CN101654409A - Divalent coloring metal citric acid ammonium salt and preparation method and application thereof - Google Patents
Divalent coloring metal citric acid ammonium salt and preparation method and application thereof Download PDFInfo
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- CN101654409A CN101654409A CN200910041926A CN200910041926A CN101654409A CN 101654409 A CN101654409 A CN 101654409A CN 200910041926 A CN200910041926 A CN 200910041926A CN 200910041926 A CN200910041926 A CN 200910041926A CN 101654409 A CN101654409 A CN 101654409A
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- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
- C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0006—Alkali metal or inorganic ammonium compounds
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0013—Iron group metal compounds
- C04B2103/0014—Fe
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0015—Noble metal or copper compounds
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/0004—Compounds chosen for the nature of their cations
- C04B2103/0015—Noble metal or copper compounds
- C04B2103/0016—Cu
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- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/54—Pigments; Dyes
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Abstract
The invention provides a divalent coloring metal citric acid ammonium salt and a preparation method thereof. The chemical general formula of the divalent coloring metal citric acid ammonium salt is NH4 MC6 H5 O7, wherein, M is divalent coloring metal ion, C6 H5 O7<3-> is a citric acid root ion with assistant permeation function. The preparation method comprises the following three steps: (1) divalent coloring metal subcarbonate synthesis; (2) divalent coloring metal citric acid salt synthesis; and (3) divalent coloring metal citric acid ammonium salt synthesis. The invention also provides an application of the divalent coloring metal citric acid ammonium salt in color-penetrated tiles production as penetrative liquid. The product of the invention is a single compound which has coloring metal ions and plays assistant permeation function radical at the same time, has the advantages of simple preparation, convenient color adjusting and stable storage; besides, the product separates out the foreign ions, such as Na, K, Cl and sulfate and the like in the synthetic process, can be as penetrative liquid to be used, can reduce baking process of impurity to the color-penetrated tiles and performance influences, and greatly improves quality and yield of the color-penetrated tiles.
Description
Technical field
The present invention relates to a kind of colorant, relate in particular to a kind of water-soluble colorant that ceramic pattern permeating tile is produced that is applied to, more specifically relate to the citric acid ammonium salt that a kind of divalence is non-ferrous metal.The invention still further relates to the preparation method and the application in ceramic pattern permeating tile is produced thereof of this divalent coloring metal citric acid ammonium salt.
Background technology
That the colored pattern permeating tile of pottery has is wear-resisting, corrosion-resistant, intensity is high, nonconducting characteristic, and the decorative effect that enriches of union marble, stamp color glazed brick is an one, and it is bright and clean as mirror, handsome free from vulgarity to have a surface of polished, the characteristics of intermingling flower colour coloured silk never drop-off.Colored pattern permeating tile is widely used in airport, market, station, harbour and large-scale place of public amusement etc., also is that household is indoor, hotel, office building ground, a kind of ideal material of decorating inner and external walls.
It generally is to adopt stronger soluble metal salt such as the copper sulfate of colour generation that chromatic ceramics oozes colored technology, venus crystals, single nickel salt, nickelous acetate, rose vitriol, cobaltous acetate or ferrous sulfate etc., with surfactant (penetration-assisting agent) as Trisodium Citrate, ammonium citrate, water-soluble together being mixed with such as EDTA disodium are oozed colored liquid, adopt method for printing screen, by designed with patterns, be printed onto on the ceramic tile blank oozing colored liquid, rely on base substrate to the adsorption of oozing colored liquid and penetration-assisting agent wetting osmosis to base substrate, the soluble metallic salt that colour generation is stronger infiltrates base substrate inside, forms multi color pattern at ceramic tile surface after high-temperature roasting.
