CN106517330A - Method for preparing copper chromite black pigment by gel process - Google Patents
Method for preparing copper chromite black pigment by gel process Download PDFInfo
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- CN106517330A CN106517330A CN201611064662.0A CN201611064662A CN106517330A CN 106517330 A CN106517330 A CN 106517330A CN 201611064662 A CN201611064662 A CN 201611064662A CN 106517330 A CN106517330 A CN 106517330A
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- temperature
- copper chromite
- powder
- chromite black
- copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention relates to a method for preparing a copper chromite black pigment by a gel process, belonging to the field of chemical industry. The spinel copper chromite black pigment is prepared by the combination of a sol-gel process and a high-temperature self-propagating combustion process. The method comprises the following steps: by using stearic acid as a gelatinizer, cupric nitrate and chromic nitrate as raw materials and PEG (polyethylene glycol) 200 as a dispersing agent, preparing a copper chromite black precursor dried gel by the sol-gel process, and carrying out precursor combustion and high-temperature calcination to successfully prepare the spinel copper chromite black pigment with perfect crystal form and uniform granularity. The holding time has smaller influence on the crystal form: when the holding time is changed, the copper chromite black crystal structure does not obviously change; and however, as the holding time becomes longer, the crystal grains increase, and the aggregation phenomenon is obvious.
Description
Technical field
The invention belongs to chemical field, more particularly to a kind of method that utilization gel method prepares copper-chrome black.
Background technology
The method for preparing copper-chrome black at present is mainly solid phase method and liquid phase method.When solid phase method prepares copper-chrome black, because of raw material hardly possible
Make so that uniform mixing causes reaction unbalanced that product impurity is more, crystalline phase is impure；Additionally, higher reaction temperature, makes product grain
Son caking is serious, particle diameter is larger, and to crude product Jing again high-energy ball milling then can badly damaged product crystalline structure, so as to lead
Soluble heavy metal ions content increase during pigment product use is caused, environment is endangered, in view of these problems so that solid phase method
The product of preparation is difficult to the needs for meeting the paint pigment with better quality and superior function.And the product prepared by liquid phase method
Product its particle diameters, purity and color and luster etc. are superior to solid phase method, but preparation process is more complicated, and technique is loaded down with trivial details, low yield, relatively costly,
And hence, limit application of the liquid phase method in industrialized great production.
Sol-tgel self-propagating combustion method is that synthesis material is first made xerogel forerunner by sol-gel process by one kind
Body, recycles the self-propagating combustion characteristic of xerogel itself come the method for preparing product, and having sol-gel process concurrently can make reactant
Reach that molecular level uniformly mixes, product purity is high, particle diameter is little and narrowly distributing, and self-propagating combustion production efficiency is high, energy
The low advantage of consumption, is applied widely in terms of the material preparation such as metal alloy, metal-oxide and metal composite oxide.
The content of the invention
The present invention is intended to provide a kind of method that utilization gel method prepares copper-chrome black.
The technical scheme is that：
A kind of method that utilization gel method prepares copper-chrome black, comprises the steps：
（1）Stoichiometrically n (Cu): n(Cr) = 1 :2 accurately take Gerhardite and Chromium nitrate (Cr(NO3)3),nonahydrate is put into
In beaker, add distilled water to dissolve which, then beaker in constant temperature blender with magnetic force is heated and stirred, until becoming blackish green
The transparent aqueous metallic ions of color, then this solution is proceeded to while hot standby in constant pressure funnel；
（2）Take analytically pure stearic acid to be put in beaker, melting is heated on electric furnace, when liquid is changed into completely stop heating；
（3）The stearic acid for having melted completely is placed in digital display constant temperature blender with magnetic force, reaction unit is fixed, temperature is set
Degree, opens magnetic agitation, when temperature rises to assigned temperature, then will be the hybrid metal ion of heat water-soluble by constant pressure funnel
It is slowly added dropwise in liquid stearic acid, after solution is dripped, adds PEG200, forms stable colloidal sol；
（4）Temperature constant magnetic stirring, gradually middle moisture gradually evaporates reactant liquor, subsequently has yellow smog to produce, and mixed solution is gradually
It is changed into green transparent colloidal sol, with the further evaporation of moisture, finally becomes blackish green wet gel；
（5）Wet gel is placed in into dry bottle green xerogel in electric drying oven with forced convection；
（6）Xerogel presoma is placed on electric furnace and is heated, and lighted in air atmosphere, grey black is obtained after fully burning
Then powder is obtained precursor powder in 1 h of planetary ball mill high speed ball milling by powder；
（7）Powder after pre-burning is placed in Muffle furnace and is calcined, be incubated 2h, after furnace cooling, obtain final product pigment product, ball milling can be obtained
Ultra-fine copper-chrome black powder pigment.
