the present invention's bronze frit for porcelain enamel is 15～16 × 10-6/ DEG C. The present invention's bronze frit for porcelain enamel can be applicable toMeet on the bronze base material of enamel requirement, also applicable on other copper base materials, such as red copper, tombac etc. Separately, forThe detection of Enamel also can adopt the coefficient of cubical expansion, the coefficient of cubical expansion=linear expansion coefficient * 3.
The invention allows for a kind of preparation method of bronze frit for porcelain enamel, chemical raw material and mineral raw material are mixed allEven, under the environment of 1100～1200 degrees Celsius, melt, then cold quenching in cold water, obtains described bronze frit for porcelain enamel frit.In the method, described raw material comprise that the mass percent of following component and each constituent content is: borax decahydrate 4-6%, albite12-14%, calcirm-fluoride 2-3%, brium carbonate 6-8%, calcium carbonate 4-7%, nickel monoxide 1-2%, zinc oxide 0.5-2%, four oxidationsThree plumbous 12-15%, potash 2-5%, lithium carbonate 5-8%, sodium nitrate 32-35%, zircon sand 5-7%, molybdenum trioxide 0.5-1%,With aluminium oxide 0.5%.
The invention allows for a kind of bronze enamelware, it comprises bronze base material and is coated in the basis on described bronze base materialInvent bronze frit for porcelain enamel.
The invention allows for a kind of preparation method of bronze enamelware, its step comprises as follows:
(1) pre-treatment of bronze base material: comprise, bronze base material is carried out to surface cleaning, in bronze substrate surface sandblast;
(2) prepare the glaze slip of bronze frit for porcelain enamel: enamel frit of the present invention, add electrolyte, pigment, deionized water is outstandingAfter floating material, the glaze slip obtaining after grinding, all by 80 eye mesh screens; Then, by using air pressure spray gun to be sprayed atOn the bronze substrate surface that step (1) makes;
(3) dry, burn till and make bronze enamelware.
In the making of the present invention's bronze enamelware, the component of the bronze frit for porcelain enamel of employing and content can be with reference in above-mentionedHold. In bronze enamelware actual production, mineral raw material and chemical raw material have through the enamel stage of founding the mistake of burning, butIn the scope that all can estimate those skilled in the art.
Wherein, the linear expansion coefficient of described bronze frit for porcelain enamel is 15～16 × 10-6/ DEG C. Bronze frit for porcelain enamel linear expansion systemThe detection method of number is, in enamel melt stage, from the enamel of crucible (being positioned in stove) the inside liquid state, to extract " a glass outGlass silk ", finally get length 100mm diameter 0.1mm left and right, be positioned in thermal dilatometer, measure and take the photograph to 200 from 20 degrees CelsiusUnder family name's degree environment, the length variations of " glass fiber ". Test environment can be 20 degrees Celsius to 100 degrees Celsius, can be also20 degrees Celsius to 300 degrees Celsius.
In the preparation method of the present invention's bronze enamelware, adopt the bronze that is applicable to enamel as base material. Medium bronze of the present invention is generalRefer to that the copper alloy that enters other elements except zinc-nickel is additional is bronze. The present invention also can be adapted to red copper, on the base materials such as tombac.
In the preparation method of the present invention's bronze enamelware, wherein the preparation method of bronze frit for porcelain enamel used is: by above-mentioned groupDivide and take in proportion, above-mentioned various materials are pulverized respectively, then mix, molten under the environment of 1100～1200 degrees CelsiusChange and form fused mass, then cold quenching in cold water, obtains the enamel frit of described bronze frit for porcelain enamel.
Detect the present invention's bronze enamel product, be positioned in baking box, be warming up to after 150 degrees Celsius and constant 30 minutes, fastSpeed drops into cold water (room temperature), circulates 5 times. Testing result shows, porcelain facing is without visible damage, without coming off, in conjunction with firm, attachedPut forth effort well, to be significantly better than prior art.
The bronze enamel product that the inventive method makes, porcelain facing exquisiteness, glossiness is high, cooling rear enamel coating and copper base material strong bondedDo not come off, adhesive force is good, has solved the problems such as the burst porcelain, crackle, burning shrinkage of traditional copper enamelware.
