CN111748222A - High-tinting strength copper-chromium black pigment and preparation method thereof - Google Patents
High-tinting strength copper-chromium black pigment and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/34—Compounds of chromium
- C09C1/346—Chromium oxides
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/041—Grinding
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
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Abstract
The invention belongs to the technical field of pigments and provides a high tinting strength copper-chromium black pigment which comprises, by mass, 122 parts of CuO by weight of 110-containing materials and 245 parts of Cr-containing materials by weight of 214-containing materials2O360-86 parts of Mn3O4(ii) a The preparation method comprises the steps of stirring and mixing the raw materials for 3-6h, drying, then preserving heat for 5-8h at 1050 ℃ and 1100 ℃, cooling and crushing to obtain the high-tinting-power copper-chromium black pigment. Through the technical scheme, the problems of large pigment particles, uneven force distribution, poor coloring power, high energy consumption of the preparation method and environmental pollution in the prior art are solved.
Description
Technical Field
The invention belongs to the technical field of pigments, and relates to a high-tinting strength copper-chromium black pigment and a preparation method thereof.
Background
Copper chromium black (CuCr)2O4) Black pigments are an important conventional pigmentThe metal oxide mixed-phase pigment is expected to replace the traditional carbon black and iron oxide black pigment due to the advantages of strong weather resistance, good heat resistance, strong tinting strength, long service life, environmental protection and the like, and is widely applied to the industries of general coatings, high-temperature anticorrosive coatings, military coatings, plastics, printing ink and the like. In addition, CuCr2O4Can also be used as a catalyst to be applied to the fields of hydrogen production by water decomposition, organic matter photodegradation and the like.
The general synthesis method of spinel type copper chromium black is generally divided into: solid phase methods and liquid phase methods.
The liquid phase method mainly includes a coprecipitation method, a sol-gel method, a molten salt method and the like. The sol-gel method needs organic substances such as epoxypropane, stearic acid, acrylic acid-styrene and the like as complexing agents and coupling agents, and the use of the organic substances not only increases the production cost, but also causes pollution to the environment; the molten salt method requires long-time ball milling in the preparation process, and the calcined molten salt method requires multiple times of washing, filter pressing, drying and crushing. The preparation process is complicated, and a large amount of water is used for rinsing, so that water resources are wasted, a large amount of waste water is generated, and the environment is seriously influenced. The coprecipitation method is a commonly used preparation method in the prior art, and is characterized in that the principle that certain metal salts or hydroxides have low solubility in a solution and are easy to precipitate is utilized, the precipitation is precipitated by controlling the conditions such as concentration, pH value, temperature, reaction time, stirring speed and the like, and then the precipitate is filtered, washed, dried, calcined and crushed to prepare the powder pigment. This method requires multiple water washes, resulting in the discharge of large amounts of waste water. Therefore, the coprecipitation method adopted in the prior art for preparing the copper-chromium black pigment still generally has the problems of complex process, uneven product granularity, high production cost, environmental pollution and the like.
The solid phase method is generally classified into a copper salt chromium oxide method and a copper oxide chromium oxide method.
The copper salt and the chromium oxide are calcined at the high temperature of 1000 ℃, and excessive harmful gas is generated. Such as: the high-temperature calcination of copper sulfate and chromium oxide can generate SO2,: high temperature calcination of copper nitrate and chromium oxide produces NO2. Both gases are harmful gases which are strictly limited to be discharged by the nation and can be harmful to the nationThe atmosphere causes serious pollution. Therefore, the copper oxide and chromium oxide method is a method for producing copper-chromium black which is commonly used in the solid phase method.
