CN113603356B - Black pigment with strong absorption to visible light and preparation method thereof - Google Patents
Black pigment with strong absorption to visible light and preparation method thereof Download PDFInfo
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- CN113603356B CN113603356B CN202111057600.8A CN202111057600A CN113603356B CN 113603356 B CN113603356 B CN 113603356B CN 202111057600 A CN202111057600 A CN 202111057600A CN 113603356 B CN113603356 B CN 113603356B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention disclosesThe black pigment with strong absorption to visible light and the preparation method thereof, the formula comprises the following raw materials by mass percent: 5-15% of CuO and Cr 2 O 3 10‑40％,Fe 2 O 3 10‑35％,MnO 2 15‑30％,NiO 15‑30％，ZnO 0‑5％,MoO 3 1‑5％,Al 2 O 3 0 to 3 percent. The preparation method comprises the following steps: uniformly mixing the raw materials and performing ball milling; compacting raw materials and carrying out preheating treatment; calcining the preheated raw materials, cooling, and carrying out ball milling and crushing; and standing the suspension slurry subjected to ball milling, removing the supernatant, drying the lower concentrated slurry, and screening. When the introduction amount of the black pigment in the glass slurry is 15-30%, the higher covering power of the common black pigment of not less than 40% can be achieved, and the cost of the glass slurry can be greatly reduced.
Description
Technical Field
The invention relates to the technical field of glass slurry processing, in particular to a black pigment with strong absorption to visible light and a preparation method thereof.
Background
With the development of science and technology and the progress of the technology level, the requirements on products in the glass industry are higher and higher. Most of glass slurry used in the household appliance kitchen and toilet industry is black, for example, black glass slurry used in a range hood and a cooking bench needs to have excellent covering power to shield a light source on the back, so that the use environment is more comfortable, and black glass slurry used in the automobile industry also has higher requirement on the covering power.
The content of the existing black pigment in the glass paste is at least 40 percent, so that the requirement of the glass paste on the covering power can be met, if too much black pigment is introduced into a glass paste system, the requirement on the performance of glass powder in the glass paste system is extremely high, and the cost of the glass paste is greatly improved. Secondly, most black colorants have slightly poor high temperature stability: if the use temperature is higher, the color difference of the glass slurry is easy to appear, and the defective rate of the glass product is greatly increased. Thirdly, with the improvement of the performance requirement of the glass product industry, the requirement of the glass product on the chemical corrosion resistance is higher and higher, the chemical stability resistance of the existing black pigment is poorer, the performance of the glass product is reduced, and the service life of the glass product is prolonged.
Chinese patent CN110790511A, "a low-temperature environment-friendly black glass slurry with high optical density and a preparation method thereof", proposes that the black glass slurry with high optical density is obtained by adjusting a preparation process of glass powder and then performing dry grinding with a black pigment for multiple times, wherein the black pigment used in the patent is a copper-chromium black pigment, and the purpose of excellent hiding power of the glass slurry is achieved by adjusting the preparation process of the glass slurry; the black pigment adopted in the Chinese patent CN110563327A 'melanin special for automobile glass and a preparation method thereof' is a copper-chromium black pigment, and the high temperature resistance stability and the chemical resistance stability of the pigment have certain defects.
Disclosure of Invention
In view of the above technical deficiencies, the present invention provides a black pigment with strong absorption of visible light and a method for preparing the same, so as to solve the problems of the background art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a black pigment with strong absorption to visible light and a preparation method thereof, and aims to provide a black pigment with strong absorption to visible light and a preparation method thereof. The optical density value of the glass slurry prepared by mixing the black pigment and the glass powder in a ratio of 15-30% is greater than 4.75, the hiding power of the glass slurry is obviously superior to that of the conventional black pigment, and the glass slurry has high chemical stability and excellent safety performance.
