CN112280330B - Attapulgite-doped cerium sulfide pigment and preparation method thereof - Google Patents
Attapulgite-doped cerium sulfide pigment and preparation method thereof Download PDFInfo
- Publication number
- CN112280330B CN112280330B CN202010786008.0A CN202010786008A CN112280330B CN 112280330 B CN112280330 B CN 112280330B CN 202010786008 A CN202010786008 A CN 202010786008A CN 112280330 B CN112280330 B CN 112280330B
- Authority
- CN
- China
- Prior art keywords
- cerium
- compound
- attapulgite
- temperature
- alkali metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/288—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Cosmetics (AREA)
Abstract
The invention disclosesAn attapulgite clay doped cerium sulfide pigment and a preparation method thereof. The rare earth pigment provided by the invention contains attapulgite and cerium sulfide. The preparation method of the rare earth pigment provided by the invention comprises the steps of uniformly mixing the attapulgite, the cerium compound, the alkali metal compound, the vulcanizing agent and the solid carbon, and heating for reaction under the protection of inert gas. The stable temperature of the cerium sulfide pigment prepared by the invention in the air is effectively increased to 460 ℃, and the thermal stability of the cerium sulfide pigment is improved. No toxic, inflammable and explosive gas H is used in the preparation process2S and CS2The attapulgite clay is safe and environment-friendly, and the attapulgite clay raw material is doped by adopting a solid phase grinding method, so that the process is simple, safe and reliable. The cerium sulfide pigment prepared by the invention is bright in color, safe and nontoxic, and can be widely applied to coloring of building materials such as plastics, coatings, paints, leather, rubber, printing ink, ceramics, paper, cosmetics, cement and the like.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to an attapulgite-doped cerium sulfide pigment and a preparation method thereof. Belongs to the synthesis technology of inorganic pigments.
Background
The red pigment is mainly divided into two categories of organic pigment and inorganic pigment, the organic red pigment is widely used for coloring primary pulp of printing ink, paint, coating and synthetic fiber, coating printing of fabrics, coloring of plastics, rubber and leather and the like due to the characteristics of bright color and strong tinting strength, and the pigment using amount of the printing ink is the largest. At present, the yield of organic pigments accounts for about one fourth of the total yield of dyes. But at the same time, because of the characteristics of poor covering power, thermal stability, light stability and ultraviolet radiation resistance, the existing inorganic pigment still has a large proportion. However, most of the currently used inorganic red pigments contain heavy metal elements harmful to human bodies, such as lead, cadmium, mercury, and the like, and the long-term use of the inorganic red pigments can cause certain damage to the health of people, so that the development of a safe, environment-friendly and high-performance inorganic red pigment is imperative. Due to the electron movement of the rare earth element 4f and the unique sublayer structure thereof, certain rare earth sulfides generate effective light absorption and can be used as inorganic pigments. Red pigment cerium sulfide (gamma-Ce)2S3) It has bright red color, no toxicity, strong covering power, strong ultraviolet absorption, and can be maintained at 1500 deg.C in inert atmosphereIs stable and can be kept below 350 ℃ in an oxygen atmosphere, and is the preferred material for replacing cadmium red. Since 1996 cerium sulfide was successfully developed as a pigment by rhodia, france and widely used in a number of coloring applications. There are many patents reporting on the synthesis of cerium sulfide pigments, and the current methods for preparing cerium sulfide can be largely classified into two categories according to the sulfur source used. One is to use H2S/CS2Or a mixed atmosphere of the two, for example, the method used in CN1201441 of Rodia, France in China is to mix a carbonate or bicarbonate of a rare earth element with an alkali metal element, dry it, and dry the product in H2,CS2And H2Heating at 800 ℃ for one hour under purging of S gave a dark red product. Another process for preparing rare earth sulfides is reported in the European patent publication EP0680930A, which uses H2S or CS2Rare earth carbonate or bicarbonate and at least one alkali metal element compound are used as raw materials for a vulcanizing agent to react for 0.25 to 2 hours at a temperature of between 500 and 800 ℃ to obtain a red product. Another method is not to use H2S and CS2Solid sulfur is used as a sulfur source instead of dangerous gas, and Chinese patent with the patent number of CN 102120602A reports a method for obtaining a rare earth colorant by taking rare earth carbonate or rare earth oxide as a raw material and two solid substances of sulfur and solid carbon as vulcanizing agents and reacting in a closed reactor at 1000-1500 ℃. Another method for producing a colorant is disclosed in japanese patent No. JP2619819, in which a mixture of cerium oxalate, sulfur and sodium carbonate is ground and mixed uniformly in a mortar, and then the mixture is placed in a tube furnace, and a mixed gas of hydrogen and argon containing 10% by volume of hydrogen is introduced to react at 1200 ℃ for 1 hour to obtain a rare earth sulfide object colorant. The methods described in the above patents, while providing a good yield of cerium sulfide colorant, have several disadvantages. (1) The preparation process uses toxic or inflammable explosive gas H2S，CS2，H2And the like, has great potential safety hazard. (2) The cerium sulfide colorant prepared by the method disclosed in the above patent is expensive, and is not suitable for mass production and wide application. (3) SulfurThe cerium oxide pigment is decomposed when the thermal stability in the air is not good enough at more than 350 ℃.