Although no harmful gas is generated during the high-temperature calcination of the copper oxide and the chromium oxide, nitrogen oxide and sulfur dioxide are generated due to the calcination of most liquefied gas or natural gas. In the process of calcining the material, lattice change is needed, the formula is single without the participation of additives, and the high temperature and the poor balance degree can generate a large amount of agglomeration and caking; wet grinding by a ball mill to a certain fineness, press filtering, drying, and pulverizing by a pulverizer to obtain the final product. The process is complicated, and waste water is generated due to filter pressing, so that the environment is influenced; the grinding fineness of the ball mill can not reach the particle size and fineness required by medium-grade and high-grade coatings; the color light, the color strength and the performance of the pigment are poor; the application range is limited.
Therefore, the solid phase method has simple synthesis process and easy operation control, but needs higher reaction temperature during product synthesis, has long heat preservation time and high energy consumption, and finally prepared materials have large particles, uneven particle size distribution and poor coloring power. Therefore, there is a drawback in application performance. The liquid phase method is to mix the reactants evenly in the liquid environment to form a homogeneous reaction system, so that the reactants are fully contacted with each other to achieve the purpose of increasing the effective collision probability of molecules.
The tinting strength (tint strength) is a measure of the ability of a colored pigment to absorb light on a white pigment to develop color according to international and domestic standards. Common copper chromium black clinker CuCr2O4In, MnO is often added2Modified product made, MnO2Is natural pyrolusite or synthetic battery grade. But due to MnO2It is very resistant to high temperature, light and chemical corrosion, and is especially used in making high temperature resistant paint and fluorocarbon paint. In these applications, the pigment is often mixed with titanium dioxide, a white pigment, in different proportions to give a variety of gray pigments, and MnO is added2Copper-chromium-manganese blackPigments have a problem of gray hue and low tinting strength.
Based on the above, how to reduce energy consumption and environmental pollution while ensuring the performance and quality of the pigment is an urgent problem to be solved.
Disclosure of Invention
The invention provides a high tinting strength copper-chromium black pigment and a preparation method thereof, provides a spinel type copper-chromium black mixed oxide black pigment without the defects, and solves the problems of large pigment particles, uneven particle size distribution, poor tinting strength, high energy consumption of the preparation method and environmental pollution in the prior art.
The spinel type copper chromium black pigment prepared by the invention selects manganous-manganic oxide (Mn)3O4) Is a manganese raw material of the early-stage material.
The technical scheme of the invention is realized as follows: the copper-chromium black pigment with high tinting strength comprises, by mass, 122 parts of CuO and 245 parts of Cr, wherein the CuO is 110-2O360-86 parts of Mn3O4。
Further, the copper-chromium black pigment also comprises 0.3-0.4% of nano silicon-based oxide or superfine aluminum silicate in mass fraction.
Furthermore, the fineness of the CuO is 500-800 meshes.
Further, the Mn3O4The fineness of the powder is 1800 meshes.
Further, the Cr is2O3Fineness D50<1μm。
A preparation method of a high-tinting strength copper-chromium black pigment comprises the following steps:
A. weighing the components according to the formula of the high tinting strength copper-chromium black pigment, stirring and mixing for 3-6h or ball-milling for 6-8h by a dry method, and drying for later use;
B. and C, preserving the heat of the material prepared in the step A at 1050-.
Further, the step A drying is flash drying, spray drying, air flow drying or rotary kiln drying.
The working principle and the beneficial effects of the invention are as follows:
1. the spinel-type copper-chromium black mixed oxide black pigment prepared by matching and designing the pigment component additives and combining a solid phase method has the advantages of small particle size, uniform particle size distribution, good tinting strength, brightness value L ranging from 52.5 to 54.5, low energy consumption in the preparation process and environmental pollution prevention.
2. The nanometer silicon-based oxide or the superfine aluminum silicate has high temperature resistance, small particles and large specific area, does not participate in solid-phase reaction and lattice change, only plays a role in filling gaps among formed mixed-phase pigment particles, prevents agglomeration and fusion among crystal lattices, separates bond adhesion among generated mixed pigments, prevents agglomeration, plays a role in fluffing in the copper-chromium black calcining process, ensures that products are loose, do not agglomerate and do not agglomerate, is beneficial to direct airflow pulverization in the later period, further omits the processes of filter pressing and drying, shortens the preparation period, simplifies the preparation process, does not generate waste gas and waste water, and avoids the influence on the environment.