In order to achieve the above purpose, the invention adopts the technical scheme that:
a black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 5-15％,Cr 2 O 3 10-40％,Fe 2 O 3 10-35％,MnO 2 15-30％,NiO 15-30％，ZnO 0-5％,MoO 3 1-5％,Al 2 O 3 0-3％。
a black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 6-12％,Cr 2 O 3 20-35％,Fe 2 O 3 14-30％,MnO 2 18-26％,NiO 16-24％，ZnO 0-2％,MoO 3 2-4％,Al 2 O 3 0-1％。
a black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 6％,Cr 2 O 3 30％,Fe 2 O 3 19％,MnO 2 20％,NiO 21％,ZnO 1％,MoO 3 2％,Al 2 O 3 1％。
the black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 8％,Cr 2 O 3 22％,Fe 2 O 3 30％,MnO 2 21％,NiO 16％,MoO 3 2％,Al 2 O 3 1％。
the black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 9％,Cr 2 O 3 23％,Fe 2 O 3 14％,MnO 2 26％,NiO 24％,ZnO 1％，MoO 3 3％。
the black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 12％,Cr 2 O 3 35％,Fe 2 O 3 15％,MnO 2 18％,NiO 16％,ZnO 2％,MoO 3 2％。
a method for preparing a black pigment with strong absorption to visible light comprises the following steps:
(1) Weighing the raw materials according to the proportion, and uniformly mixing the raw materials by using a high-speed mixer;
(2) Ball milling the mixed raw materials;
(3) Placing the mixed and ball-milled raw materials in a crucible for compaction, and placing the crucible in a closed muffle furnace for preheating;
(4) And heating the preheated raw material in a closed muffle furnace for calcining, directly taking out the calcined crucible, and cooling at room temperature.
(5) Carrying out ball milling on the pigment cooled to room temperature;
(6) And standing the suspension slurry subjected to ball milling, removing the supernatant, drying the lower concentrated slurry, and screening to obtain the finished black pigment.
Preferably, in step (1), the mixing time is not less than 10min.
Preferably, in the step (2), the mixed raw materials are placed in a horizontal ball mill for medium-free mixed ball milling, wherein the volume of the pot body is 1L, the rotating speed is 10-200rad/min, and the raw materials: the proportion of the balls is 1 (5-20), and the mixing and ball milling time is 5-24h.
Preferably, in the step (3), the temperature of the preheating treatment is 600-800 ℃, and the time of the preheating treatment is 2-6h.
Preferably, in the step (4), the calcining treatment temperature is 900-1250 ℃, and the calcining time is 2-8h.
Preferably, in the step (5), one or more of zirconium balls or agate balls with the diameter of 1-10mm are used for ball milling and crushing, the ball milling medium is water, and the pigment: ball: the proportion of water is 1: (4-12): (0.3-1), the ball milling time is 0.5-1h, and the ball milling rotating speed is 150-300rad/min.
Preferably, in the step (6), the suspension slurry after ball milling needs to be kept stand for 1 to 6 hours at room temperature, and after the suspension slurry is kept stand, the supernatant is removed and dried at the temperature of 100 to 180 ℃, wherein the drying time is 1 to 6 hours.
Preferably, in the step (6), the dried black bulk pigment is sieved by using a screen, and the mesh number of the screen is 200-300 meshes.
Preferably, the glass paste prepared by mixing the black pigment with strong absorption to visible light and inorganic glass powder according to the conventional production process has excellent covering performance and OD value of 4.75-6.
Compared with the prior art, the invention has the beneficial effects that:
1) The black pigment of the invention mainly takes metal oxides such as chromium oxide, ferric oxide and the like as raw materials, the elements involved in the raw materials are transition metal elements of a fourth period, each element has a plurality of valence states, and a plurality of spinel structures formed after high-temperature calcination are mutually cooperated to strongly absorb light in a visible light-near infrared light region. When the introduction amount of the black pigment in the glass slurry is 15-30%, the higher covering power of the common black pigment of not less than 40% can be achieved, and the cost of the glass slurry can be greatly reduced.