Because it is compound that the preparation of oozing colored liquid needs plurality of raw materials to dissolve, sometimes also need heat, therefore there are problems such as process for preparation is consuming time, toning is inconvenient, preparation rear stability difference, in addition, the Na that chlorion that solubility inorganic metal salt is brought into or sulfate ion, penetration-assisting agent are brought into
+Or K
+Ion all will become the impurity that oozes colored liquid, and these impurity can influence performances such as the colored degree of depth of oozing of pattern permeating tile, hardness and fragility, reduce the quality and the yield of pattern permeating tile.
Summary of the invention
For overcoming the problem of above existence, the purpose of this invention is to provide and a kind ofly itself both had the colour generation metal ion, have again to rise and help the divalent coloring metal citric acid ammonium salt that oozes the action function group.
Another object of the present invention provides a kind of preparation method of above-mentioned divalent coloring metal citric acid ammonium salt.
A further object of the invention provides the application of above-mentioned divalent coloring metal citric acid ammonium salt in pattern permeating tile is produced.
For realizing above first purpose, divalent coloring metal citric acid ammonium salt of the present invention, its chemical general formula are NH
4MC
6H
5O
7, wherein M is a divalence colour generation metal ion, C
6H
5O
7 3-For having the citrate ion that helps the effect of oozing.
The divalent ion of metals such as the preferred Cu of above-mentioned divalence colour generation metal ions M, Fe, Ni or Co.
Because ammonium salt is easy to moisture absorption, in order to guarantee the stability of product in storage process, also for easy to use, above-mentioned divalent coloring metal citric acid ammonium salt exists with aqueous solution form, the components by weight percent of divalence colour generation metal ion is 6.5-7.5% in the aqueous solution, and pH value of aqueous solution is 7-8.
For realizing above-mentioned second purpose, the preparation method of above-mentioned divalent coloring metal citric acid ammonium salt in turn includes the following steps:
(1) divalence colour generation metal subcarbonate is synthetic;
(2) divalence colour generation metal citrate acid salt is synthetic;
(3) divalent coloring metal citric acid ammonium salt is synthetic.
Above-mentioned preparation method also comprises step (4), and this step is that the divalent coloring metal citric acid ammonium salt that above-mentioned steps (3) obtains is mixed with divalence colour generation metal ion components by weight percent with pure water is that 6.5-7.5%, pH value are the aqueous solution of 7-8.
Among the above-mentioned preparation method, the divalence colour generation metal subcarbonate of step (1) is to be reacted under 50-80 ℃ of temperature by solubility divalence colour generation aqueous metal salt (being designated as A solution) and carbonate or bicarbonate aqueous solution (being designated as B solution), the reaction end pH value of A solution and B solution is controlled at 7.5-8.5, when reaction finishes, continuation was at 50-80 ℃ of following insulated and stirred 30-40 minute, standing sedimentation is more than 1 hour then, extract supernatant out with siphon mode, stir to wash with pure water again and obtain throw out.
The reaction of above-mentioned steps (1) is that A solution or B solution are heated to 50-80 ℃, B solution or A solution is joined under whipped state in A solution or the B solution with the thread form again; The preferred divalence colour generation of A solution metal sulfate, nitrate, acetate or aqueous chloride solution, wherein divalence colour generation metal sulfate, nitrate, acetate or muriatic components by weight percent are 18-22%; The preferred yellow soda ash of B solution, sodium bicarbonate or the ammonium hydrogencarbonate aqueous solution, wherein the components by weight percent of yellow soda ash, sodium bicarbonate or ammonium hydrogencarbonate is 15-20%.
Above-mentioned steps (2) is the throw out that step (1) is obtained, stir the furnishing pulpous state with an amount of pure water, under constantly stirring, progressively add Citric acid monohydrate Food grade then, the add-on of the Citric acid monohydrate Food grade mol ratios such as divalence colour generation metal ion of (1) is set by step calculated, during reinforced finishing, heating and insulation under 70-80 ℃ are dissolved solids fully and solution does not have till the gas generation.If fail dissolving fully by the calculated amount postprecipitation thing that feeds intake, can suitably replenish Citric acid monohydrate Food grade.