3. The invention adopts nano silicon-based oxide or superfine aluminum silicate and CuO and Mn3O4、Cr2O3The copper-chromium black pigment finished product is uniform in particle size distribution, small in grain size and complete in crystal form by mutual synergistic compounding; excellent high temperature stability and chemical stability; the tinting strength is greatly improved, compared with American Shepherd1G, the tinting strength is improved by 15 percent, compared with German Heubach935-1, the tinting strength is improved by 28 percent, and the advanced level in the world is achieved; therefore, the improvement of tinting strength is beneficial to improving the covering power of the coating, and particularly, the far infrared absorption capacity is greatly improved on the military coating.
4. The copper-chromium black raw material in the invention completely adopts nano-scale, high specific surface area and superfine material, thereby further increasing the fusion degree of crystal lattices among the materials, accelerating the production speed of the product and shortening the heat preservation time under the same condition.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a particle size distribution diagram of a copper-chromium black pigment prepared in example 1 of the present invention.
FIG. 2 is a comparison of a copper chromium black pigment prepared in example 6 of the present invention and a United states Sauter Shepherd1G color chart;
wherein 1G represents a paint color chip made with the American Shepherd1G pigment, and example 6 represents a paint color chip made with the pigment of example 6 of the present invention.
FIG. 3 is a color chart comparing copper chromium black pigment prepared in example 7 of the present invention with German Heubach 935-1;
wherein 935-1 represents a paint color chip made using Heubach935-1 pigment from Heubach, Germany, and example 7 represents a paint color chip made using the pigment of example 7 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The raw materials used in the following examples are all available from the market, wherein the content of copper oxide is 98.5 percent, and the fineness is 500 meshes to 800 meshes; mangano manganic oxide (Mn)3O4)1800 mesh, chromium oxide Green (Cr)2O3) New friendship material produced by itself, content 98.5%, fineness D50<1 μm. The nano silicon-based oxide is a nano-scale substance of silicon dioxide, and the specific surface area of the adopted nano silicon-based oxide is more than 220m2The grain diameter is 18 plus or minus 5nm, the tap density is less than 0.15g/ml, the phase is amorphous, and the superfine aluminum silicate has the fineness of 2000 meshes and is purchased from Zhejiang Zhoushanhui nanometer material company.
Example 1
A high tinctorial strength copper chromium black pigment comprising: 115gCuO, 60gMn3O4、245gCr2O3(friendship high grade GM), 1.3g nanometer silicon based oxide.
The preparation method of the high tinting strength copper-chromium black pigment comprises the following steps:
A. preparing CuO and Cr according to the above-mentioned mixing ratio2O3、Mn3O4Stirring and mixing the nano silicon-based oxide at a high speed of 1100r/min for 6 hours, and carrying out flash evaporation drying for later use;
B. and C, preserving the heat of the material prepared in the step A for 5 hours at 1050 ℃, cooling, and crushing to obtain the high-tinting strength copper-chromium black pigment with the fineness D50 of 1.5-2 microns.
Example 2
A high tinctorial strength copper chromium black pigment comprising: 115gCuO, 60gMn3O4、245gCr2O3(friendship high grade GM), 1.3g of aluminum silicate.
The preparation method of the high tinting strength copper-chromium black pigment comprises the following steps:
A. preparing CuO and Cr according to the above-mentioned mixing ratio2O3、Mn3O4Stirring and mixing aluminum silicate at a high speed of 1100r/min for 3h, and spray drying for later use;
B. and C, preserving the heat of the material prepared in the step A for 5-8h at 1100 ℃, cooling, and crushing to obtain the copper-chromium black pigment with high tinting strength after the fineness D50 is 1.5-2 mu m.