The method that utilization gel method of the present invention prepares copper-chrome black, freeze-day with constant temperature at 120 DEG C of the drying baker
2 h。
The method that utilization gel method of the present invention prepares copper-chrome black, the calcining heat are 600 ~ 1000 DEG C.
The method have technical effect that：
The method that utilization gel method of the present invention prepares copper-chrome black, is burnt with self-propagating high-temperature using sol-gal process
The method that method combines prepares spinel-type copper-chrome black.With stearic acid as gel, copper nitrate and chromic nitrate are raw material,
PEG200 is dispersant, prepares copper-chrome black presoma xerogel by sol-gal process, then the burning of premenstrual body and high-temperature calcination into
Work(has prepared that crystal formation is perfect, even-grained spinel-type copper-chrome black.
Specific embodiment
Embodiment 1
A kind of method that utilization gel method prepares copper-chrome black, comprises the steps：
（1）Stoichiometrically n (Cu): n(Cr) = 1 :2 accurately take Gerhardite and Chromium nitrate (Cr(NO3)3),nonahydrate is put into
In beaker, add distilled water to dissolve which, then beaker in constant temperature blender with magnetic force is heated and stirred, until becoming blackish green
The transparent aqueous metallic ions of color, then this solution is proceeded to while hot standby in constant pressure funnel；
（2）Take analytically pure stearic acid to be put in beaker, melting is heated on electric furnace, when liquid is changed into completely stop heating；
（3）The stearic acid for having melted completely is placed in digital display constant temperature blender with magnetic force, reaction unit is fixed, temperature is set
Degree, opens magnetic agitation, when temperature rises to assigned temperature, then will be the hybrid metal ion of heat water-soluble by constant pressure funnel
It is slowly added dropwise in liquid stearic acid, after solution is dripped, adds PEG200, forms stable colloidal sol；
（4）Temperature constant magnetic stirring, gradually middle moisture gradually evaporates reactant liquor, subsequently has yellow smog to produce, and mixed solution is gradually
It is changed into green transparent colloidal sol, with the further evaporation of moisture, finally becomes blackish green wet gel；
（5）Wet gel is placed in into dry bottle green xerogel in electric drying oven with forced convection；
（6）Xerogel presoma is placed on electric furnace and is heated, and lighted in air atmosphere, grey black is obtained after fully burning
Then powder is obtained precursor powder in 1 h of planetary ball mill high speed ball milling by powder；
（7）Powder after pre-burning is placed in Muffle furnace and is calcined, be incubated 2h, after furnace cooling, obtain final product pigment product, ball milling can be obtained
Ultra-fine copper-chrome black powder pigment.
The method that utilization gel method of the present invention prepares copper-chrome black, freeze-day with constant temperature at 120 DEG C of the drying baker
2 h。
The method that utilization gel method of the present invention prepares copper-chrome black, the calcining heat are 600 DEG C.
Stearic addition is larger to the formation of colloidal sol and the particle size influences of product, when stearic acid and slaine mole
Than less than 1.25:When 1, it is difficult to form the colloidal sol of homogeneous transparent, products obtained therefrom particle size distribution width, fine particle and big particle
Mass fraction is all larger, and stearic amount is fewer, and particle size distribution is wider；When stearic acid reaches 1.25 with the mol ratio of slaine
:When 1, the colloidal sol for comparing homogeneous transparent can be formed, the distribution of particles of products obtained therefrom is narrower, is concentrated mainly on 0.10 ~ 1.00 μ
M, big particle and fine particle mass fraction it is less.This is because stearic amount is very little, part metals salt fails and Hard Fat
Acid is combined, it is also possible that partial hydrolysiss, cause micelle uneven in colloidal sol, gel process is formed, therefore, doing for generation is solidifying
Glue is substantially uneven.In self-propagating combustion, react uneven.On the other hand, due to stearic amount not enough, to intergranular
Hinder to reduce, therefore, the reunion of granule is more serious, so the large percentage of big particle.To be formed as stearic acid is primarily served
The effect of the colloidal sol and prevention particle agglomeration of stable homogeneous, is burned off in self-propagating combustion, therefore, as long as its amount can guarantee that
Homogeneous transparent colloidal sol is formed, consumption can excessively cause wastage of material, cause cost to raise.Therefore, stearic addition
With stearic acid and the mol ratio 1.25 ~ 1.50 of slaine:1 is advisable.
