CN104311151A - Technique for firing spinel-type black ceramic material with tunnel kiln - Google Patents
Technique for firing spinel-type black ceramic material with tunnel kiln Download PDFInfo
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- CN104311151A CN104311151A CN201410515159.7A CN201410515159A CN104311151A CN 104311151 A CN104311151 A CN 104311151A CN 201410515159 A CN201410515159 A CN 201410515159A CN 104311151 A CN104311151 A CN 104311151A
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Abstract
The invention discloses a technique for firing a spinel-type black ceramic material with a tunnel kiln, which comprises the following steps: 1) uniformly mixing 25-40 wt% of chrome oxide green, 30-45 wt% of iron oxide red, 2-25 wt% of cobalt oxide, 10-20 wt% of nickel protoxide and 0-20 wt% of dopant; 2) filling the mixture obtained in the step 1) into a saggar by 70-80% full, calcining in a tunnel kiln, and naturally cooling the calcining product, wherein the technological conditions for calcination are as follows: the temperature of the preheating region is 1170-1250 DEG C, the temperature of the high-temperature region is 1200-1300 DEG C, and the transmission speed is 12-20 hours from charging to discharging; 3) pulverizing and grinding the cooled calcining product; and 4) adding concentrated hydrochloric acid to wash the calcining substance powder obtained in the step 3), stirring to sufficiently react, stirring, washing with water until the pH value is 7, drying and screening. The ceramic pigment has the advantages of high color development capacity and low cost.
Description
Technical field
The invention provides the processing method that a kind of tunnel furnace burns till spinel type black ceramic material, improve high-temperature stability and the chemical stability of spinel type stupalith.
Background technology
In ceramic pigment, spinel type ceramic coloring material enjoys ceramic industry to favor because of its high-temperature stability and chemical stability.Spinel type ceramic coloring material kind is extensive, comprises black, blueness, green etc., and wherein blue and black ceramic colorant is one of maximum product of ceramic industry consumption always.Now, popular due to black unburnt brick, makes base black ceramic colorant consumption surge.Blue, black ceramic colorant is most of for the production of high-grade ornamental brick or high-grade household china, but because such spinel type Pigment Material is expensive and process for processing cost is high, thus limit its use range, therefore reduce its production cost and improve the research emphasis that color development quality is ceramic pigment industry.
The traditional method preparing spinel type ceramic coloring material is solid reaction process, adopts this kind of usual calcining temperature of method more than 1200 DEG C.The blue colorant of spinel type take aluminum oxide as carrier, and cobalt oxide is coloring element, makes by the mineral such as doping zinc-oxide, silica powder the mazarine ceramic pigment obtaining partially green tune or red tune after high temperature sintering.Black ceramic colorant be generally with red iron oxide, chrome green for main raw material by adding cobalt oxide, the oxide compound of manganese, the oxide compound etc. of nickel make to obtain the product from dark brown to the different tone of blue-black, because cobalt oxide is expensive, existing most of producer by mixing manganese, the mode of nickel compound carrys out alternative cobalt oxide, or reduced costs by the mode changing production technique, as the improvement of calcining process, select the calcining manners of less energy-consumption high production capacity.Existing calcining technology generally adopts shuttle kiln, belongs to the intermittent mode of production, and production capacity is low, energy consumption is high.
As can be seen here, how to provide a kind of technique of burning till spinel type black ceramic colorant, improve coloring intensity and reduce manufacturing cost simultaneously, this is the technical problem that this area will solve at present.
Summary of the invention
In order to solve above-mentioned the deficiencies in the prior art, the object of the invention is to, a kind of tunnel furnace is provided to burn till the technique of spinel type black ceramic colorant, spinel type ceramic coloring material calcining temperature can be met higher and require the requirement of oxidizing roasting atmosphere, can coloring intensity be improved and reduce production cost simultaneously.
