CN108219536A - A kind of aluminium oxide coated γ ~ Ce2S3The preparation method of red colorant and its product obtained - Google Patents
A kind of aluminium oxide coated γ ~ Ce2S3The preparation method of red colorant and its product obtained Download PDFInfo
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000001062 red colorant Substances 0.000 title claims description 24
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 16
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims description 32
- 239000004530 micro-emulsion Substances 0.000 claims description 20
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 150000000703 Cerium Chemical class 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004073 vulcanization Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 3
- 239000003153 chemical reaction reagent Substances 0.000 claims 3
- 239000002244 precipitate Substances 0.000 claims 3
- 241000219307 Atriplex rosea Species 0.000 claims 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 2
- 159000000013 aluminium salts Chemical class 0.000 claims 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 claims 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims 1
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 239000001054 red pigment Substances 0.000 abstract description 17
- 239000003086 colorant Substances 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000005486 sulfidation Methods 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AQCDIIAORKRFCD-UHFFFAOYSA-N cadmium selenide Chemical compound [Cd]=[Se] AQCDIIAORKRFCD-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本发明公开了一种氧化铝包裹型γ～Ce2S3红色色料的制备方法，首先通过液相法制备由氢氧化铝包裹的CeO2前驱体，然后进一步通过硫化气氛与惰性气氛高温硫化热处理而制得氧化铝包裹型γ～Ce2S3红色色料。此外，还公开了利用上述制备方法制得的产品。本发明通过氧化铝的包覆，有效稳定了γ～Ce2S3，使包裹改性后色料的高温稳定性得到大幅提升，极大地拓展了其应用领域；而且工艺简单、反应易于控制，制备过程以及产品性能更加稳定可靠，从而有利于工业化的推广和应用。
The invention discloses a preparation method of alumina-wrapped γ-Ce 2 S 3 red pigment. Firstly, a CeO 2 precursor wrapped by aluminum hydroxide is prepared by a liquid phase method, and then further vulcanized by a sulfide atmosphere and an inert atmosphere at high temperature. Heat treatment to obtain alumina-wrapped γ-Ce 2 S 3 red pigment. In addition, the product prepared by the above-mentioned preparation method is also disclosed. The invention effectively stabilizes γ-Ce 2 S 3 through the coating of alumina, greatly improves the high-temperature stability of the coated and modified colorant, and greatly expands its application field; moreover, the process is simple and the reaction is easy to control. The preparation process and product performance are more stable and reliable, thereby facilitating industrial promotion and application.
Description
技术领域technical field
本发明涉及无机色料技术领域，尤其涉及一种包裹型γ～Ce2S3红色色料的制备方法及其制得的产品。The invention relates to the technical field of inorganic pigments, in particular to a method for preparing a packaged γ-Ce 2 S 3 red pigment and a product thereof.
背景技术Background technique
γ～Ce2S3其主波长为608nm左右，呈大红的颜色，其色泽鲜艳、遮盖力强；且γ～Ce2S3的S3p→Ce5d的电子跃迁对紫外线具有较强的吸收能力，使得γ～Ce2S3能够耐受紫外辐射。同时，由于γ～Ce2S3安全无毒，因此已成为有毒镉硒红的首选替代色料。但是，γ～Ce2S3色料氧化分解温度为350℃，超过该温度会迅速分解而变黑，从而影响了其在高温下的应用。γ～Ce 2 S 3 has a dominant wavelength of about 608nm and is bright red in color with bright color and strong hiding power; and the electronic transition of S 3p →Ce 5d of γ～Ce 2 S 3 has a strong absorption capacity for ultraviolet rays , so that γ～Ce 2 S 3 can withstand ultraviolet radiation. At the same time, because γ～Ce 2 S 3 is safe and non-toxic, it has become the preferred alternative colorant for toxic cadmium selenium red. However, the oxidative decomposition temperature of γ～Ce 2 S 3 pigment is 350°C, and if it exceeds this temperature, it will decompose rapidly and turn black, which affects its application at high temperature.