Moisture contained by xerogel is evaporated in a large number, and weightless process is obvious；Continue to heat up, reach 110 DEG C or so, lose
Weight is gradually steady；At 183 DEG C, the nitrate anion of the remaining of correspondence xerogel decomposes produced heat when being heated；204-258
DEG C occur a shallower endothermic peak, this for xerogel mid-boiling point higher composition evaporation；Because hard in this temperature range
Fat acid salt starts to decompose, and redox reaction occurs with nitrate anion, causes Organic substance residue to burn rapidly, releases a large amount of burning
Heat.Mass loss in this section of exothermic process is up to 50%, and reaction is just basically completed until 440.5 DEG C or so, and subsequent oxide is opened
Begin to absorb heat, occur an endothermic peak on DTA curve at 637.1 DEG C, herein spinel-type CuCr2O4Crystal is gradually opened
Begin to be formed, to 800 DEG C of reactions substantially completely, mass loss is few.
Due to stearic acid opposing metallic salt be it is excessive, therefore, the copper chromium stearate of generation can also coating it is a certain amount of hard
Fat acid, makes the product that calcining is generated keep less size.Therefore, preferable gelation can be played using stearic acid, its into
This is lower than by gellant of citric acid.
Spinel-type CuCr2O4Crystal is initially formed, but develops bad, and the temperature is theoretical significantly lower than in heat analysis to turn crystalline substance
Temperature, is primarily due in the heating atmosphere of differential thermal-thermogravimetric simulation, the nitrate ion contained in Gel Precursor and Hard Fat
There is violent burning in acid group in 300 ~ 450 DEG C of temperature ranges, cause moment to release substantial amounts of heat to the reaction system,
So as to thermal analyzer institute temp. displaying function is drastically raised, and the xerogel of pre-burning is placed in Muffle furnace, burning no longer occurs
Phenomenon, therefore the brilliant temperature that turns of reality is far below turn brilliant temperature shown by heat analysis.As calcining heat continues to increase, diffraction
Peak intensity strengthens, when calcining heat reaches 800 DEG C, CuCr2O4Principal character diffraction maximum manifests completely, and crystal development is good
It is good, the pure cubic spinel-type CuCr of well-crystallized can be obtained2O4.Grain of the different calcination temperatures to copper-chrome black particle
Footpath size and agglomeration have a significant impact, and when calcination temperature is 500 DEG C, the main component of sample is oxide, is not gone out
The copper-chrome black particle of existing spinel-type, and dispersibility extreme difference.When calcining heat reaches 600 DEG C, now start spinel-type occur
Copper-chrome black crystal, but still suffer from the mixture of substantial amounts of cupric and chromic oxide.Start a large amount of generation spinel type crystals from 700 DEG C,
Until 800 DEG C of mixture are completely converted into spinel structure, now particle is relatively fine, and good dispersion, does not almost occur
Agglomeration.Hereafter, as temperature continues to raise, the particle diameter of pigment particles gradually increases and skewness, and some particles are very
Little, part ion causes reunion because of high temperature sintering, causes particle diameter to become big.
The oil absorption of pigment is to characterize index of the pigment to Resin Absorbent amount, and its resin needed for little then dispensing of value is few, material
Low cost, and viscosity is low, machine-shaping property is good.Although preparing the mean diameter of product less than commercially available prod, fine particle ratio
Commercially available prod is few, but its regular crystal forms, defect are few, therefore, absorb oil mass low.Hydrotrope amount is low and volatile matter shows to produce at least
In thing composition be all be difficult to volatilize, insoluble crystal, purity is high, and in preparation, raw material transformation ratio is more complete；Temperature tolerance Gao Zebiao
The lattice of bright product is stable at relatively high temperatures, illustrates regular crystal forms of product, perfect.
Embodiment 2
The method that utilization gel method of the present invention prepares copper-chrome black, the calcining heat are 1000 DEG C.Remaining preparation
Mode is identical with embodiment.
When calcining heat is 500 DEG C, copper oxide and chromic oxide in reaction system, are only formed.From the beginning of 600 DEG C, say
Bright spinel-type CuCr2O4Crystal is initially formed, but develops bad, the temperature theoretical turn of brilliant temperature significantly lower than in heat analysis, main
If because in the heating atmosphere of differential thermal-thermogravimetric simulation, the nitrate ion contained in Gel Precursor is existed with stearate radical
There is violent burning in 300 ~ 450 DEG C of temperature ranges, cause moment substantial amounts of heat to be released to the reaction system, so as to heat
Analyser institute temp. displaying function is drastically raised, and the xerogel of pre-burning is placed in Muffle furnace, and combustion phenomena no longer occurs, because
The brilliant temperature that turns of this reality is far below turn brilliant temperature shown by heat analysis.As calcining heat continues to increase, diffraction peak intensity
Strengthen, when calcining heat reaches 800 DEG C, crystal development is good, can obtain the pure cubic spinelle of well-crystallized.With
Calcining heat continues to be increased to 900 DEG C, and the intensity of diffraction maximum gradually increases, crystal form gets over perfection.Start at these elevated temperatures few
Part starts oxidation.Coloured product also fades to bright black by grey black, last to be changed in black slightly band yellow phase again.Work as forging
When burning temperature is 500 DEG C, the main component of sample is oxide, the copper-chrome black particle of spinel-type, and dispersibility does not occur
Extreme difference.When calcining heat reaches 600 DEG C, now start spinel-type copper-chrome black crystal occur, but still suffer from substantial amounts of copper chromium oxygen
The mixture of compound.Start a large amount of generation spinel type crystals from 700 DEG C, until 800 DEG C of mixture are completely converted into sharp crystalline substance
Stone-type structure, now particle is relatively fine, and good dispersion, agglomeration does not almost occur.Hereafter, as temperature continues to rise
Height, the particle diameter of pigment particles gradually increase and skewness, and some particles very little, part ion cause group because of high temperature sintering
It is poly-, cause particle diameter to become big.