Example 3
A high tinctorial strength copper chromium black pigment comprising: 122gCuO, 63gMn3O4、235gCr2O3(friendship high grade GM), nanometer silicon based oxide 1.26 g.
The preparation method of the high tinting strength copper-chromium black pigment comprises the following steps:
A. preparing CuO and Cr according to the above-mentioned mixing ratio2O3、Mn3O4Carrying out dry ball milling or mixing on the nano silicon-based oxide for 6 hours, and carrying out airflow drying for later use;
B. and C, preserving the heat of the material prepared in the step A for 6 hours at 1080 ℃, cooling, and crushing to obtain the high-tinting-strength copper-chromium black pigment with the fineness D50 of 1.5-2 microns.
Example 4
A high tinctorial strength copper chromium black pigment comprising: 122gCuO, 63gMn3O4、235gCr2O3(friendship high grade GM), silicic acid1.26g of aluminum.
The preparation method of the high tinting strength copper-chromium black pigment comprises the following steps:
A. preparing CuO and Cr according to the above-mentioned mixing ratio2O3、Mn3O4Ball-milling and mixing the nano silicon-based oxide for 8 hours by a dry method for later use;
B. and D, preserving the heat of the material prepared in the step A for 6 hours at 1080 ℃, cooling, performing wet ball milling until the fineness D50 is 1.5-2 mu m, and performing spray drying to obtain the high tinting strength copper-chromium black pigment.
Example 5
A high tinctorial strength copper chromium black pigment comprising: 120gCuO, 86gMn3O4、214ggCr2O3(friendship high grade GM) nanometer silicon based oxide 1.68 g. The preparation method is the same as example 1.
Example 6
A high tinctorial strength copper chromium black pigment comprising: 110gCuO, 86gMn3O4、214gCr2O3(friendship high grade GM) nanometer silicon based oxide 1.3 g. The preparation method is the same as example 1.
Example 7
A high tinctorial strength copper chromium black pigment comprising: 110gCuO, 86gMn3O4、214gCr2O3(friendship high grade GM), aluminium silicate 1.68 g. The preparation method is the same as example 1.
Comparative example 1
A conventional copper chromium black pigment comprising: 115gCuO and 60gMnO2、245gCr2O3(friendship high grade GM), 1.3g nanometer silicon based oxide. The preparation method is the same as example 1.
Comparative example 2
A conventional copper chromium black pigment comprising: 115gCuO and 60gMnO2、245gCr2O3(friendship high grade GM), 1.3g of aluminum silicate. The preparation method is the same as example 1.
Comparative example 3
A high tinctorial strength copper chromium black pigment comprising: 115gCuO, 60gMn3O4、245gCr2O3(friendship high grade GM) without adding nano silicon base oxide. The preparation method is the same as example 1. The product is obviously agglomerated.
Comparative example 4
A high tinctorial strength copper chromium black pigment comprising: 115gCuO, 60gMn3O4、245gCr2O3(friendship high grade GM) no aluminium silicate is added. The preparation method is the same as example 1. The product is obviously agglomerated.
Comparative example 5
A conventional copper chromium black pigment comprising: 115CuO, 60gMnO2、245g Cr2O3(friendship high grade GM) no nano silicon based oxide is added. The preparation method is the same as example 1. The product has agglomeration.
Measurement of Brightness and tinting Strength
The copper-chromium black pigments prepared in the above examples 1 to 7 and comparative examples 1 to 5 were uniformly mixed in a PM240-2 plain grinding machine according to the mixing ratio of 1g pigment, 5g titanium dioxide and 1 ml linseed oil; applying pressure of about 4.5 kg, grinding for 50 times multiplied by 2 times to prepare colored paint; the color chart was prepared according to the method of GB5211.19-88 standard, and the results were measured and calculated by Konica Minolta CR-10 color difference meter and shown in Table 1, wherein the results of the coloring power measurement are 100% in comparative example 2.