For solving above technical problem, technical scheme of the present invention is:
Tunnel furnace burns till a technique for spinel type black ceramic colorant, comprises the steps:
1) be the chromoxide green of 25%-40% by weight percent, the red iron oxide of 30%-45%, the cobalt oxide of 2%-25%, the nickel protoxide of 10%-20%, the hotchpotch of 2%-20% mix;
2) by step 1) mixture that is mixed to get loads saggar, and load 7-8 and divide full, send into tunnel furnace calcining, the calcined material naturally cooling will obtained after calcining; The processing condition of calcining are: the temperature of preheating zone is 1170 DEG C-1250 DEG C, and high-temperature zone temperature is: 1200 DEG C-1300 DEG C; Transmission speed is: from being dosed to discharging 12-20H;
3) cooled calcined material is pulverized levigate;
4) add concentrated hydrochloric acid acid pickling step 3) pulverize levigate after the calcined material powder that obtains, stirring reacts fully, then stirs that to be washed to PH be 7, then dry, sieve and get final product.
Preferably, step 4) in, concentrated hydrochloric acid: calcined material powder: the mass ratio of water is (1.5-3): 100:50.
Preferably, step 4) in, concentrated hydrochloric acid: calcined material powder: the mass ratio of water is 2:100:50.
Preferably, step 4) in, concentrated hydrochloric acid: calcined material powder: the mass ratio of water is 2.5:100:50.。
Preferably, step 2) in, transmission speed is: from being dosed to discharging 14-18H.
Preferably, step 2) in, preheating zone temperature is 1200 DEG C-1240 DEG C.
Preferably, step 2) in, high-temperature zone temperature is: 1250 DEG C-1280 DEG C.
Preferably, step 2) in, during calcining, exhausting makes to form negative pressure in tunnel furnace.
Preferably, step 2) in, tunnel furnace used is the kiln of consecutive production mode, and both ends open opens wide.
Preferably, step 2) in, tunnel furnace used is provided with the vacuum fan of frequency-adjustable.
Shuttle kiln of the prior art, owing to being closed calcining kiln, realize strong oxidizing atmosphere and then be difficult to reach the calcining temperature needed for product synthesis, and conventional shuttle kiln temperature difference being comparatively large, is unfavorable for the product synthesizing high-quality.In technique of the present invention, tunnel furnace used is the kiln of consecutive production mode, both ends open opens wide, arbitrarily furnace atmosphere can be regulated by regulating the frequency of vacuum fan, kiln divides preheating proparea, preheating zone, high-temperature zone simultaneously, cooling zone, realize the change of stablizing temperature control and temperature curve, calcination time is by transmission frequency adjustment.The present invention's tunnel furnace used changes the batch production mode that prior art adopts shuttle kiln, improves production capacity, makes more energy-conservation.
In technical scheme of the present invention, by being optimized the proportioning of raw material, carry out reasonably optimizing according to processing condition during raw material pairing tunnel furnace calcining, the ceramic pigment color development ability thus obtained is strong, and cost is low simultaneously simultaneously.
Embodiment
For making technical scheme of the present invention clearly, below in conjunction with being come by specific embodiment, the present invention is described in detail.
Of the present inventionly to be contemplated that: strengthen in view of reaching the target that product coloring intensity and high-temperature stability reduce production cost simultaneously, the present invention is by Material synthesis colorant crystal principles and calcination atmosphere impact, select the tunnel furnace of strong oxidizing atmosphere, less energy-consumption, work out suitable calcining curve and the atmospheric condition being conducive to product synthesis.In the present invention, more easily high temperature solid state reaction occurs according to the uniform material of solid state reaction mechanism altitude distribution through calcining, so raw material more easily forms spinel carrier after Homogeneous phase mixing, coloring element enters in lattice more and goes simultaneously.Pulverize refinement again after the calcining of mixture process of passing through tunnel kiln, make particle diameter D
90reach 13-18 μm, finally obtain product.
Technical scheme of the present invention is:
Tunnel furnace burns till a technique for spinel type black ceramic colorant, comprises the steps:
1) be the chromoxide green of 25%-40% by weight percent, the red iron oxide of 30%-45%, the cobalt oxide of 2%-25%, the nickel protoxide of 10%-20%, the hotchpotch of 2%-20% mix;
2) by step 1) mixture that is mixed to get loads saggar, and load 7-8 and divide full, send into tunnel furnace calcining, wherein, in tunnel furnace, the temperature of preheating zone is 1170 DEG C-1250 DEG C, and high-temperature zone temperature is: 1200 DEG C-1300 DEG C; Transmission speed: be about 12-20H from being dosed to discharging; In calcination process, exhausting makes to form negative pressure in tunnel furnace, last naturally cooling;
3) cooled calcined material is pulverized levigate;
4) add concentrated hydrochloric acid acid pickling step 3) pulverize levigate after the calcined material powder that obtains, stirring reacts fully, then stirs that to be washed to PH be 7, then dry, sieve and get final product.