Disclosure of Invention
The invention mainly aims at the problems of insufficient preparation technology, high price, poor thermal stability and the like of the existing cerium sulfide coloring agent, and develops an attapulgite-doped cerium sulfide pigment and a preparation method thereof.
The invention provides a rare earth pigment which contains attapulgite and cerium sulfide.
The invention also provides a preparation method of the rare earth pigment, which comprises the steps of uniformly mixing the attapulgite, the cerium compound, the alkali metal compound, the vulcanizing agent and the solid carbon, and heating for reaction under the protection of inert gas. Wherein the heating reaction temperature is 800-1100 ℃.
More specifically, the attapulgite, the cerium compound, the alkali metal compound, the vulcanizing agent and the solid carbon are ground and uniformly mixed, under the protection of inert gas, the temperature is increased to 900 ℃ at the heating rate of 6 ℃/min, then the temperature is preserved for one hour at 900 ℃, the temperature is increased to 1100 ℃ at the heating rate of 3 ℃/min, the temperature is preserved for one hour, and finally the temperature is reduced to the room temperature at the cooling rate of 7 ℃/min.
Wherein the mass ratio of the attapulgite to the cerium in the cerium compound is 1: 3-5; the molar ratio of the alkali metal compound to cerium in the cerium compound is 1: 0.05-0.4, preferably 1: 0.15; the mol ratio of the vulcanizing agent to the cerium in the cerium compound is 1: 2-6, preferably 1: 4; the molar ratio of cerium in the solid carbon and the cerium compound is 1: 1 to 4, preferably 1: 2.
Wherein the cerium compound is selected from cerium dioxide, or one or more of carbonate, nitrate, oxalate, sulfate and hydrochloride of cerium.
Wherein the alkali metal compound is one or more of alkali metal carbonate, sulfate, sulfide and sulfite.
The preparation method of the rare earth dye provided by the invention comprises the steps of mixing attapulgite and a water-soluble cerium compound in water, adding sufficient alkaline substances to completely precipitate cerium, filtering, drying, grinding to obtain a coprecipitation precursor, then adding an alkali metal compound, a vulcanizing agent and solid carbon, uniformly mixing, and heating for reaction under the protection of inert gas.
Wherein the alkaline substance is selected from one or more of ammonia water, sodium hydroxide, potassium hydroxide, and sodium carbonate.
Wherein the attapulgite may be purified.
Wherein, the purity of the cerium compound is more than 99 percent, the vulcanizing agent is sublimed sulfur, and the mass percent of the fixed carbon is more than 80 percent.
Specifically, the preparation method of the rare earth dye provided by the invention comprises the following steps:
firstly, attapulgite clay pretreatment: adding 1-6% of dispersing agent by mass into raw attapulgite, heating in a water bath at 50-90 ℃, performing ultrasonic treatment for about 1-2 hours, and stirring for 2-4 hours. Centrifuging the reaction mixture, decanting to obtain upper suspension, and drying in a freeze-drying machine to obtain coarse purified attapulgite raw material. Stirring the roughly purified attapulgite for about 20 hours by using concentrated acid at the temperature of 70-80 ℃, filtering, washing to be neutral, and drying. The attapulgite precursor which can be used for the next experiment is obtained.