为此，目前也研究开发了采用包裹技术在色料表面包覆一层或多层透明的高温稳定性材料，通过改性以提高色料的高温稳定性。现有技术中，通常是以氧化硅、氧化锆或硅酸锆作为包覆层，虽然对γ～Ce2S3色料的高温稳定性有所改进，但在制备过程中仍然存在着包裹率低、反应控制困难、产品包裹层致密性差等问题，从而影响了生产制备的稳定可靠性、以及产品的稳定性，为工业化的推广和应用带来了不利。因此，急需研究开发新的包裹制备技术或新的包裹材料，以解决现有研究和生产所出现的问题，从而有利于促进包裹型γ～Ce2S3红色色料技术的应用和发展。For this reason, at present, research and development have also been conducted to coat one or more layers of transparent high-temperature-stable materials on the surface of the colorant by encapsulation technology, and improve the high-temperature stability of the colorant through modification. In the prior art, silicon oxide, zirconium oxide or zirconium silicate is usually used as the coating layer. Although the high-temperature stability of the γ-Ce 2 S 3 pigment has been improved, there is still a coating rate in the preparation process. Low, difficult reaction control, poor compactness of the product coating layer, etc., which affect the stability and reliability of production and preparation, and the stability of the product, and bring disadvantages to the promotion and application of industrialization. Therefore, it is urgent to research and develop new packaging preparation technology or new packaging materials to solve the problems in existing research and production, so as to promote the application and development of wrapped γ-Ce 2 S 3 red colorant technology.
发明内容Contents of the invention
本发明的目的在于克服现有技术的不足，提供一种以氧化铝为包覆层、基于 CeO2前驱体的氧化铝包裹型γ～Ce2S3红色色料的制备方法，通过简单易控、稳定的制备工艺获得包裹型γ～Ce2S3红色色料产品，从而有效提高γ～Ce2S3色料的高温稳定性，拓展其应用领域。本发明的另一目的在于提供利用上述制备方法制得的产品。The purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a method for preparing an alumina-wrapped γ- Ce2S3 red color material with alumina as a coating layer and based on a CeO2 precursor. , Stable preparation process to obtain packaged γ～Ce 2 S 3 red colorant products, thereby effectively improving the high temperature stability of γ～Ce 2 S 3 colorant and expanding its application field. Another object of the present invention is to provide a product prepared by the above-mentioned preparation method.
本发明的目的通过以下技术方案予以实现：The purpose of the present invention is achieved through the following technical solutions:
本发明提供的一种氧化铝包裹型γ～Ce2S3红色色料的制备方法，包括以下步骤：The preparation method of an alumina-wrapped γ-Ce 2 S 3 red colorant provided by the present invention comprises the following steps:
(1)液相法制备包裹型CeO2前驱体沉淀(1) Preparation of encapsulated CeO 2 precursor precipitation by liquid phase method
(1-1)将水溶性+3价铈盐、水溶性+3价铝盐，按照摩尔比Ce3+∶Al3+＝1～20∶ 1～5溶于水中，形成所述水溶性+3价铈盐的浓度为1.5～3.5mol/L的混合溶液；然后将所述混合溶液加入溶剂A中进行搅拌，制得微乳液A；其中，按照体积比水∶溶剂A＝1～10∶20～100；(1-1) Dissolving water-soluble+3-valent cerium salt and water-soluble+3-valent aluminum salt in water according to the molar ratio Ce 3+ :Al 3+ =1～20:1～5 to form the water-soluble+ The concentration of trivalent cerium salt is a mixed solution of 1.5～3.5mol/L; then the mixed solution is added into solvent A and stirred to obtain microemulsion A; wherein, according to the volume ratio water: solvent A=1～10: 20～100;
(1-2)将沉淀剂加入溶剂B中进行搅拌，制得微乳液B；其中，按照体积比沉淀剂∶溶剂B＝1～10∶20～100，所述溶剂A和溶剂B其组成及配比均相同；(1-2) The precipitating agent is added into the solvent B and stirred to prepare the microemulsion B; wherein, according to the volume ratio of the precipitating agent: solvent B=1～10:20～100, the composition of the solvent A and the solvent B and The proportions are the same;
(1-3)按照体积比所述溶剂A∶溶剂B＝1∶1，将微乳液A与微乳液B混合后进行搅拌，然后加入破乳剂破乳，获得氢氧化铝包裹的CeO2前驱体沉淀；(1-3) According to the volume ratio of solvent A:solvent B=1:1, microemulsion A and microemulsion B are mixed and then stirred, and then a demulsifier is added to break the emulsion to obtain the CeO2 precursor wrapped in aluminum hydroxide precipitation;
(2)制备包裹型CeO2前驱体粉料(2) Preparation of encapsulated CeO 2 precursor powder
所述氢氧化铝包裹的CeO2前驱体沉淀，经水洗、醇洗、干燥后，制得包裹型 CeO2前驱体粉料；The CeO wrapped by aluminum hydroxide Precipitation, after washing with water, alcohol washing, and drying, the wrapped CeO precursor powder is obtained;
(3)硫化热处理制备γ～Ce2S3红色色料(3) Preparation of γ～Ce 2 S 3 red pigment by vulcanization heat treatment
将所述包裹型CeO2前驱体粉料在以硫化气氛与惰性气氛形成的共同保护气氛中进行热处理，即制得氧化铝包裹型γ～Ce2S3红色色料。The wrapped CeO 2 precursor powder is heat-treated in a common protective atmosphere formed by a sulfidation atmosphere and an inert atmosphere to obtain an alumina-wrapped γ-Ce 2 S 3 red pigment.