The black ceramic pigment that the present invention obtains, has following all characteristics:
Outward appearance: black powder
Fineness: D90 is 13-18 μm
Lightness: 27≤L≤40;
Form and aspect: 1≤a≤5;
Form and aspect :-26≤b≤-10.
Embodiment one
The technique of burning till spinel type black ceramic colorant with tunnel furnace of the present embodiment, comprises the steps:
1) by matrix material chromoxide green, red iron oxide, cobalt oxide, nickel protoxide in mass ratio 30:38:18:14 mix;
2) said mixture is loaded saggar, load 8 points completely, saggar intersects folded, is placed in conventional gas shuttle kiln and tunnel furnace calcining respectively;
Gas shuttle kiln calcining process: 25 DEG C-500 DEG C, intensification 2H, 500 DEG C-1000 DEG C, intensification 3H, 1000 DEG C-1250 DEG C, intensification 3H; 1250 DEG C of constant temperature 4H, Temperature fall less than 200 DEG C dischargings, reprocess to fineness particle diameter D90 be 13-18 μm.Be designated as C;
Tunnel furnace calcining process: 1200 DEG C, preheating zone, 1250 DEG C, high-temperature zone; Transmission speed: be about 17H from being dosed to discharging; Exhausting makes to form negative pressure, last naturally cooling in kiln; Be designated as D;
3) cooled calcined material is pulverized levigate, adds concentrated hydrochloric acid pickling powder, concentrated hydrochloric acid: powder: water in mass ratio example is 1.5:100:50, adds rear stirring and reacts fully, then stirring to be washed to PH be 7;
4) step 3) product drying, sieves powder and get final product.
The black ceramic colorant obtained above is carried out comparison of production and color development detection contrast, result is as follows:
1, energy consumption comparison
C: gas shuttle kiln calcining output every day is about 900kg, product combustion gas power consumption about 2.5 yuan/kg;
D: tunnel furnace calcining output every day is about 1800kg, product energy consumption about 1.3 yuan/kg
2, color development comparison and detection
The glaze colours basis glaze formula that black ceramic colorant uses:
0.276 K
2O 0.003 Fe
2O
3 3.5 SiO
2
0.066 Na
2O 0.522 Al
2O
3 0.658 CaO
In the present embodiment, in parent glaze additional massfraction be 5% the present invention synthesize colorant D and gas shuttle kiln synthesis products C do color development contrast, temperature of glaze firing is 1100 DEG C, and firing time is 60 minutes, soaking time 15-30 minute, test color difference:
Test the data obtained: C sample: L:35.30 a:3.53 b:-16.45
Test the data obtained: D sample: L:32.54 a:3.01 b:-20.38
The product that black ceramic colorant production cost prepared by above data declaration tunnel furnace of the present invention is prepared than gas shuttle kiln is lower, and color development quality is better simultaneously, and color development is darker, and green degree is higher than it, and blue angle value is high, and aobvious aterrimus, quality improves about 20%.And the black ceramic colorant product that shuttle kiln burns till partially shallow and partially palm fibre adjust, the black ceramic colorant product of bluish-green tune is more had a preference in market, thus tunnel furnace calcining black ceramic colorant quality better.
Embodiment two
The technique of burning till spinel type black ceramic colorant with tunnel furnace of the present embodiment, comprises the steps:
1) by matrix material chromoxide green, red iron oxide, cobalt oxide, nickel protoxide in mass ratio 30:38:18:14 mix;
2) said mixture is loaded saggar, load 8 points completely, saggar intersects folded, is placed in tunnel furnace calcining, but regulates kiln atmosphere respectively, test as follows:
Tunnel furnace is calcined, 1200 DEG C, preheating zone, 1250 DEG C, high-temperature zone; Transmission speed: be about 17H from being dosed to discharging; Exhausting makes to form negative pressure, last naturally cooling in kiln; Be designated as D;
Tunnel furnace is calcined, 1200 DEG C, preheating zone, 1250 DEG C, high-temperature zone; Transmission speed: be about 17H from being dosed to discharging; Not exhausting in kiln, natural draught system, last naturally cooling; Be designated as E;
3) cooled calcined material is pulverized levigate, adds concentrated hydrochloric acid pickling powder, concentrated hydrochloric acid: powder: water in mass ratio example is 3:100:50, adds rear stirring and reacts fully, then stirring to be washed to PH be 7;
4) step 3) product drying, sieves powder and get final product.