The main component of enamel be by the refractory mineral such as feldspar, quartz raw material and the meltable chemical raw material such as borax, sodium nitrate andOther raw material, coordinates by a certain percentage, process high-temperature fusion and sharply cooling forming. Steel, stainless steel and iron in the marketFrit for porcelain enamel is applicable on the base material of steel, stainless steel and iron, but is not suitable on copper/copper alloy base material, is due to common (thisPlace general reference steel plate, cast iron, stainless steel enamel) linear expansion coefficient 10～14 × 10 of frit for porcelain enamel-6/ DEG C the linearity far below copperThe coefficient of expansion 17 × 10-6/ DEG C, therefore, in the time that these common frit for porcelain enamel are applied on copper/bronze base material, can cause enamel coatingProduce lines and split porcelain. And the present invention bronze frit for porcelain enamel has exactly solved common frit for porcelain enamel and copper base material linear expansion coefficient notThis technical problem of coupling. And the coefficient of expansion of the present invention's bronze frit for porcelain enamel reaches 15 × 10-6/℃～16×10-6/ DEG C, connectBe bordering on the linear expansion coefficient of bronze base material. Preferably, the linear expansion coefficient of copper enamel glaze of the present invention is 15 × 10-6/℃。
Result of study of the present invention shows, utilizes the present invention's bronze frit for porcelain enamel to fire copper enamel product, enamel can with copper/bronzeBase material is realized extraordinary combination, uses the copper enamel product of the present invention's bronze frit for porcelain enamel to ask without burst porcelain, crackle, burning shrinkage etc., there is not lines or split porcelain phenomenon in topic, porcelain facing exquisiteness, and glossiness is high, and enamel coating and bronze base material strong bonded do not come off.
Detailed description of the invention
In conjunction with following specific embodiment, the present invention is described in further detail, and protection content of the present invention is not limited to followingEmbodiment. Do not deviating under the spirit and scope of inventive concept, the variation that those skilled in the art can expect and advantage are all wrappedDraw together in the present invention, and taking appending claims as protection domain. Implement process of the present invention, condition, reagent, realityProved recipe methods etc., except the content of mentioning specially below, are universal knowledege and the common practise of this area, and the present invention does not have spyOther limiting content.
The making of embodiment 1 bronze frit for porcelain enamel
Take raw material and consumption: 40.8 grams of borax decahydrates, 132.1 grams of albites, 25 grams, calcirm-fluoride, 75 grams of brium carbonates, carbon52.6 grams of acid calcium, 13.5 grams of nickel monoxides, 8.8 grams, zinc oxide, 139.8 grams of lead orthoplumbates, 39.9 grams, potash, carbon68.6 grams of acid lithiums, 332.6 grams, sodium nitrate, 59.5 grams of zircon sands, 6.8 grams of molybdenum trioxides, 5 grams, aluminium oxide.
Manufacturing process: above-mentioned raw materials is mixed, melt under the environment of approximately 1200 degrees Celsius, form fused mass, thenBy this fused mass cold quenching in cold water, obtain enamel frit, i.e. bronze frit for porcelain enamel. In bronze frit for porcelain enamel finished product, partRaw material have through the enamel stage of founding the mistake of burning, but within the zone of reasonableness that all can estimate those skilled in the art.
The making of medium bronze frit for porcelain enamel of the present invention can be carried out with reference to prior art usual method. After testing, the above-mentioned bronze makingThe linear expansion coefficient of frit for porcelain enamel is 15 × 10-6/℃。
The raw material that the present invention is applicable and consumption are to comprise the mass percent of following component and each constituent content: borax decahydrate4-6%, albite 12-14%, calcirm-fluoride 2-3%, brium carbonate 6-8%, calcium carbonate 4-7%, nickel monoxide 1-2%, zinc oxide0.5-2%, lead orthoplumbate 12-15%, potash 2-5%, lithium carbonate 5-8%, sodium nitrate 32-35%, zircon sand 5-7%, threeMolybdenum oxide 0.5-1%, aluminium oxide 0.5%. Raw material are all Powdered, without pulverizing.
The making of embodiment 2 bronze enamelwares
The bronze frit for porcelain enamel that above-described embodiment is made is applied on bronze base material, makes bronze enamelware.