Secondly, mixing the attapulgite and the cerium compound uniformly by a solid phase grinding method and a liquid phase coprecipitation method
Solid phase grinding method: the attapulgite clay and cerium compound treated in the above steps are used as raw materials, alkali metal compound is used as additive, reaction auxiliary agents such as vulcanizing agent and solid carbon are added, the mass ratio of the added reactants is that the attapulgite clay to cerium is 1: 3-5, the adding mole ratio of the additive is alkali metal: cerium is 1:0.05 to 0.4, and the optimum addition ratio is about 0.15. The addition molar ratio of the vulcanizing agent is sulfur: the cerium is 1: 2-6, and the optimal addition ratio is about 4. The addition molar ratio of the auxiliary carbon is 1-4, and the optimal addition ratio is about 2. The treated attapulgite, the cerium compound and the alkali metal compound are uniformly mixed according to the proportion and fully ground. Then mixing the vulcanizing agent and the solid carbon uniformly according to the proportion, and fully grinding. And finally, uniformly mixing all reactants, placing the mixture into an alumina reaction boat, and reacting in a tubular furnace. Before the reaction begins, argon is firstly introduced to drive the air in the tube furnaceAnd after heating is started, continuously introducing argon to protect the system. Heating to 900 ℃ at a heating rate of 6 ℃/min, then preserving heat for one hour at 900 ℃, heating to 1100 ℃ at a heating rate of 3 ℃/min, preserving heat for one hour, and finally cooling to room temperature at a cooling rate of 7 ℃/min. Grinding the product, washing with water, filtering, and drying to obtain red attapulgite clay doped with gamma-Ce2S3And (3) powder. Liquid-phase coprecipitation method: the method is the same as the solid phase grinding method, the attapulgite clay treated by concentrated acid is used as a raw material, the two precursors are mixed according to the mass ratio of 1: 3-5, and a proper amount of distilled water is added and stirred overnight. Adding enough alkali to completely precipitate cerium under continuous stirring, continuously stirring for about ten minutes, performing suction filtration, washing with water to neutrality, and washing with a small amount of ethanol. Drying in an oven at 80 ℃, and grinding to obtain the coprecipitation precursor. The addition mole ratio of the additive is alkali metal: cerium is 0.05 to 0.4, and the optimum addition ratio is about 0.15. The addition molar ratio of the vulcanizing agent is sulfur: the cerium is 2-6, and the optimal adding proportion is about 4. The addition molar ratio of the auxiliary solid carbon is 1-4, and the optimal addition ratio is about 2. The treated coprecipitation precursor and alkali metal compound are mixed uniformly according to the proportion and fully ground. Then mixing the vulcanizing agent and the solid carbon uniformly according to the proportion, and fully grinding. And finally, uniformly mixing all reactants, placing the mixture into an alumina reaction boat, and reacting in a tubular furnace. Before the reaction starts, argon is firstly introduced to drive air in the tube furnace, and after heating is started, argon is continuously introduced to protect the reaction. Heating to 900 ℃ at a heating rate of 6 ℃/min, then preserving heat for one hour at 900 ℃, heating to 1100 ℃ at a heating rate of 3 ℃/min, preserving heat for one hour, and finally cooling to room temperature at a cooling rate of 7 ℃/min. Grinding the product, washing with water, filtering, and drying to obtain red attapulgite clay doped with gamma-Ce2S3And (3) powder.
The invention has the following beneficial effects:
the stable temperature of the cerium sulfide pigment prepared by the invention in the air is effectively increased to 460 ℃, and the thermal stability of the cerium sulfide pigment is improved. No toxic, inflammable and explosive gas H is used in the preparation process2S and CS2The attapulgite clay is safe and environment-friendly, and the attapulgite clay raw material is doped by adopting a solid phase grinding method, so that the process is simple, safe and reliable. The liquid-phase coprecipitation method provides a new idea for preparing cerium sulfide. The cerium sulfide pigment prepared by the invention is bright in color, safe and nontoxic, and can be widely applied to coloring of building materials such as plastics, coatings, paints, leather, rubber, printing ink, ceramics, paper, cosmetics, cement and the like.
Drawings
FIG. 1 is a thermogram of a sample prepared in example 1
FIG. 2 is a thermogram of a sample prepared in example 2
FIG. 3 is an XRD contrast of attapulgite doped cerium sulfide pigment with cerium sulfide
Detailed description of the invention
In order to better understand the present invention, the following examples are further provided to illustrate the present invention.