2) Compared with the black pigment disclosed in the Chinese patent CN110790511A, namely the low-temperature environment-friendly black glass slurry with high optical density and the preparation method thereof, and the black pigment disclosed in the Chinese patent CN110563327A, namely the special melanin for automobile glass and the preparation method thereof, the two black pigments belong to the melanin of the copper-chromium system, and the high-temperature resistance stability and the chemical resistance stability of the pigment have certain defects. The acid corrosion resistance of the black pigment is obviously superior to that of a copper-chromium system pigment, and the black pigment has small expansion coefficient and high safety performance when being applied to a glass slurry system;
3) The mixed oxide crystal structure prepared by the chemical method when the black pigment with strong absorption to visible light is provided by the invention has the advantages of wide raw material source, simple and controllable preparation process, wide firing range, good firing stability, guarantee of finished product rate and relatively stable color when fired under a high-temperature condition;
4) The black pigment with strong absorption to visible light provided by the invention is especially suitable for automobile glass slurry, and has the advantages of low sintering temperature, excellent chemical corrosion resistance and excellent shielding performance. The black pigment meets the excellent performance of the automobile glass slurry, reduces the cost of a glass slurry industry company, is beneficial to the development of the domestic automobile glass slurry in the field of automobile glass, and lays a solid foundation for the domestic automobile glass slurry to move to the world.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, 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 present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the invention, and it is within the scope of the invention that modifications and variations can be made by one skilled in the art without departing from the basic concept of the invention.
Example 1
A black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 6％,Cr 2 O 3 30％,Fe 2 O 3 19％,MnO 2 20％,NiO 21％,ZnO 1％,MoO 3 2％,Al 2 O 3 1％。
a method for preparing a black pigment with strong absorption to visible light comprises the following steps:
(1) Weighing raw materials according to a ratio, and uniformly mixing the raw materials by using a high-speed mixer at a rotating speed of 50rad/min for 15min;
(2) Placing the mixed raw materials into a horizontal ball mill for medium-free mixed ball milling, wherein the volume of a tank body is 1L, the rotating speed is 50rad/min, and the raw materials are as follows: the ball proportion is 1;
(3) Placing the mixed and ball-milled raw materials in a crucible for compaction, placing the crucible in a closed muffle furnace for preheating treatment, wherein the preheating treatment temperature is 700 ℃, and the preheating treatment time is 3 hours;
(4) And (3) heating the preheated raw material in a closed muffle furnace for calcining, wherein the calcining temperature is 1000 ℃, the calcining time is 4h, and directly taking out the calcined crucible, and cooling the crucible at room temperature.
(5) And (3) carrying out ball milling on the pigment cooled to room temperature by using 1-5mm zirconium balls, wherein the ball milling medium is water, and the pigment: ball: the proportion of water is 1:8:0.8, the ball milling time is 0.5h, and the ball milling rotating speed is 150rad/min;
(6) Standing the suspension slurry subjected to ball milling for 1h at room temperature, removing supernatant after standing, and drying at 100 ℃ for 6h;
(7) And screening the dried black blocky pigment by using a screen, wherein the mesh number of the screen is 200 meshes, and thus obtaining the finished product black pigment.
The black pigment with strong absorption to visible light obtained in the example is mixed with inorganic glass powder according to a conventional production process to prepare glass slurry, the covering performance of the glass slurry is excellent, and the OD value of the optical density value is 5.11.