Manufacturing process is as follows:
(1) bronze pretreatment of base material: comprise, bronze base material is carried out to surface cleaning, and bronze base material carries out surface sand-blasting processing.
Particularly, bronze substrate surface sandblast, is used superfine quartz sand, spray in bronze substrate surface by air pressure,Effectively remove surface contaminant, impurity, oxide etc. As coarse in bronze substrate surface, there is the defects such as sand holes, can be by sandblastAfter bronze base material be soaked in dilute sulfuric acid and hydrogen peroxide mixing material, until bronze base material presents copper red look, clear after taking outWater rinses, sandblast again.
(2) preparation of glaze slip: prepare the glaze slip of bronze frit for porcelain enamel, through grinding, by using air pressure spray gun to be sprayed at green grass or young cropsCopper substrate surface.
First prepare the glaze slip of bronze frit for porcelain enamel, get the bronze frit for porcelain enamel that above-described embodiment makes, grind according to following proportioningMill: enamel (bronze frit for porcelain enamel) 100g, electrolyte 0.3g, suspension material 1-5g, pigment 5g-15g, deionized water45ml, puts in high aluminium ball grinding jar, grinds 5 minutes through Quick ball grinder, and the glaze slip obtaining, all by 80 eye mesh screens, obtainsTo the glaze slip of bronze frit for porcelain enamel. Then, use air pressure spray gun, aforementioned gained glaze slip is sprayed to the bronze base through pre-treatmentMaterial surface. The length of milling time can be adjusted according to the difference of milling apparatus. The present invention can adopt Quick ball grinder, productionWith grinding machines such as large-size ball mills. The granularity scope of the particle obtaining after grinding is 1-3 gram/50 milliliters/200 orders. ItsIn, electrolyte comprises natrium nitrosum, borax, potassium chloride etc. Suspension material comprises gum arabic, sodium carboxymethylcelluloseDeng.
(3) dry, burn till and make described bronze enamelware.
To spray the bronze enamelware of glaze slip, after within approximately 15 minutes under the ventilated environment of 80-150 degree Celsius, being dried, placedIn the electric furnace of the oxygen abundance of 780-820 degree Celsius, keep 5-8 minute, obtain bronze enamelware.
The bronze enamelware making comprises bronze base material and is coated in the bronze frit for porcelain enamel on this bronze base material. Estimate this green grass or young cropsThe smooth exquisiteness of porcelain facing of copper enamel goods, glossiness is high, and enamel coating and bronze base material strong bonded do not come off, and adhesive force is goodGood. The bronze enamelware making comprises the bronze enamelware of board with enamel panel layer, enamel bottle, enamelled cup or other arbitrary shapes. ThisInvent bronze frit for porcelain enamel and be also equally applicable on fine copper base material, make the copper enamel goods with above-mentioned advantage.
Adhesion test method and test result: the above-mentioned bronze enamelware making is positioned in baking box, is warming up to 150 and takes the photographFamily name's degree and after constant 30 minutes, drops into cold water (room temperature) fast, and iterative cycles operation 5 times, detects. Testing result shows,Porcelain facing is without visible damage, and without coming off, enamel coating is combined firmly with bronze base material.
Claims (6)
1. a bronze frit for porcelain enamel, is characterized in that, described bronze frit for porcelain enamel comprises the quality of following component and each constituent contentPercentage is: borax decahydrate 4-6%, and albite 12-14%, calcirm-fluoride 2-3%, brium carbonate 6-8%, calcium carbonate 4-7%,Nickel monoxide 1-2%, zinc oxide 0.5-2%, lead orthoplumbate 12-15%, potash 2-5%, lithium carbonate 5-8%, nitric acidSodium 32-35%, zircon sand 5-7%, molybdenum trioxide 0.5-1%, and aluminium oxide 0.5%.
2. bronze frit for porcelain enamel as claimed in claim 1, is characterized in that, it comprises the quality of following component and each constituent contentPercentage is: borax decahydrate 4.08%; Albite 13.21%; Calcirm-fluoride 2.50%; Brium carbonate 7.50%; Calcium carbonate5.26%; Nickel monoxide 1.35%; Zinc oxide 0.88%; Lead orthoplumbate 13.98%; Potash 3.99%; Lithium carbonate6.86%; Sodium nitrate 33.26%; Zircon sand 5.95%; Molybdenum trioxide 0.68%; With aluminium oxide 0.5%.