Example 1
0.1g of acid-treated attapulgite clay, 0.5g of cerium dioxide and 0.022g of Na2CO3Mixing, and grinding. Then 0.4g of sublimed sulfur and 0.085g of active carbon are weighed, evenly mixed and fully ground, and finally all reactants are evenly mixed and placed in an alumina reaction boat for reaction in a tube furnace. Argon gas is introduced at a relatively fast rate for about ten minutes to drive the air in the system, and then argon gas is introduced at a gas flow rate of about one bubble per second to protect the reaction. The temperature is between room temperature and 900 ℃, the temperature rise time is 150 minutes, the temperature rise time is between 900 and 900 ℃, the heat preservation time is 60 minutes, the temperature rise time is between 900 and 1100 ℃, the heat preservation time is 60 minutes, the temperature preservation time is 1100 to 1100 ℃, the temperature fall time is 150 minutes, and the temperature rise time is 1100 to room temperature. The temperature rising and heat preservation processes are automatically controlled by programs, and each temperature rising section heats at a constant speed. Cooling the furnace to room temperature, taking out the product, washing with deionized water for 3 times, floating a small amount of active carbon on the water surface in the washing process, separating the active carbon by a water pouring method, filtering, drying at 80 ℃, and grinding to obtain red attapulgite clay doped gamma-Ce2S3And (3) powder. The rare earth colorant prepared in this example had a color scale of (L × 22.45, a × 48.32, b × 38.55)
Example 2
Weighing 0.5g of acid-treated attapulgite clay and 5.4g of CeCl3·7H2O into a 100mL round bottom flask, add about 50mL deionized water and stir overnight. Adding 1.8g NaOH under continuous stirring to completely precipitate cerium, continuously stirring for about ten minutes, performing suction filtration, washing with water to neutrality, and washing with a small amount of ethanol. Drying in an oven at 80 ℃, and grinding to obtain a reaction precursor. 1.32g of the prepared reaction precursor was weighed and 0.68g of Na was added2CO3Mixing, and grinding. Then 0.8g of sublimed sulfur and 0.170g of active carbon are weighed, evenly mixed and fully ground, and finally all reactants are evenly mixed and placed in an alumina reaction boat for reaction in a tube furnace. Argon gas is introduced at a relatively fast rate for about ten minutes to drive the air in the system, and then argon gas is introduced at a gas flow rate of about one bubble per second to protect the reaction. The temperature is between room temperature and 900 ℃, the temperature rise time is 150 minutes, the temperature rise time is between 900 and 900 ℃, the heat preservation time is 60 minutes, the temperature rise time is between 900 and 1100 ℃, the heat preservation time is 60 minutes, the temperature preservation time is 1100 to 1100 ℃, the temperature fall time is 150 minutes, and the temperature rise time is 1100 to room temperature. The temperature rising and heat preservation processes are automatically controlled by programs, and each temperature rising section heats at a constant speed. Cooling the furnace to room temperature, taking out the product, washing with deionized water for 3 times, floating a small amount of active carbon on the water surface in the washing process, separating the active carbon by a water pouring method, filtering, drying at 80 ℃, and grinding to obtain red attapulgite clay doped gamma-Ce2S3And (3) powder. The rare earth colorant prepared in this example had a color scale of (L ═ 22.00, a ═ 49.19, b ═ 37.77)
Claims (5)
1. A preparation method of rare earth pigment containing attapulgite and cerium sulfide is characterized in that the attapulgite and a water-soluble cerium compound are mixed in water, sufficient alkaline substances are added to completely precipitate cerium, the mixture is dried after filtration and ground to obtain a coprecipitation precursor, then an alkali metal compound, a vulcanizing agent and solid carbon are added to be uniformly mixed, under the protection of inert gas, the temperature is increased to 900 ℃ at the temperature increase rate of 6 ℃/min, then the temperature is kept at 900 ℃ for one hour, then the temperature is increased to 1100 ℃ at the temperature increase rate of 3 ℃/min, the temperature is kept for one hour, and finally the temperature is decreased to room temperature at the temperature decrease rate of 7 ℃/min; wherein the mass ratio of the attapulgite to the cerium in the cerium compound is 1: 3-5; the molar ratio of the alkali metal compound to cerium in the cerium compound is 1:0.05 to 0.4; the mol ratio of the vulcanizing agent to the cerium in the cerium compound is 1: 2-6; the molar ratio of cerium in the solid carbon and the cerium compound is 1: 1 to 4.
2. The method of claim 1, wherein the molar ratio of the alkali metal compound to the cerium in the cerium compound is 1: 0.15; the mol ratio of the vulcanizing agent to cerium in the cerium compound is 1: 4; the molar ratio of the solid carbon to the cerium in the cerium compound is 1: 2.
3. The method according to claim 1, wherein the cerium compound is selected from one or more of nitrate, sulfate and hydrochloride of cerium.
4. The method according to claim 1, wherein the alkali metal compound is one or more of alkali metal carbonate, sulfate, sulfide, and sulfite.