Above-mentioned steps (3) is that the solution that step (2) obtains is cooled to 40 ℃ between the room temperature, under agitation slowly adds components by weight percent again and is 25% ammoniacal liquor and react; The add-on of the ammoniacal liquor mol ratios such as divalence colour generation metal ion of (1) is set by step calculated, and the pH value of reaction end is controlled at 7-8.
The present invention also provides the application that colored liquid is oozed in conduct in pattern permeating tile production of above-mentioned divalent coloring metal citric acid ammonium salt.This application is the depth of the pattern permeating tile color of producing as required, adds directly to carry out silk screen printing as oozing colored liquid on ceramic tile blank after water is regulated the concentration of divalent coloring metal citric acid ammonium salt, forms multi color pattern again after high-temperature roasting on the surface.
Divalent coloring metal citric acid ammonium salt of the present invention, owing to self not only had the colour generation metal ion, but also had and to work the functional group that helps the effect of oozing, therefore single compound just can play good colour developing osmosis, and exist with ammonium salts, can make citrate under neutral meta-alkalescence condition, have stronger penetrating power, and the ammonium salt back ammonia volatilization of being heated, can not stay foreign ion.Divalent coloring metal citric acid ammonium salt of the present invention, at room temperature place more than 1 year and deposited phenomenon do not occur, only need during use suitably to get final product after the dilution, and several solns can arbitrarily mix according to the toning needs, can not produce precipitation after the mixing, decompose the iso-metamorphism phenomenon, thereby avoid oozing the appearance of problems such as colored liquid process for preparation is consuming time, toning inconvenience, poor stability in the past.Preparation method of the present invention, step (1) is just separated foreign ions such as Na, K, Cl, sulfate radical when obtaining divalence colour generation metal base formula carbonate crystallization, and the reaction of step (2) and step (3) obtains is target product and water, do not bring new foreign ion into, therefore colored liquid is oozed in the divalent coloring metal citric acid ammonium salt conduct that is obtained by preparation method of the present invention, can reduce impurity to pattern permeating tile roasting process and Effect on Performance thereof, improve the quality and the recovery rate of pattern permeating tile greatly.
Embodiment
Be specific embodiments of the invention below, these embodiment to the specifying of divalent coloring metal citric acid ammonium salt synthetic method of the present invention, are not in order to restriction protection scope of the present invention just.
Embodiment 1
(1) with anhydrous sodium carbonate 10kg, in the synthetic pot of 100 liters of stainless steels, dissolve wiring solution-forming with pure water 45kg, be heated to 70-80 ℃ after insulation; With nickel sulfate hexahydrate 16kg, with being drawn into high-order charging tank after the pure water 30kg dissolving, under agitation join in the sodium carbonate solution and react in the thread mode, reaction process constantly has precipitation to generate, control reaction end pH value 8.0-8.5; When reaction does not have the precipitation generation, continuation was 70-80 ℃ of following insulated and stirred 30 minutes, standing sedimentation is 90 minutes then, siphon off supernatant, add pure water again to about 80 liters, be heated to 70-80 ℃ down insulation stir and washed 10 minutes, standing sedimentation siphon off supernatant liquor after 90 minutes again, so stir wash, quiet heavy, siphon 2 times repeatedly;
(2) in above-mentioned throw out, add about 10kg pure water, stir the furnishing pulpous state, under agitation add the Citric acid monohydrate Food grade of 13.5kg in batches, during reinforced finishing, reactant is heated to 70-80 ℃ of insulation down, solids is dissolved fully and solution does not have till the gas generation; Because reaction process has CO
2Gas produces, so Citric acid monohydrate Food grade will add in batches, divides what batches so that reaction is too not fierce and spill to be principle;
(3) open water coolant above-mentioned solution is cooled off, slowly add the 7.5kg components by weight percent and be 25% ammoniacal liquor under agitation condition and react, reaction end pH value is controlled between the 7-8; In order to prevent ammoniacal liquor volatilization and overreaction, above-mentioned solution is cooled to below 40 ℃, and room temperature is above for well;
(4) solution that step (3) is obtained moves to plastic tank, adds pure water to solution nt wt net weight 50kg, stirs evenly the back sampling and detects, and recording the pH value of solution value is 7.50, and nickel (Ni) content is 6.80%.