The black ceramic colorant obtained above is carried out comparison of production and color development detection contrast, result is as follows:
The glaze colours basis glaze formula that black ceramic colorant uses:
0.276 K
2O 0.003 Fe
2O
3 3.5 SiO
2
0.066 Na
2O 0.522 Al
2O
3 0.658 CaO
In the present embodiment, in parent glaze additional massfraction be 5% synthesis colorant E and synthesis colorant F do color development contrast, temperature of glaze firing is 1100 DEG C, and firing time is 60 minutes, soaking time 15-30 minute, test color difference:
Test the data obtained: D sample: L:32.54 a:3.01 b:-20.38
Test the data obtained: E sample: L:33.80 a:3.32 b:-18.65
During above data declaration calcining, exhausting makes formation negative pressure in kiln better than the product color development quality obtained by natural exhaust, and color development is darker, and green degree is higher than it, blue angle value is high, aobvious aterrimus, quality improves about 10%, the obtained black product of tunnel furnace calcination process natural exhaust partially shallow and partially palm fibre adjust; Secondly, glaze paint can be caused after the product application that natural exhaust is calcined to have a large amount of pin hole or bubble.The synthesis of spinel type black product is solid state reaction process, and strong oxidizing atmosphere is favourable to reaction.The impurity existed in raw material during solid state reaction needs to drain, and natural exhaust makes the foreign gas of reacting generation have little time to drain, and cause can not get strong oxidizing atmosphere and reduce product synthesis quality, more seriously residual impurity is also difficult to wash through overpickling.Impurity decomposes under the high temperature conditions once again, therefore for there will be a large amount of pin hole and bubble during ornamental brick.
Embodiment three
The technique of burning till spinel type black ceramic colorant with tunnel furnace of the present embodiment, comprises the steps:
1) by matrix material chromoxide green, red iron oxide, cobalt oxide, nickel protoxide in mass ratio 25:30:25:20 mix;
2) said mixture is loaded saggar, load 8 points completely, saggar intersects folded, and be placed in tunnel furnace calcining, calcining process condition is as follows:
1170 DEG C, preheating zone, 1200 DEG C, high-temperature zone; Transmission speed: be about 15H from being dosed to discharging; Exhausting makes to form negative pressure, last naturally cooling in kiln;
3) cooled calcined material is pulverized levigate, adds concentrated hydrochloric acid pickling powder, concentrated hydrochloric acid: powder: water in mass ratio example is 2.5:100:50, adds rear stirring and reacts fully, then stirring to be washed to PH be 7;
4) step 3) product drying, sieves powder and get final product.
The black ceramic colorant obtained above is carried out comparison of production and color development detection contrast, result is as follows:
The glaze colours basis glaze formula that black ceramic colorant uses:
0.276 K
2O 0.003 Fe
2O
3 3.5 SiO
2
0.066 Na
2O 0.522 Al
2O
3 0.658 CaO
In the present embodiment, in parent glaze additional massfraction be 5% the present invention synthesize colorant F and gas shuttle kiln synthesis products C do color development contrast, temperature of glaze firing is 1100 DEG C, and firing time is 60 minutes, soaking time 15-30 minute, test color difference:
Test the data obtained: F sample: L:32.34 a:3.21 b:-20.48
Test the data obtained: C sample: L:35.30 a:3.53 b:-16.45
The product that the black ceramic colorant production cost that above data declaration the present invention utilizes tunnel furnace to prepare is prepared than gas shuttle kiln is lower, and color development quality is better simultaneously, and color development is darker, and green degree is higher than it, and blue angle value is high, and aobvious aterrimus, quality improves about 20%.And the black ceramic colorant product that shuttle kiln burns till partially shallow and partially palm fibre adjust, the black ceramic colorant product of bluish-green tune is more had a preference in market, thus tunnel furnace calcining black ceramic colorant quality better.