TABLE 1 measurement results of lightness and tinting strength
| L value of luminance | Coloring power% | Colour(s) | |
| Example 1 | 53.1 | 177 | Blue phase black |
| Example 2 | 53.7 | 171 | Blue phase black |
| Example 3 | 54.5 | 163 | Blue phase black |
| Example 4 | 54.3 | 166 | Blue phase black |
| Example 5 | 54.0 | 168 | Blue phase black |
| Example 6 | 52.5 | 183 | Blue phase black |
| Example 7 | 52.7 | 170 | Blue phase black |
| Comparative example 1 | 61.3 | 95 | Partial gray |
| Comparative example 2 | 60.8 | 100 | Partial gray |
| Comparative example 3 | 52.8 | 180 | Blue phase black |
| Comparative example 4 | 53.0 | 178 | Blue phase black |
| Comparative example 5 | 60.9 | 99 | Partial gray |
The pigments of the present invention are black pigments having a brightness value L in the range of 52.5 to 54.5, with conventional manganese dioxide having an L value of > 60.
The copper-chromium black pigments of the invention are distinguished by a low lightness of pure hue, the lower the L value the higher the tinctorial strength.
The copper-chromium black pigment samples (friendship YY-BLK2810), American Xuete Shepherd1G, Germany Heubach935-1 and titanium dioxide are respectively mixed and prepared into paint according to the mass ratio of 1:5, namely 1g of pigment 5g of titanium dioxide and 1 ml of linseed oil are uniformly mixed and ground into paint in a PM240-2 plain grinding machine, then the color card is prepared according to the GB5211.19-88 standard operation, and the result is measured and calculated by a Konica Minolta CR-10 color difference meter, and the result is shown in tables 2-5.
TABLE 2 example 6 comparison of copper chromium black pigment Brightness to American Shepherd1G
| Difference value | DL* | Da* | Db* | DE* | Coloring power |
| Friendship YY-BLK2810 (example 6) | -1.3 | 0.0 | 0.0 | 1.3 | 115％ |
Note: the tinting strength was determined at 100% Softer Shepherd1G, USA.
TABLE 3 EXAMPLE 6 comparison of the tinting strength of copper chromium black pigment with that of the United states Shepherd1G
| Absolute value | L* | a* | b* |
| U.S. sauter Shepherd1G | 53.8 | -3.1 | -6.4 |
| Friendship YY-BLK2810 (example 6) | 52.5 | -3.1 | -6.4 |
It can be seen that the brightness of the pigment in the invention is 52.5 in example 6, the brightness of the American Shepherd1G is 53.8, the tinting strength is 100% by taking the American Shepherd1G as the tinting strength, the tinting strength of the pigment in example 6 is 115%, the brightness value of the pigment in the invention is low, and the tinting strength is obviously superior to that of foreign products.
TABLE 4 comparison of the brightness of example 7 copper chromium black pigment with Heubach935-1 Haubach, Germany
| Difference value | DL* | Da* | Db* | DE* | Coloring power |
| Example 6 | -2.4 | -0.2 | -0.5 | 2.4 | 128％ |
Note: the tinting strength was determined at 100% with Heubach935-1, Heubach, Germany.
TABLE 5 comparison of the tinting strength of example 7 copper chromium black pigment with Heubach935-1 Heubach, Germany
| Absolute value | L* | a* | b* |
| German Heubach935-1 | 54.1 | -2.7 | -5.8 |
| Example 7 | 52.7 | -2.9 | -6.3 |
The brightness of the pigment in the embodiment 7 of the invention is 52.7, the brightness of German Haubach 935-1 is 54.1, the tinting strength of German Haubach 935-1 is 100 percent, and the tinting strength of the embodiment 7 is 128 percent, so that the brightness of the pigment is obviously lower than that of foreign products, and the tinting strength is obviously better than that of the foreign products.