Embodiment 2
(1) anhydrous sodium carbonate 10kg is dissolved wiring solution-forming with pure water 45kg in the synthetic pot of 100 liters of stainless steels, be heated to 50-60 ℃ after insulation; Cupric sulfate pentahydrate 14kg is drawn into high-order charging tank with after the pure water 35kg dissolving, under agitation joins in the sodium carbonate solution in the thread mode and react, reaction process constantly has precipitation to generate, control reaction end pH value 8.0-8.5; When reaction does not have the precipitation generation, continuation was 70-80 ℃ of following insulated and stirred 30 minutes, standing sedimentation is 60 minutes then, siphon off supernatant, add pure water again to about 80 liters, be heated to 70-80 ℃ down insulation stir and washed 10 minutes, standing sedimentation siphon off supernatant liquor after 60 minutes again, so stir wash, quiet heavy, siphon 2 times repeatedly;
(2) in above-mentioned throw out, add about 10kg pure water, stir the furnishing pulpous state, under agitation add the Citric acid monohydrate Food grade of 13kg in batches, during reinforced finishing, reactant is heated to 60-70 ℃ of insulation down, solids is dissolved fully and solution does not have till the gas generation;
(3) open water coolant above-mentioned solution is cooled to below 40 ℃, slowly add the 8.0kg components by weight percent and be 25% ammoniacal liquor under agitation condition and react, reaction end pH value is controlled between the 7-8;
(4) solution that step (3) is obtained moves to plastic tank, adds pure water to solution nt wt net weight 50kg, stirs evenly the back sampling and detects, and recording the pH value of solution value is 8.00, and copper (Cu) content is 6.85%.
Embodiment 3
(1) iron vitriol 20kg is dissolved wiring solution-forming with pure water 35kg in the synthetic pot of 100 liters of stainless steels, be heated to 50-60 ℃ after insulation; Bicarbonate of ammonia 12kg is drawn into high-order charging tank with after the pure water 45kg dissolving, under agitation joins in the copperas solution in the thread mode and react, reaction process constantly has precipitation to generate, control reaction end pH value 7.5-8.0; When reaction does not have the precipitation generation, continuation was 50-60 ℃ of following insulated and stirred 30 minutes, standing sedimentation is 120 minutes then, siphon off supernatant, add pure water again to about 80 liters, be heated to 50-60 ℃ down insulation stir and washed 10 minutes, standing sedimentation siphon off supernatant liquor after 90 minutes again, so stir wash, quiet heavy, siphon 2 times repeatedly;
(2) in above-mentioned throw out, add about 10kg pure water, stir the furnishing pulpous state, under agitation add the Citric acid monohydrate Food grade of 15kg in batches, during reinforced finishing, reactant is heated to 60-70 ℃ of insulation down, solids is dissolved fully and solution does not have till the gas generation;
(3) open water coolant above-mentioned solution is cooled to below 40 ℃, slowly add the 9.0kg components by weight percent and be 25% ammoniacal liquor under agitation condition and react, reaction end pH value is controlled between the 7-8;
(4) solution that step (3) is obtained moves to plastic tank, adds pure water to solution nt wt net weight 50kg, stirs evenly the back sampling and detects, and recording the pH value of solution value is 8.00, and iron (Fe) content is 7.40%.