5. The method according to claim 1, wherein the alkaline substance is selected from one or more of ammonia, sodium hydroxide, potassium hydroxide, and sodium carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010786008.0A CN112280330B (en) | 2020-08-05 | 2020-08-05 | Attapulgite-doped cerium sulfide pigment and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010786008.0A CN112280330B (en) | 2020-08-05 | 2020-08-05 | Attapulgite-doped cerium sulfide pigment and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112280330A CN112280330A (en) | 2021-01-29 |
| CN112280330B true CN112280330B (en) | 2022-04-26 |
Family
ID=74420663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010786008.0A Active CN112280330B (en) | 2020-08-05 | 2020-08-05 | Attapulgite-doped cerium sulfide pigment and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112280330B (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009092103A1 (en) * | 2008-01-17 | 2009-07-23 | Mayan Pigments, Inc. | Organic-inorganic hybrid pigment compositions |
| CN102107902B (en) * | 2010-12-22 | 2012-09-26 | 包头市宏博特科技有限责任公司 | Method for preparing cerium sesquisulphide for red pigment by sulfur melting method |
| CN102634237A (en) * | 2012-03-30 | 2012-08-15 | 内蒙古大学 | Preparation method of novel composite pigment gamma-Ce2S3/SiO2 |
| CN102757666B (en) * | 2012-07-03 | 2013-11-06 | 中国科学院兰州化学物理研究所盱眙凹土应用技术研发中心 | Method for preparing concave-convex clay-based nanometer composite pigment by high-pressure induction |
| CN105199435B (en) * | 2015-10-15 | 2018-01-09 | 中国科学院兰州化学物理研究所 | A kind of preparation method of cobalt blue/clay mineral hybrid pigment |
-
2020
- 2020-08-05 CN CN202010786008.0A patent/CN112280330B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112280330A (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR0183392B1 (en) | Compositions based on rare earth sulfides, preparation and use thereof | |
| AU714049B2 (en) | A sulphide of a rare earth and an alkali, a process for its preparation and its use as a coloured pigment | |
| KR950032505A (en) | Compositions based on rare earth metal sulfides having at least one alkali metal element, processes for their preparation and use as color pigments thereof | |
| CA2326765A1 (en) | Process for producing iron oxide pigments | |
| CN114455626B (en) | Beta-type active zinc sulfide and preparation method thereof | |
| CN105131806A (en) | Waterborne fluorescent polyurethane coating and preparation method thereof through prepolymer mixing | |
| CN102414129A (en) | Preparation of green colorant from mixed rare earth and molybdenum compounds and process of surface coatings thereof | |
| CN112280330B (en) | Attapulgite-doped cerium sulfide pigment and preparation method thereof | |
| CN1406874A (en) | Manufacture of granular hematite corpuscle | |
| CN103896325B (en) | Calcined zinc oxide production technology | |
| EP3447093B1 (en) | Colorant and preparation method therefor | |
| KR20000057133A (en) | Use of a Beta Rare Earth Sulphide as Colouring Pigment and Method for Preparing Same | |
| ATE126250T1 (en) | DOPPED ZIRCONIUM MIXED SILICATE PIGMENT, PRODUCTION PROCESS AND PRODUCTS CONTAINING THE PIGMENT OR A PIGMENT PRODUCED IN THIS WAY. | |
| CN101200604A (en) | Tin-doped (IV) sulfide lanthanum pigment and preparation method thereof | |
| CN102414128A (en) | A novel yellow inorganic pigment from samarium and molybdenum compounds and a process for preparing the same | |
| US20010038815A1 (en) | Process for the preparation of a rare-earth metal sulphide of beta form, the rare-earth metal being lanthanum, cerium, praseodymium, samarium or neodymium | |
| CN108101118A (en) | A kind of waste water extraction iron of iron content containing zinc and the method for preparing iron oxide | |
| CN1028646C (en) | Producing process of inorganic green pigment | |
| CN110407246A (en) | A kind of preparation method based on methionine nitric acid synthesis root cutting layer zinc-aluminum hydrotalcite | |
| CN101177552B (en) | Tin-doped (IV) calcium sulfide lanthanum pigment and preparation method thereof | |
| CN108516593A (en) | The preparation method of cobalt blue dye | |
| CN109110800A (en) | A kind of preparation method of zinc oxide micron/nano material | |
| CN108862294A (en) | A kind of nanometer of praseodymium zirconium yellow material and preparation method thereof | |
| US4486236A (en) | Ceramic pigment | |
| CN114231053A (en) | Preparation method of needle-shaped cluster calcium carbonate-silver composite antibacterial material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |