CN100519668C

CN100519668C - Novel chromium-tin purple dye and its preparing method

Info

Publication number: CN100519668C
Application number: CNB2005100178128A
Authority: CN
Inventors: 胡秋帆; 赵玛
Original assignee: Individual
Current assignee: Individual
Priority date: 2005-07-21
Filing date: 2005-07-21
Publication date: 2009-07-29
Anticipated expiration: 2025-07-21
Also published as: CN1900176A

Abstract

The present invention discloses one new kind of chromium-tin purple dye and its wet preparation process. The chromium-tin purple dye is prepared with tin salt, chromium oxide or salt, RE metal compound, precipitant and dispersant, and through liquid phase reaction and high temperature sintering. The prepared chromium-tin purple dye is RE blended crystal in nanometer level, and has the advantages of high grinding resistance, high heat resistance, high stability, pure color and excellent colorating property. It may be used in glaze and ceramic to result in excellent effect.

Description

A kind of novel chromium-tin purple dye and preparation method thereof

Technical field

The bright a kind of pigment and preparation method thereof that relates to of this law relates in particular to a kind of chromium-tin purple dye and preparation method thereof.

Background technology

Beramic color is to introduce the most basic chromonic material in the ceramic colour glaze, and violet pigment is a kind of in the beramic color, traditional technology be oxide compound by the oxide compound of tin and chromium through mixing, ball milling, sintering, in tindioxide, fuse into chromium admittedly and form just usually said dry method.The problem that this method for preparing the purple material is brought is, because raw material particle size is thicker, it is wide to distribute, and to sintering reaction requirement condition height, the crystalline form instability is difficult for making, and form and aspect are inclined to one side, and instability.Beramic color is one of novel material kind of China's current urgent need development, for this reason, develops stable crystal formation, the positive chromium-tin purple dye of form and aspect is that market is required.

Summary of the invention

The object of the invention is to provide that a kind of colour generation is pure, bright-coloured, good stability, high temperature resistant sintering novel chromium-tin purple dye, and another purpose of the present invention is to provide the preparation method of this violet pigment.

For realizing the object of the invention, technical solution of the present invention is as follows:

The present invention adopts inorganic salt sol-gel wet method preparation process, and by the oxide compound of metal pink salt, chromium or its salt, rare earth compound or their mixture, viscosity modifier, dispersion agent, sinking agent, through liquid phase reaction, high temperature sintering forms.Concrete technology is as follows: be dissolved in oxide compound or its salt of an amount of metal pink salt and chromium in the distilled water respectively, solvent pink salt is placed reactor, be warming up to 40-95 ℃ of temperature of reaction, add rare earth compound or their mixture, viscosity modifier, dispersion agent and regulator solution PH are 2-7, oxide compound or its salts solution with chromium drips then, add in the reactor, in 2-5 minute, dropwise, reacted 2-3 hour, add the sinking agent precipitation, liquid-solid separation, wash impurity elimination with distilled water, after 45-100 ℃ of following drying, in 700-1400 ℃ of sintering, obtain chromium-tin purple dye of the present invention, this pigment is the nanoscale solids powder, has nuclear/shell crystalline structure, and its crystal is by rear-earth-doped.

The weight percent of the reactant composition that the present invention is selected is: metal pink salt 10%-65% is preferably 15%-55%, the oxide compound of chromium or its salt 0.05%-5%, be preferably 0.2%-3%, rare earth compound 0.2%-5% is preferably 0.5%-2%, dispersion agent 0.05%-0.5%, be preferably 0.2%-0.4%, viscosity modifier 0.1-10% is preferably 0.2-8%, sinking agent 0.1-10%, be preferably 0.3-7%, surplus is a distilled water.

Used metal pink salt is one of following kind: tin sulphate, stannous sulfate, tin acetate, stannous acetate, nitric acid tin, tin chloride, tin protochloride.

The oxide compound of used chromium and salt thereof are one of following kind: chromium sesquioxide, Sodium chromate, sodium dichromate 99, potassium bichromate, ammonium dichromate.

Used rare-earth compound or their mixture are following kind: yttrium sulfate, Neodymium trichloride, europium sulfate, praseodymium sulfate.

The dispersion agent that adds in the reaction solution is a tensio-active agent, is one of following kind: alkylphenol polyoxyethylene, sodium methylene bis-naphthalene sulfonate.

The viscosity modifier that adds in the reaction solution is one of following kind: polyvinyl alcohol, low molecular weight sodium polyacrylate, Xylo-Mucine, gelatin.

The sinking agent that adds in the reaction solution is one of following kind: potassium alum, polyacrylamide.

Beneficial effect of the present invention is: this chromium-tin purple dye particle carefully reaches nano level, and narrowly distributing, its crystal have been reduced the sintering reaction condition by rear-earth-doped; The experiment proved that this chromium-tin purple dye is anti-mills, high temperature resistant, good stability, and color and luster is pure, and colour generation is good.With this pigment be used to ward off, the glaze of pottery is bedyed and decorate, and has extraordinary effect.Obtained high-quality chromium-tin purple dye with this technology.

Embodiment

For the present invention is described in detail better, as follows especially exemplified by embodiment:

Embodiment 1

Getting 15 parts of tin protochlorides is dissolved in 45 parts of water, add 0.5 part of Neodymium trichloride, 0.07 part alkylphenol polyoxydivinyl ether dispersion agent, 0.4 part Xylo-Mucine viscosity agent, adjusting pH value is 2, get 0.5 part of sodium dichromate 99 and be dissolved in 20 parts of water, in 3 minutes, be added dropwise in the aforementioned solution, reacted 2 hours down at 65 ℃.Add 0.3 part of potassium alum, precipitate 5 hours,,, obtain violet pigment of the present invention at 1250 ℃ of sintering 100 ℃ of dryings 30 minutes.

Embodiment 2

Getting 45 parts of tin protochlorides is dissolved in 40 parts of water, add 1.5 parts of yttrium sulfates, 0.1 the alkylphenol polyoxydivinyl ether dispersion agent of part, 1 part of Xylo-Mucine viscosity agent, adjusting pH value is 2, get 1.4 parts of chromium sesquioxides and be dissolved in 13 parts of water, be added dropwise in the kind in the aforementioned solution, 65 ℃ of reactions 2 hours at 3 minutes.Go into 1 part of potassium alum, precipitate 5 hours,,, obtain violet pigment of the present invention at 1300 ℃ of sintering in 30 fens kinds of 75 ℃ of dryings.

Embodiment 3

Get 20 parts of stannous sulfates and be dissolved in 45 parts of water, add 3 parts of praseodymium sulfates, 0.7 part sodium methylene bis-naphthalene sulfonate dispersion agent, add 2 parts of polyvinyl alcohol viscosity agents, adjusting pH value is 5, and getting that ammonium dichromate is dissolved in for 5 parts is in 20 parts of water, adds in 2 minutes in the aforementioned solution, 45 ℃ of reactions 2.5 hours, add 2 parts of polyacrylamide precipitation agents, precipitate 4 hours, 100 ℃ of dryings 30 minutes, at 1350 ℃ of sintering, obtain purple dye of the present invention.

Embodiment 4

Get 22 parts of tin protochlorides and be dissolved in 45 parts of water, add 3 parts of europium sulfates, 0.5 part sodium methylene bis-naphthalene sulfonate dispersion agent, add 3 parts of polyvinyl alcohol viscosity agents, adjusting pH value is 2, gets 3 parts of potassium bichromate and is dissolved in 20 parts of water, is added dropwise in the aforementioned solution in 3 minutes, 65 ℃ of reactions 2 hours, add 3 parts of polyacrylamide precipitation agents, precipitate 4 hours, 90 ℃ of dryings 30 minutes, at 1250 ℃ of sintering, obtain violet pigment of the present invention.

Embodiment 5

Get 30 parts of nitric acid tin and be dissolved in 35 parts of water, add 0.5 part of yttrium sulfate, 0.5 part Neodymium trichloride, 0.3 the alkylphenol polyoxydivinyl ether dispersion agent of part adds 5 parts of polyvinyl alcohol viscosity agents, adjusting pH value is 2, getting 2 parts of sodium dichromate 99s is dissolved in 20 parts of water, in 2 minutes, be added dropwise in the aforementioned solution,, add 5 parts of potassium alums 85 ℃ of reactions 3 hours, precipitate 5 hours, 70 ℃ of dryings 30 minutes,, obtain violet pigment of the present invention at 1200 ℃ of sintering.

Embodiment 6

Get 40 parts of nitric acid tin and be dissolved in 45 parts of water, add 0.7 part of yttrium sulfate, 0.3 part europium sulfate, 0.5 the alkylphenol polyoxydivinyl ether dispersion agent of part adds 3 parts of gelatin, adjusting pH value is 3, Sodium chromate is dissolved in 22 parts of water for 1 part, in 4 minutes, be added dropwise in the aforementioned solution,, add 3 parts of polyacrylamide precipitation agents 70 ℃ of reactions 3 hours, precipitate 4 hours, 100 ℃ of dryings 50 minutes,, obtain violet pigment of the present invention at 1000 ℃ of sintering.

Claims

1, a kind of chromium-tin purple dye preparation method adopts inorganic salt sol-gel wet method preparation process, it is characterized in that, by the oxide compound of metal pink salt, chromium or its salt, rare earth compound or their mixture, dispersion agent, viscosity modifier, sinking agent, through liquid phase reaction, high temperature sintering forms; Concrete technology is as follows: be dissolved in oxide compound or its salt of an amount of metal pink salt and chromium in the distilled water respectively, solvent pink salt is placed reactor, be warming up to 40-95 ℃ of temperature of reaction, add rare earth compound or their mixture, viscosity modifier, dispersion agent, and regulator solution PH is 2-7, oxide compound or its salts solution with chromium is added dropwise in the reactor then, dropwises in 2-5 minute, reacts 2-3 hour, add the sinking agent precipitation, liquid-solid separation is washed impurity elimination with distilled water, after 45-100 ℃ of following drying, in 700-1400 ℃ of sintering, obtain this violet pigment;

The weight percent of reactant composition is: metal pink salt 10%-65%, the oxide compound of chromium or its salt 0.05%-5%, rare earth compound 0.2%-5%, viscosity modifier 0.1-10%, dispersion agent 0.05%-0.5%, sinking agent 0.1-10%, surplus is a distilled water.

2, chromium-tin purple dye preparation method as claimed in claim 1, it is characterized in that, the weight percent of reactant composition is: the metal pink salt is 15%-55%, the oxide compound of chromium and salt thereof are 0.2%-3%, rare earth compound is 0.5%-2%, and viscosity modifier 0.2-8%, dispersion agent are 0.2%-0.4%, sinking agent 0.3-7%, surplus is a water.

3, chromium-tin purple dye preparation method as claimed in claim 1 or 2 is characterized in that, used metal pink salt is one of following kind: tin sulphate, stannous sulfate, tin acetate, stannous acetate, nitric acid tin, tin chloride or tin protochloride.

As claim 1 or 2 chromium-tin purple dye preparation methods, it is characterized in that 4, the oxide compound of used chromium and salt thereof are one of following kind: chromium sesquioxide, Sodium chromate, sodium dichromate 99, potassium bichromate or ammonium dichromate.

As claim 1 or 2 chromium-tin purple dye preparation methods, it is characterized in that 5, rare-earth compound or their mixture are following kind: yttrium sulfate, Neodymium trichloride, europium sulfate or praseodymium sulfate.

As claim 1 or 2 chromium-tin purple dye preparation methods, it is characterized in that 6, the dispersion agent that adds in the reaction solution is a tensio-active agent, is one of following kind: alkylphenol polyoxyethylene or sodium methylene bis-naphthalene sulfonate.

7, chromium-tin purple dye preparation method as claimed in claim 1 or 2 is characterized in that, the viscosity modifier that adds in the reaction solution is one of following kind, polyvinyl alcohol, low molecular weight sodium polyacrylate, Xylo-Mucine or gelatin.

8, chromium-tin purple dye preparation method as claimed in claim 1 or 2 is characterized in that, the sinking agent that adds in the reaction solution is one of following kind: potassium alum or polyacrylamide.

9, a kind of chromium-tin purple dye is characterized in that, the pigment that it makes for the described method of claim 1.