Claims (3)
1. a kind of method that utilization gel method prepares copper-chrome black, it is characterised in that comprise the steps：
（1）Stoichiometricallyn(Cu) : n(Cr) = 1 :2 accurately take Gerhardite and Chromium nitrate (Cr(NO3)3),nonahydrate is put into
In beaker, add distilled water to dissolve which, then beaker in constant temperature blender with magnetic force is heated and stirred, until becoming blackish green
The transparent aqueous metallic ions of color, then this solution is proceeded to while hot standby in constant pressure funnel；
（2）Take analytically pure stearic acid to be put in beaker, melting is heated on electric furnace, when liquid is changed into completely stop heating；
（3）The stearic acid for having melted completely is placed in digital display constant temperature blender with magnetic force, reaction unit is fixed, temperature is set
Degree, opens magnetic agitation, when temperature rises to assigned temperature, then will be the hybrid metal ion of heat water-soluble by constant pressure funnel
It is slowly added dropwise in liquid stearic acid, after solution is dripped, adds PEG200, forms stable colloidal sol；
（4）Temperature constant magnetic stirring, gradually middle moisture gradually evaporates reactant liquor, subsequently has yellow smog to produce, and mixed solution is gradually
It is changed into green transparent colloidal sol, with the further evaporation of moisture, finally becomes blackish green wet gel；
（5）Wet gel is placed in into dry bottle green xerogel in electric drying oven with forced convection；
（6）Xerogel presoma is placed on electric furnace and is heated, and lighted in air atmosphere, grey black is obtained after fully burning
Then powder is obtained precursor powder in 1 h of planetary ball mill high speed ball milling by powder；
（7）Powder after pre-burning is placed in Muffle furnace and is calcined, be incubated 2h, after furnace cooling, obtain final product pigment product, ball milling can be obtained
Ultra-fine copper-chrome black powder pigment.
2. the method that utilization gel method according to claim 1 prepares copper-chrome black, it is characterised in that：The drying baker
2 h of freeze-day with constant temperature at 120 DEG C.
3. the method that utilization gel method according to claim 1 prepares copper-chrome black, it is characterised in that：The calcining temperature
Spend for 600 ~ 1000 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611064662.0A CN106517330A (en) | 2016-11-28 | 2016-11-28 | Method for preparing copper chromite black pigment by gel process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611064662.0A CN106517330A (en) | 2016-11-28 | 2016-11-28 | Method for preparing copper chromite black pigment by gel process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059187A (en) * | 2017-12-29 | 2018-05-22 | 华南协同创新研究院 | Copper-chrome black and preparation method and application is precipitated in a kind of low Cr VI |
| CN116023805A (en) * | 2022-12-29 | 2023-04-28 | 淄博颜光颜料有限公司 | High-tinting strength copper-chromium black pigment and preparation process thereof |
| CN118387925A (en) * | 2024-06-26 | 2024-07-26 | 湖南汇帮环保科技有限公司 | Low-temperature preparation method and application of copper-chromium black |
-
2016
- 2016-11-28 CN CN201611064662.0A patent/CN106517330A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059187A (en) * | 2017-12-29 | 2018-05-22 | 华南协同创新研究院 | Copper-chrome black and preparation method and application is precipitated in a kind of low Cr VI |
| CN108059187B (en) * | 2017-12-29 | 2020-03-24 | 华南协同创新研究院 | Low hexavalent chromium separated copper-chromium black pigment and preparation method and application thereof |
| CN116023805A (en) * | 2022-12-29 | 2023-04-28 | 淄博颜光颜料有限公司 | High-tinting strength copper-chromium black pigment and preparation process thereof |
| CN118387925A (en) * | 2024-06-26 | 2024-07-26 | 湖南汇帮环保科技有限公司 | Low-temperature preparation method and application of copper-chromium black |
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Application publication date: 20170322 |