Example 2
The black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 8％,Cr 2 O 3 22％,Fe 2 O 3 30％,MnO 2 21％,NiO 16％,MoO 3 2％,Al 2 O 3 1％。
a method for preparing a black pigment with strong absorption to visible light comprises the following steps:
(1) Weighing the raw materials according to the proportion, and uniformly mixing the raw materials by using a high-speed mixer at the rotating speed of 80 rad/min for 12min;
(2) Placing the mixed raw materials into a horizontal ball mill for medium-free mixed ball milling, wherein the volume of a tank body is 1L, the rotating speed is 100rad/min, and the raw materials are as follows: the ball proportion is 1;
(3) Placing the mixed and ball-milled raw materials in a crucible for compaction, placing the crucible in a closed muffle furnace for preheating treatment, wherein the preheating treatment temperature is 700 ℃, and the preheating treatment time is 2 hours;
(4) And heating the preheated raw material in a closed muffle furnace for calcination treatment at 1180 ℃ for 5h, directly taking out the calcined crucible, and cooling at room temperature.
(5) And (3) carrying out ball milling on the pigment cooled to room temperature by using 1-5mm zirconium balls, wherein the ball milling medium is water, and the pigment: ball: the proportion of water is 1:6:1, ball milling time is 45min, and the rotating speed of ball milling is 240rad/min;
(6) Standing the suspension slurry subjected to ball milling for 6 hours at room temperature, removing supernatant after standing, and drying at 180 ℃, wherein the drying time is 1 hour;
(7) And screening the dried black blocky pigment by using a screen, wherein the mesh number of the screen is 300 meshes, so as to obtain the finished product black pigment.
The black pigment with strong absorption to visible light is mixed with inorganic glass powder according to a conventional production process to prepare the glass slurry, the covering performance is excellent, and the OD value is 5.16.
Example 3
The black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 9％,Cr 2 O 3 23％,Fe 2 O 3 14％,MnO 2 26％,NiO 24％,ZnO 1％，MoO 3 3％。
a method for preparing a black pigment with strong absorption to visible light comprises the following steps:
(1) Weighing the raw materials according to the proportion, and uniformly mixing the raw materials by using a high-speed mixer at the rotating speed of 120 rad/min for 10min;
(2) Placing the mixed raw materials into a horizontal ball mill for medium-free mixed ball milling, wherein the volume of a tank body is 1L, the rotating speed is 150rad/min, and the raw materials are as follows: the ball proportion is 1;
(3) Placing the mixed and ball-milled raw materials in a crucible for compaction, placing the crucible in a closed muffle furnace for preheating treatment, wherein the preheating treatment temperature is 780 ℃, and the preheating treatment time is 6 hours;
(4) And (3) heating the preheated raw material in a closed muffle furnace to perform calcination treatment, wherein the calcination treatment temperature is 1250 ℃, the calcination time is 8h, and directly taking out the calcined crucible, and placing the crucible at room temperature for cooling.
(5) And (3) performing ball milling crushing on the pigment cooled to room temperature by using 6-10mm agate balls, wherein the ball milling medium is water, and the pigment: ball: the proportion of water is 1:6:0.5, the ball milling time is 1h, and the ball milling rotating speed is 300rad/min;
(6) Standing the suspension slurry subjected to ball milling for 3h at room temperature, removing supernatant after standing, and drying at 140 ℃ for 3.5h;
(7) And screening the dried black blocky pigment by using a screen, wherein the mesh number of the screen is 250 meshes, so as to obtain the finished product black pigment.
The black pigment with strong absorption to visible light prepared in this example was mixed with inorganic glass powder according to a conventional production process to prepare a glass paste, which has excellent hiding performance and an OD value of 5.22.