Embodiment four
The technique of burning till spinel type black ceramic colorant with tunnel furnace of the present embodiment, comprises the steps:
1) by matrix material chromoxide green, red iron oxide, cobalt oxide, nickel protoxide in mass ratio 40:45:5:10 mix;
2) said mixture is loaded saggar, load 8 points completely, saggar intersects folded, and be placed in tunnel furnace calcining, calcining process condition is as follows:
1250 DEG C, preheating zone, 1300 DEG C, high-temperature zone; Transmission speed: be about 15H from being dosed to discharging; Exhausting makes to form negative pressure, last naturally cooling in kiln;
3) cooled calcined material is pulverized levigate, adds concentrated hydrochloric acid pickling powder, concentrated hydrochloric acid: powder: water in mass ratio example is 3:100:50, adds rear stirring and reacts fully, then stirring to be washed to PH be 7;
4) step 3) product drying, sieves powder and get final product.
The black ceramic colorant obtained above is carried out comparison of production and color development detection contrast, result is as follows:
The glaze colours basis glaze formula that black ceramic colorant uses:
0.276 K
2O 0.003 Fe
2O
3 3.5 SiO
2
0.066 Na
2O 0.522 Al
2O
3 0.658 CaO
In the present embodiment, in parent glaze additional massfraction be 5% the present invention synthesize colorant G and gas shuttle kiln synthesis products C do color development contrast, temperature of glaze firing is 1100 DEG C, and firing time is 60 minutes, soaking time 15-30 minute, test color difference:
Test the data obtained: F sample: L:32.35 a:3.28 b:-20.34
Test the data obtained: C sample: L:35.30 a:3.53 b:-16.45
The product that the black ceramic colorant production cost that above data declaration the present invention utilizes tunnel furnace to prepare is prepared than gas shuttle kiln is lower, and color development quality is better simultaneously, and color development is darker, and green degree is higher than it, and blue angle value is high, and aobvious aterrimus, quality improves about 20%.And the black ceramic colorant product that shuttle kiln burns till partially shallow and partially palm fibre adjust, the black ceramic colorant product of bluish-green tune is more had a preference in market, thus tunnel furnace to calcine the black ceramic colorant quality obtained better.
As can be seen from the above embodiments, the shuttle kiln of black ceramic colorant than traditional in average energy consumption that technique of the present invention obtains is lower, reduces production cost, the product color development better quality of simultaneously digital proof tunnel furnace calcining and stability is high.
Below be only the preferred embodiment of the present invention, it should be pointed out that above-mentioned preferred implementation should not be considered as limitation of the present invention, protection scope of the present invention should be as the criterion with claim limited range.For those skilled in the art, without departing from the spirit and scope of the present invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. burn till a technique for spinel type black ceramic colorant with tunnel furnace, it is characterized in that, comprise the steps:
1) be the chromoxide green of 25%-40% by weight percent, the red iron oxide of 30%-45%, the cobalt oxide of 2%-25%, the nickel protoxide of 10%-20%, the hotchpotch of 0-20% mix;
2) by step 1) mixture that is mixed to get loads saggar, and load 7-8 and divide full, send into tunnel furnace calcining, the calcined material naturally cooling will obtained after calcining; The processing condition of calcining are: the temperature of preheating zone is 1170 DEG C-1250 DEG C, and high-temperature zone temperature is: 1200 DEG C-1300 DEG C; Transmission speed is: from being dosed to discharging 12-20H;
3) cooled calcined material is pulverized levigate;
4) add concentrated hydrochloric acid acid pickling step 3) pulverize levigate after the calcined material powder that obtains, stirring reacts fully, then stirs that to be washed to PH be 7, then dry, sieve and get final product.
2. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 4) in, concentrated hydrochloric acid: calcined material powder: the mass ratio of water is (1.5-3): 100:50.
3. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 4) in, concentrated hydrochloric acid: calcined material powder: the mass ratio of water is 2:100:50.
4. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 4) in, concentrated hydrochloric acid: calcined material powder: the mass ratio of water is 2.5:100:50.
5. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 2) in, transmission speed is: from being dosed to discharging 14-18H.
6. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 2) in, preheating zone temperature is 1200 DEG C-1240 DEG C.
7. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 2) in, high-temperature zone temperature is: 1250 DEG C-1280 DEG C.
8. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 2) in, during calcining, exhausting makes to form negative pressure in tunnel furnace.
9. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 2) in, tunnel furnace used is the kiln of consecutive production mode, and both ends open opens wide.
10. tunnel furnace as claimed in claim 1 burns till the technique of spinel type black ceramic colorant, it is characterized in that, step 2) in, tunnel furnace used is provided with the vacuum fan of frequency-adjustable.
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| CN109135337A (en) * | 2018-07-18 | 2019-01-04 | 佛山市三水金鹰无机材料有限公司 | A kind of preparation method of Portoro ceramic ink jet colorant |
| CN109321029A (en) * | 2018-05-14 | 2019-02-12 | 四会市中达化工颜料有限公司 | A kind of low magnetic cobalt black ceramic ink pigments and preparation method thereof |
| CN111533562A (en) * | 2020-04-30 | 2020-08-14 | 中国科学院上海硅酸盐研究所 | Black silicon nitride ceramic mobile phone backboard material and method for preparing mobile phone backboard by using same |
| CN112143256A (en) * | 2020-09-23 | 2020-12-29 | 佛山市三水天宇陶瓷颜料有限公司 | High-temperature-resistant black ceramic pigment, preparation process and ceramic tile using high-temperature-resistant black ceramic pigment |
| CN113801496A (en) * | 2021-09-26 | 2021-12-17 | 广东精英无机材料有限公司 | Cobalt-containing ceramic black pigment and preparation method and application thereof |
| CN114369376A (en) * | 2022-01-28 | 2022-04-19 | 湖南信诺颜料科技有限公司 | High-brightness cobalt melanin and preparation method thereof |
| CN117264440A (en) * | 2023-11-14 | 2023-12-22 | 山东陶正新材料科技有限公司 | Manufacturing process of black pigment for high-temperature-resistant alumina and zirconia ceramics |
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| CN109321029A (en) * | 2018-05-14 | 2019-02-12 | 四会市中达化工颜料有限公司 | A kind of low magnetic cobalt black ceramic ink pigments and preparation method thereof |
| CN109135337A (en) * | 2018-07-18 | 2019-01-04 | 佛山市三水金鹰无机材料有限公司 | A kind of preparation method of Portoro ceramic ink jet colorant |
| CN111533562A (en) * | 2020-04-30 | 2020-08-14 | 中国科学院上海硅酸盐研究所 | Black silicon nitride ceramic mobile phone backboard material and method for preparing mobile phone backboard by using same |
| CN112143256A (en) * | 2020-09-23 | 2020-12-29 | 佛山市三水天宇陶瓷颜料有限公司 | High-temperature-resistant black ceramic pigment, preparation process and ceramic tile using high-temperature-resistant black ceramic pigment |
| CN112143256B (en) * | 2020-09-23 | 2022-02-01 | 佛山市三水天宇陶瓷颜料有限公司 | High-temperature-resistant black ceramic pigment, preparation process and ceramic tile using high-temperature-resistant black ceramic pigment |
| CN113801496A (en) * | 2021-09-26 | 2021-12-17 | 广东精英无机材料有限公司 | Cobalt-containing ceramic black pigment and preparation method and application thereof |
| CN113801496B (en) * | 2021-09-26 | 2022-10-14 | 广东精英无机材料有限公司 | Cobalt-containing ceramic black pigment and preparation method and application thereof |
| CN114369376A (en) * | 2022-01-28 | 2022-04-19 | 湖南信诺颜料科技有限公司 | High-brightness cobalt melanin and preparation method thereof |
| CN117264440A (en) * | 2023-11-14 | 2023-12-22 | 山东陶正新材料科技有限公司 | Manufacturing process of black pigment for high-temperature-resistant alumina and zirconia ceramics |
| CN117264440B (en) * | 2023-11-14 | 2024-01-30 | 山东陶正新材料科技有限公司 | Manufacturing process of black pigment for high-temperature-resistant alumina and zirconia ceramics |
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