As can be seen from Table 1, the manganese dioxide is adopted as the raw material for the pigments in comparative examples 1-2 and 5, the brightness and the tinting strength of the product are poorer than those of the pigments in examples 1-7, and the color is gray, so that the mangano-manganic oxide is adopted as the raw material in the invention, the blackness and the tinting strength of the pigment are obviously improved, and the problems of gray color phase and low tinting strength of the product are solved; in comparative examples 3-4, the pigment product obtained by adding no nano silicon-based oxide or aluminum silicate obviously has agglomeration phenomenon, which affects the use, while in examples 1-7, the agglomeration phenomenon does not exist, which shows that the dispersibility of the pigment product is obviously improved after the nano silicon-based oxide or aluminum silicate is added.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The high-tinting strength copper-chromium black pigment is characterized by comprising, by mass, 122 parts of CuO 110-2O360-86 parts of Mn3O4。
2. The high tinting strength copper-chromium black pigment of claim 1, wherein the copper-chromium black pigment further comprises 0.3-0.4% by mass of nano silicon-based oxide or ultrafine aluminum silicate.
3. The high tinting strength copper chromium black pigment of claim 1 in which the CuO has a fineness of 500 to 800 mesh.
4. The high tinctorial strength copper chromium black pigment according to claim 1, wherein the Mn is present in the pigment3O4The fineness of the powder is 1800 meshes.
5. The high tinctorial strength copper chromium black pigment according to claim 1, wherein the Cr is2O3Fineness D50<1μm。
6. A preparation method of a high-tinting strength copper-chromium black pigment is characterized by comprising the following steps:
A. according to the formula of the high tinting strength copper-chromium black pigment of any one of claims 1 to 5, weighing the components, stirring and mixing for 3 to 6 hours or ball-milling for 6 to 8 hours, and drying for later use;
B. and C, preserving the heat of the material prepared in the step A at 1050-.
7. The method for preparing a high tinctorial strength copper chromium black pigment according to claim 6, wherein the step A drying is flash drying, spray drying, air-stream drying or rotary kiln drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621604A (en) * | 2022-03-21 | 2022-06-14 | 景德镇陶瓷大学 | Preparation method of infrared-reflecting pure black pigment and product prepared by preparation method |
| 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 |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4469521A (en) * | 1982-09-29 | 1984-09-04 | Union Carbide Corporation | Corrosion inhibitive pigments |
| CN101157547A (en) * | 2007-09-11 | 2008-04-09 | 高淳县水秀焊接材料厂 | Stoneware cordierite solid solution welding cushioning material |
| CN103050680A (en) * | 2012-12-19 | 2013-04-17 | 中钢集团安徽天源科技股份有限公司 | High-density doped trimanganese tetroxide and preparation method thereof |
| CN103717534A (en) * | 2011-07-07 | 2014-04-09 | 谢珀德颜色公司 | Low-loading titanate inorganic pigments for use in infrared reflective colors |
| CN105086524A (en) * | 2015-09-15 | 2015-11-25 | 广西七色珠光材料股份有限公司 | Black nacreous pigment and preparation method thereof |
| CN108473361A (en) * | 2016-01-21 | 2018-08-31 | 费罗公司 | Black spinel pigments for glass and the modification of ceramic enamel application |
| CN109054452A (en) * | 2018-09-07 | 2018-12-21 | 中山市华山高新陶瓷材料有限公司 | Copper-chromium black pigment and preparation method thereof |
| CN110615481A (en) * | 2019-09-19 | 2019-12-27 | 北京科技大学 | Silica type Bi24Al2-xMnxO39Grass green inorganic pigment and preparation method thereof |
| CN110730766A (en) * | 2017-06-15 | 2020-01-24 | 中岛产业株式会社 | Black mixed oxide material and method for producing same |
| CN110951280A (en) * | 2019-11-28 | 2020-04-03 | 黄山市晶特美新材料有限公司 | Copper-chromium black toner prepared by solid-phase sintering method promoted by molybdenum oxide and manganese oxide and preparation method thereof |
| CN110951281A (en) * | 2019-11-28 | 2020-04-03 | 黄山市晶特美新材料有限公司 | Copper-chromium black toner prepared by solid-phase sintering method promoted by molybdenum oxide and zinc oxide and preparation method thereof |
| CN110982303A (en) * | 2019-11-29 | 2020-04-10 | 黄山市晶特美新材料有限公司 | Method for preparing copper-chromium black toner by promoting solid-phase sintering by using V-Mn and application thereof |
-
2020
- 2020-07-07 CN CN202010647153.0A patent/CN111748222B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4469521A (en) * | 1982-09-29 | 1984-09-04 | Union Carbide Corporation | Corrosion inhibitive pigments |
| CN101157547A (en) * | 2007-09-11 | 2008-04-09 | 高淳县水秀焊接材料厂 | Stoneware cordierite solid solution welding cushioning material |
| CN103717534A (en) * | 2011-07-07 | 2014-04-09 | 谢珀德颜色公司 | Low-loading titanate inorganic pigments for use in infrared reflective colors |
| CN103050680A (en) * | 2012-12-19 | 2013-04-17 | 中钢集团安徽天源科技股份有限公司 | High-density doped trimanganese tetroxide and preparation method thereof |
| CN105086524A (en) * | 2015-09-15 | 2015-11-25 | 广西七色珠光材料股份有限公司 | Black nacreous pigment and preparation method thereof |
| CN108473361A (en) * | 2016-01-21 | 2018-08-31 | 费罗公司 | Black spinel pigments for glass and the modification of ceramic enamel application |
| CN110730766A (en) * | 2017-06-15 | 2020-01-24 | 中岛产业株式会社 | Black mixed oxide material and method for producing same |
| CN109054452A (en) * | 2018-09-07 | 2018-12-21 | 中山市华山高新陶瓷材料有限公司 | Copper-chromium black pigment and preparation method thereof |
| CN110615481A (en) * | 2019-09-19 | 2019-12-27 | 北京科技大学 | Silica type Bi24Al2-xMnxO39Grass green inorganic pigment and preparation method thereof |
| CN110951280A (en) * | 2019-11-28 | 2020-04-03 | 黄山市晶特美新材料有限公司 | Copper-chromium black toner prepared by solid-phase sintering method promoted by molybdenum oxide and manganese oxide and preparation method thereof |
| CN110951281A (en) * | 2019-11-28 | 2020-04-03 | 黄山市晶特美新材料有限公司 | Copper-chromium black toner prepared by solid-phase sintering method promoted by molybdenum oxide and zinc oxide and preparation method thereof |
| CN110982303A (en) * | 2019-11-29 | 2020-04-10 | 黄山市晶特美新材料有限公司 | Method for preparing copper-chromium black toner by promoting solid-phase sintering by using V-Mn and application thereof |
Non-Patent Citations (6)
| Title |
|---|
| MINGQUAN YE ET AL.: "Synthesis and characterization of Mn-doped copper chromite black pigments", 《ADVANCED MATERIALS RESEARCH》 * |
| 储周硕: "复合无机颜料铜铬黑的制备与性能研究", 《中国优秀硕士学位论文全文数据库》 * |
| 刘兴泉等: "低温液相合成甲醇及甲酸甲酯用Cu-Cr-M-O催化剂的制备与表征 ", 《催化学报》 * |
| 叶菲等: "Cr_2O_3-MnO_2系高温红外陶瓷涂层的制备与研究 ", 《红外技术》 * |
| 晏波等: "黑色耐高温铁酸锰颜料生产工艺研究 ", 《中国涂料》 * |
| 王伟文等: "高能球磨高温固相法制备尖晶石型铜铬黑颜料 ", 《化工进展》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114621604A (en) * | 2022-03-21 | 2022-06-14 | 景德镇陶瓷大学 | Preparation method of infrared-reflecting pure black pigment and product prepared by preparation method |
| 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 |
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