Example 4
The black pigment with strong absorption to visible light comprises the following raw materials in percentage by mass:
CuO 12％,Cr 2 O 3 35％,Fe 2 O 3 15％,MnO 2 18％,NiO 16％,ZnO 2％,MoO 3 2％。
a method for preparing a black pigment with strong absorption to visible light comprises the following steps:
(1) Weighing the raw materials according to the proportion, and uniformly mixing the raw materials by using a high-speed mixer at the rotating speed of 150rad/min for 20min;
(2) Placing the mixed raw materials into a horizontal ball mill for medium-free mixed ball milling, wherein the volume of a tank body is 1L, the rotating speed is 50rad/min, and the raw materials are as follows: the ball proportion is 1;
(3) Placing the mixed and ball-milled raw materials in a crucible for compaction, placing the crucible in a closed muffle furnace for preheating treatment, wherein the preheating treatment temperature is 650 ℃, and the preheating treatment time is 2 hours;
(4) And (3) heating the preheated raw material in a closed muffle furnace to perform calcination treatment, wherein the calcination treatment temperature is 950 ℃, the calcination time is 3 hours, and directly taking out the calcined crucible and placing the crucible at room temperature for cooling.
(5) And (3) carrying out ball milling on the pigment cooled to room temperature by using 1-5mm zirconium balls, wherein the ball milling medium is water, and the pigment: ball: the proportion of water is 1:12:1, ball milling time is 45min, and the ball milling rotating speed is 240rad/min;
(6) Standing the suspension slurry subjected to ball milling for 4h at room temperature, removing supernatant after standing, and drying at 150 ℃ for 4h;
(7) And screening the dried black blocky pigment by using a screen, wherein the mesh number of the screen is 300 meshes, so as to obtain the finished product black pigment.
The black pigment with strong absorption to visible light prepared in the example is mixed with inorganic glass powder according to a conventional production process to prepare glass slurry, the covering performance is excellent, and the OD value is 5.51.
Example 5
Example 5 the black pigment and glass frit described in example 1 were used in the proportions of 15:85 according to the conventional production process, the glass slurry has excellent covering performance and an OD value of 4.75.
Example 6
Example 6 the black pigment and glass frit described in example 1 were used in a ratio of 2:8 according to the conventional production process, the glass slurry prepared by mixing the components has excellent covering performance, and the OD value is 5.12.
Example 7
Example 7 the black pigment and glass frit described in example 1 were used in the ratio of 4:6 according to the conventional production process, the glass slurry prepared by mixing the components in the proportion has excellent covering performance and the OD value of 6.
Comparative example 1
Compared with example 1, the differences are: the following steps were not carried out:
placing the mixed raw materials into a horizontal ball mill for medium-free mixed ball milling, wherein the volume of a tank body is 1L, the rotating speed is 50rad/min, and the raw materials are as follows: the proportion of the balls is 1.
Comparative example 2
Compared with example 2, the difference is that: the following steps were not performed:
and putting the mixed and ball-milled raw materials into a crucible for compaction, putting the crucible into a closed muffle furnace, heating the crucible to 700 ℃ along with the furnace, and carrying out preheating treatment for 2 hours.
Comparative example 3
Compared with example 3, the differences are that:
and (3) performing ball milling crushing on the pigment cooled to room temperature by using 6-10mm agate balls, wherein the ball milling medium is water, and the pigment: ball: the proportion of water is 1:6:0.5, the ball milling time is 1.5h, and the rotating speed of the ball milling is 300rad/min.
Comparative example 4
Compared with example 4, the difference is that:
the black pigment used was a conventional copper-chromium black pigment on the market
Comparative example 5
Compared with example 5, the difference is that:
the black pigment used is a conventional copper-chromium black pigment sold on the market
Comparative example 6
Compared with example 7, the difference is that:
the black pigment used was a commercially available conventional copper chromium black pigment.
Comparative example 7
Compared with example 7, the difference is that:
the black pigment used was a commercially available conventional copper chromium black pigment.
In the embodiment of the invention, the glass slurry is prepared by mixing the black pigment and the inorganic glass powder according to a conventional production process, wherein the conventional production process comprises the following steps: and weighing the finished black pigment and the finished glass powder according to a certain proportion, adding the ink mixing oil, and grinding for 3-5 times by using a three-roll grinder to obtain the glass slurry.
1. Experimental testing
1. Black pigment particle size test
The prepared black pigment was subjected to particle size testing using a laser particle sizer, and particle size D90 data is shown in table 1.