3. bronze frit for porcelain enamel as claimed in claim 1, is characterized in that, the linear expansion coefficient of described bronze frit for porcelain enamel is15～16×10-6/℃。
4. a preparation method for bronze frit for porcelain enamel, is characterized in that, raw material is mixed, at 1100～1200 degrees CelsiusUnder environment, fusing obtains fused mass, by aforementioned fused mass cold quenching in cold water, obtains bronze as claimed in claim 1 or 2 and wards offGlaze frit; Wherein, described raw material comprise that the mass percent of following component and each constituent content is: borax decahydrate4-6%, albite 12-14%, calcirm-fluoride 2-3%, brium carbonate 6-8%, calcium carbonate 4-7%, nickel monoxide 1-2%, oxidationZinc 0.5-2%, lead orthoplumbate 12-15%, potash 2-5%, lithium carbonate 5-8%, sodium nitrate 32-35%, zircon sand5-7%, molybdenum trioxide 0.5-1%, and aluminium oxide 0.5%.
5. a bronze enamelware, is characterized in that, described bronze enamel product comprises bronze base material and is coated in described bronzeBronze frit for porcelain enamel on base material, wherein, described bronze frit for porcelain enamel is bronze vitreous enamel as claimed in claim 1 or 2Material.
6. a preparation method for bronze enamelware, is characterized in that, it comprises the steps:
(1) pre-treatment of bronze base material: bronze base material is carried out to surface cleaning, and bronze base material carries out surface sand-blasting;
(2) prepare the glaze slip of bronze frit for porcelain enamel, after being ground, be sprayed at bronze substrate surface; Wherein, described bronze enamelGlaze is bronze frit for porcelain enamel as claimed in claim 1;
(3) drying, burn till and make bronze enamelware as claimed in claim 5.
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| CN108569849A (en) * | 2018-06-26 | 2018-09-25 | 浙江开尔新材料股份有限公司 | A kind of enamel suspending agent and the enamelled pressed steel with it |
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|---|---|---|---|---|
| CN1799873A (en) * | 2006-01-10 | 2006-07-12 | 张维 | Process for preparing metallic enamel embossment |
| FR2904329A1 (en) * | 2006-07-28 | 2008-02-01 | Critt Z3T Ass Loi De 1901 | Bronze object enamel coating process to give artistic looks involves heat treatment,stripping,enameling and baking |
| CN101565273A (en) * | 2009-05-08 | 2009-10-28 | 张立涛 | Vitreous enamel material, preparation method thereof and method for preparing vitreous enamel blue-white porcelain from vitreous enamel material |
| CN103060804A (en) * | 2012-12-25 | 2013-04-24 | 佛山市唯艺金属制品有限公司 | Aluminum enamel process and building material products manufactured by the same |
| CN103276396A (en) * | 2013-05-31 | 2013-09-04 | 哈尔滨工业大学 | Method for enameling temperature-resistant enamel materials for 1Cr18Ni9Ti stainless steel surface |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1799873A (en) * | 2006-01-10 | 2006-07-12 | 张维 | Process for preparing metallic enamel embossment |
| FR2904329A1 (en) * | 2006-07-28 | 2008-02-01 | Critt Z3T Ass Loi De 1901 | Bronze object enamel coating process to give artistic looks involves heat treatment,stripping,enameling and baking |
| CN101565273A (en) * | 2009-05-08 | 2009-10-28 | 张立涛 | Vitreous enamel material, preparation method thereof and method for preparing vitreous enamel blue-white porcelain from vitreous enamel material |
| CN103060804A (en) * | 2012-12-25 | 2013-04-24 | 佛山市唯艺金属制品有限公司 | Aluminum enamel process and building material products manufactured by the same |
| CN103276396A (en) * | 2013-05-31 | 2013-09-04 | 哈尔滨工业大学 | Method for enameling temperature-resistant enamel materials for 1Cr18Ni9Ti stainless steel surface |
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