Embodiment 4
(1) anhydrous sodium carbonate 10kg is dissolved wiring solution-forming with pure water 45kg in the synthetic pot of 100 liters of stainless steels, be heated to 60-70 ℃ after insulation; Cobalt nitrate hexahydrate 18kg is drawn into high-order charging tank with after the pure water 35kg dissolving, under agitation joins in the sodium carbonate solution in the thread mode and react, reaction process constantly has precipitation to generate, control reaction end pH value 7.5-8.0; When reaction does not have the precipitation generation, continuation was 60-70 ℃ of following insulated and stirred 30 minutes, standing sedimentation is 120 minutes then, siphon off supernatant, add pure water again to about 80 liters, be heated to 60-70 ℃ down insulation stir and washed 10 minutes, standing sedimentation siphon off supernatant liquor after 90 minutes again, so stir wash, quiet heavy, siphon 2 times repeatedly;
(2) in above-mentioned throw out, add about 10kg pure water, stir the furnishing pulpous state, under agitation add the Citric acid monohydrate Food grade of 13.5kg in batches, during reinforced finishing, reactant is heated to 50-60 ℃ of insulation down, solids is dissolved fully and solution does not have till the gas generation;
(3) open water coolant above-mentioned solution is cooled to below 40 ℃, slowly add the 8.0kg components by weight percent and be 25% ammoniacal liquor under agitation condition and react, reaction end pH value is controlled between the 7-8;
(4) solution that step (3) is obtained moves to plastic tank, adds pure water to solution nt wt net weight 50kg, stirs evenly the back sampling and detects, and recording the pH value of solution value is 7.40, and cobalt (Co) content is 6.85%.
The divalent coloring metal citric acid ammonium salt aqueous solution that above embodiment obtains, be equivalent to produce the concentrated solution that oozes colored liquid that uses in the ceramic pattern permeating tile, during use, the depth of the pattern permeating tile color that can produce as required, add pure water and regulate the concentration of the divalent coloring metal citric acid ammonium salt aqueous solution, with in the past to ooze colored liquid the same, directly on ceramic tile blank, carry out silk screen printing, after high-temperature roasting, form multi color pattern again on the surface.
Claims (10)
1, a kind of divalent coloring metal citric acid ammonium salt is characterized in that: the chemical general formula of described divalent coloring metal citric acid ammonium salt is NH
4MC
6H
5O
7, wherein M is a divalence colour generation metal ion, C
6H
5O
7 3-For having the citrate ion that helps the effect of oozing.
2, divalent coloring metal citric acid ammonium salt according to claim 1 is characterized in that: the divalent ion of metals such as the preferred Cu of described divalence colour generation metal ions M, Fe, Ni or Co.
3, divalent coloring metal citric acid ammonium salt according to claim 1 and 2, it is characterized in that: described divalent coloring metal citric acid ammonium salt exists with aqueous solution form, the components by weight percent of divalence colour generation metal ion is 6.5-7.5% in the aqueous solution, and pH value of aqueous solution is 7-8.
4, the preparation method of the described divalent coloring metal citric acid ammonium salt of a kind of claim 1 in turn includes the following steps:
(1) divalence colour generation metal subcarbonate is synthetic;
(2) divalence colour generation metal citrate acid salt is synthetic;
(3) divalent coloring metal citric acid ammonium salt is synthetic.
5, the preparation method of divalent coloring metal citric acid ammonium salt according to claim 4, it is characterized in that: described preparation method also comprises step (4), and this step is that the divalent coloring metal citric acid ammonium salt that described step (3) obtains is mixed with divalence colour generation metal ion components by weight percent with pure water is that 6.5-7.5%, pH value are the aqueous solution of 7-8.
6, according to the preparation method of claim 4 or 5 described divalent coloring metal citric acid ammonium salts, it is characterized in that: the divalence colour generation metal subcarbonate of described step (1) is to be reacted under 50-80 ℃ of temperature by solubility divalence colour generation aqueous metal salt (being designated as A solution) and carbonate or bicarbonate aqueous solution (being designated as B solution), the pH value of A solution and B solution reaction terminal point is controlled at 7.5-8.5, when reaction finishes, continuation was at 50-80 ℃ of following insulated and stirred 30-40 minute, standing sedimentation is more than 1 hour then, stirs to wash with pure water again to obtain throw out.
7, want the preparation method of 6 described divalent coloring metal citric acid ammonium salts according to right, it is characterized in that: the reaction of described step (1) is that A solution or B solution are heated to 50-80 ℃, B solution or A solution is joined under whipped state in A solution or the B solution with the thread form again; The preferred divalence colour generation of A solution metal sulfate, nitrate, acetate or aqueous chloride solution, wherein divalence colour generation metal sulfate, nitrate, acetate or muriatic components by weight percent are 18-22%; The preferred yellow soda ash of B solution, sodium bicarbonate or the ammonium hydrogencarbonate aqueous solution, wherein the components by weight percent of yellow soda ash, sodium bicarbonate or ammonium hydrogencarbonate is 15-20%.
8, the preparation method of divalent coloring metal citric acid ammonium salt according to claim 6, it is characterized in that: described step (2) is the throw out that step (1) is obtained, stir the furnishing pulpous state with an amount of pure water, under constantly stirring, progressively add Citric acid monohydrate Food grade then, the add-on of the Citric acid monohydrate Food grade mol ratios such as divalence colour generation metal ion of (1) is set by step calculated, during reinforced finishing, heating and insulation under 70-80 ℃ are dissolved solids fully and solution does not have till the gas generation.
9, the preparation method of divalent coloring metal citric acid ammonium salt according to claim 8, it is characterized in that: described step (3) is that the solution that step (2) obtains is cooled to 40 ℃ between the room temperature, under agitation slowly adds components by weight percent again and is 25% ammoniacal liquor and react; The add-on of the ammoniacal liquor mol ratios such as divalence colour generation metal ion of (1) is set by step calculated, and the pH value of reaction end is controlled at 7-8.
10, the described divalent coloring metal citric acid ammonium salt of claim 1 is direct as the application of oozing colored liquid in pattern permeating tile production.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910041926 CN101654409B (en) | 2009-08-12 | 2009-08-12 | Preparation method of water soluble coloring metal for producing ceramic permeation pattern brick |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910041926 CN101654409B (en) | 2009-08-12 | 2009-08-12 | Preparation method of water soluble coloring metal for producing ceramic permeation pattern brick |
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| CN101654409B CN101654409B (en) | 2013-04-17 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112593234A (en) * | 2020-12-03 | 2021-04-02 | 南通恒兴电子材料有限公司 | Preparation method of ammonium citrate |
| CN116606167A (en) * | 2023-07-18 | 2023-08-18 | 广东新润成陶瓷有限公司 | Amazon texture pattern-penetrated brick and preparation method thereof |
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| CN1408679A (en) * | 2002-08-28 | 2003-04-09 | 佛山欧神诺陶瓷有限公司 | Method for producing pattern permeating ceramic tile |
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2009
- 2009-08-12 CN CN 200910041926 patent/CN101654409B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1408679A (en) * | 2002-08-28 | 2003-04-09 | 佛山欧神诺陶瓷有限公司 | Method for producing pattern permeating ceramic tile |
Non-Patent Citations (3)
| Title |
|---|
| 张太平 等: "柠檬酸铁铵的制备方法", 《高等函授学报(自然科学版)》 * |
| 罗耀宗 等: "代镉镀层-锡锌合金工艺", 《化学世界》 * |
| 赵庆生 等: "柠檬酸铁铵的制备", 《山西化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112593234A (en) * | 2020-12-03 | 2021-04-02 | 南通恒兴电子材料有限公司 | Preparation method of ammonium citrate |
| CN116606167A (en) * | 2023-07-18 | 2023-08-18 | 广东新润成陶瓷有限公司 | Amazon texture pattern-penetrated brick and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101654409B (en) | 2013-04-17 |
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