TABLE 1
As can be seen from Table 1, the absorption of light by the black colorant is mainly by the intrinsic components and structure of the colorant when the black colorant is close in size; if the components and structures of the black pigment are uniform and the particle sizes are different, the absorption of the black pigment to light is different, and the absorption is generally greater when the particle size is smaller. Table 1 shows that the black colorant of the present invention has a strong absorption of light due to the difference in the components and structures, by the data that the absorption of light is different when the particle sizes of the examples and comparative examples are close to each other.
2. Black pigment Performance test
The black pigment prepared in the above examples is mixed with a certain amount of glass powder, and the glass slurry prepared by adding the vehicle such as varnish is subjected to performance test, wherein the mixing ratio of the black pigment to the glass powder is as follows: 30%:70 percent. Printing the finished glass slurry on plate glass, and testing various performances after tempering at 700 ℃ for 150-200 s.
TABLE 2
3. Influence of different proportions on optical density values
Respectively mixing the black pigment prepared in the above embodiments with a certain amount of glass powder, adding carriers such as varnish and the like to prepare glass slurry for optical density test, printing the finished glass slurry on plate glass, and tempering at 700 ℃ for 150-200s, wherein the mixing ratio of the black pigment to the glass powder is as follows: 15%:85%, 20%:80%,30%:70%,40%:60 percent.
TABLE 3
As shown in tables 2 and 3, the black pigment with strong absorption to visible light prepared by the present invention has excellent hiding power, large optical density value, excellent blackness and high strength after being mixed with glass powder in a ratio of 30%.
The influence of different proportions on the light density value is simultaneously researched, and the result is shown in table 3, the black pigment with strong absorption on visible light, which is prepared by the invention, is obviously better than the glass slurry prepared by the conventional black pigment in hiding power after being mixed with glass powder in a proportion of 15-30%.
In the invention, after the raw materials are mixed and ball-milled by using the horizontal ball mill, the mixing uniformity of the raw materials is improved, the particles collide with each other between interfaces in the ball milling process, and metal ions are diffused between the interfaces. The mixed raw materials are subjected to a preheating treatment process to reduce the solid-phase reaction activity, and the components are fully reacted during high-temperature calcination to form mixed spinel structures of Cu-Cr-Mn, ni-Cr-Mn, ni-Fe-Mn and the like. The above elements are transition metal elements of the fourth period, each element has a plurality of valence states, and a plurality of spinel structures formed after high-temperature calcination are mutually cooperated to strongly absorb light in a visible light-near infrared light region. The black pigment prepared by controlling the crushing process is mixed with the glass powder in a small amount to prepare the glass slurry, so that the glass slurry has strong light absorption capacity and excellent covering performance. Meanwhile, the spinel obtained by calcining the black pigment system at high temperature has stable structure, good high temperature resistance and chemical stability and excellent safety, greatly reduces the cost of the glass slurry, can be applied to the fields of household appliances, buildings, automobiles and the like, and is particularly suitable for the field of automobile glass.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A black pigment with strong absorption to visible light is characterized by comprising the following raw materials in percentage by mass:
CuO 5-15%, Cr 2 O 3 10-40%, Fe 2 O 3 10-35%, MnO 2 15-30%, NiO 15-30%，ZnO 0-5%, MoO 3 1-5%, Al 2 O 3 0-3%；
the black pigment with strong absorption to visible light is prepared by the following preparation method, and specifically comprises the following steps:
(1) Weighing the raw materials according to the proportion, and uniformly mixing the raw materials by using a high-speed mixer;
(2) Ball milling the mixed raw materials;
(3) Placing the mixed and ball-milled raw materials in a crucible for compaction, and placing the crucible in a closed muffle furnace for preheating;
(4) Heating the preheated raw material in a closed muffle furnace for calcination, directly taking out the calcined crucible, and cooling at room temperature;
(5) Carrying out ball milling on the pigment cooled to room temperature;
(6) And standing the suspension slurry subjected to ball milling, removing the supernatant, drying and screening the lower concentrated slurry to obtain the finished black pigment.
2. The black pigment having strong absorption of visible light according to claim 1, comprising the following raw materials in percentage by mass:
CuO 6-12%, Cr 2 O 3 20-35%, Fe 2 O 3 14-30%, MnO 2 18-26%, NiO 16-24%，ZnO 0-2%, MoO 3 2-4%, Al 2 O 3 0-1%。
3. the black pigment having strong absorption of visible light according to claim 2, comprising the following raw materials in percentage by mass:
CuO 6%, Cr 2 O 3 30%, Fe 2 O 3 19%,MnO 2 20%, NiO 21%, ZnO 1%, MoO 3 2%, Al 2 O 3 1%。
4. the black pigment having strong absorption of visible light according to claim 2, comprising the following raw materials in percentage by mass:
CuO 8%, Cr 2 O 3 22%, Fe 2 O 3 30%,MnO 2 21%, NiO 16%,MoO 3 2%, Al 2 O 3 1%。
5. a black colorant having a strong absorption of visible light according to any one of claims 1 to 4, wherein the glass paste prepared by mixing it with an inorganic glass frit according to a conventional production process has an OD of 4.75 to 6.
6. A black colorant having strong absorption of visible light according to claim 1, wherein in the step (1), the mixing time is not less than 10min;
in the step (2), the mixed raw materials are placed in a horizontal ball mill for medium-free mixed ball milling, wherein the volume of a tank body is 1L, the rotating speed is 10-200rad/min, and the raw materials are as follows: the proportion of the balls is 1 (5-20), and the mixing and ball milling time is 5-24h.
7. The black coloring material having a strong absorption of visible light according to claim 1, wherein in the step (3), the temperature of the preheating treatment is 600 to 800 ℃ and the time of the preheating treatment is 2 to 6 hours;
in the step (4), the calcining treatment temperature is 900-1250 ℃, and the calcining time is 2-8h.
8. A black pigment with strong absorption of visible light according to claim 1, wherein in step (5), one or more of zirconium balls or agate balls with the diameter of 1-10mm are used for ball milling, the ball milling medium is water, and the pigment: ball: the proportion of water is 1: (4-12): (0.3-1), the ball milling time is 0.5-1h, and the ball milling rotating speed is 150-300rad/min.
9. The black pigment with strong absorption of visible light according to claim 1, wherein in step (6), the suspension slurry after ball milling needs to be left to stand at room temperature for 1-6h, and after standing, the supernatant is removed and then dried at 100-180 ℃ for 1-6h;
in the step (6), the dried black blocky pigment is screened by using a screen, and the mesh number of the screen is 200-300 meshes.
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| US4205996A (en) * | 1979-04-26 | 1980-06-03 | Scm Corporation | CoO Free black spinel ceramic pigment containing NiO, Fe2 O3 and Cr2 O3 |
| DE4140118A1 (en) * | 1991-12-05 | 1993-06-09 | Bayer Ag, 5090 Leverkusen, De | SPINEL BLACK PIGMENT BASED ON COPPER CHROME MANGANE MIXED OXIDS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| CN102660152B (en) * | 2012-04-20 | 2014-04-16 | 湖南信诺颜料科技有限公司 | Formulation of dry burning-resistant and burning-resistant inorganic pigment and preparation method of pigment |
| CN103880286B (en) * | 2014-01-25 | 2015-11-25 | 陕西科技大学 | A kind of sheet glass high temperature black colorant raw powder's production technology |
| CN110951280B (en) * | 2019-11-28 | 2021-10-08 | 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 |
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| CN111662570B (en) * | 2020-05-25 | 2021-09-24 | 武汉科技大学 | Mixed spinel type black ceramic pigment and preparation method thereof |
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