进一步地，本发明所述水溶性+3价铈盐为Ce(NO3)3·6H2O、CeCl3·7H2O、 Ce2(SO4)3·8H2O或Ce(Ac)3·nH2O；所述水溶性+3价铝盐为Al(NO3)3·9H2O、 Al2(SO4)3·18H2O或AlCl3·6H2O。所述溶剂A和溶剂B为按照体积比曲拉通∶环己烷∶正己醇＝2～20∶15～50∶0.5～10的混合液。所述沉淀剂为浓氨水；所述破乳剂为丙酮、乙醇或异丙醇。Further, the water-soluble +3-valent cerium salt of the present invention is Ce(NO 3 ) 3 ·6H 2 O, CeCl 3 ·7H 2 O, Ce 2 (SO 4 ) 3 ·8H 2 O or Ce(Ac) 3 ·nH 2 O; the water-soluble +3-valent aluminum salt is Al(NO 3 ) 3 ·9H 2 O, Al 2 (SO 4 ) 3 ·18H 2 O or AlCl 3 ·6H 2 O. The solvent A and the solvent B are a mixed solution of Triton: cyclohexane: n-hexanol = 2-20: 15-50: 0.5-10 by volume. The precipitant is concentrated ammonia water; the demulsifier is acetone, ethanol or isopropanol.
上述方案中，本发明所述步骤(1-1)、步骤(1-2)、步骤(1-3)中，搅拌时间分别为 1～8h。In the above scheme, in the step (1-1), step (1-2) and step (1-3) of the present invention, the stirring time is 1-8 hours respectively.
进一步地，本发明所述步骤(3)中，硫化气氛为CS2或H2S，惰性气氛为N2或 Ar。按照体积比所述硫化气氛∶惰性气氛＝1～30∶1～300。Further, in step (3) of the present invention, the sulfide atmosphere is CS 2 or H 2 S, and the inert atmosphere is N 2 or Ar. According to the volume ratio, the sulfide atmosphere: inert atmosphere = 1-30: 1-300.
上述方案中，本发明所述步骤(3)中，热处理制度为：以2～10℃/min升温至650～1200℃，保温50～600min，冷却至室温，即制得氧化铝包裹型γ～Ce2S3红色色料。In the above scheme, in the step (3) of the present invention, the heat treatment system is as follows: heat up to 650-1200°C at 2-10°C/min, keep warm for 50-600min, and cool to room temperature to obtain alumina-wrapped γ- Ce 2 S 3 red pigment.
本发明的另一目的通过以下技术方案予以实现：Another object of the present invention is achieved through the following technical solutions:
本发明提供的利用上述氧化铝包裹型γ～Ce2S3红色色料的制备方法制得的产品，所述产品其红度值a*≥32；所述产品在空气气氛下于600℃温度煅烧后其红度值a* ≥30，仍呈红色外观。The product provided by the present invention using the above-mentioned preparation method of alumina-wrapped γ-Ce 2 S 3 red colorant has a redness value a*≥32; After calcination, its redness value a* ≥ 30, still has a red appearance.
本发明具有以下有益效果：The present invention has the following beneficial effects:
(1)本发明首先通过液相法制备由氢氧化铝包裹的CeO2前驱体，然后进一步通过硫化气氛与惰性气氛高温硫化热处理而制得氧化铝包裹型γ～Ce2S3红色色料。通过氧化铝的包覆，有效稳定了γ～Ce2S3，使包裹改性后色料的高温稳定性得到大幅提升。(1) In the present invention, the CeO 2 precursor wrapped by aluminum hydroxide is firstly prepared by the liquid phase method, and then the aluminum oxide-wrapped γ-Ce 2 S 3 red pigment is obtained by further high-temperature sulfidation heat treatment in a sulfidation atmosphere and an inert atmosphere. Through the coating of alumina, the γ-Ce 2 S 3 is effectively stabilized, and the high-temperature stability of the pigment after coating modification is greatly improved.
(2)本发明通过液相法有效保证了分散性和均匀性，而且工艺简单、反应易于控制；通过引入氧化铝，硫化过程中比较稳定，且不容易出现杂相，使得制备过程以及产品性能更加稳定可靠，有利于工业化的推广和应用。(2) The present invention effectively guarantees dispersion and uniformity through the liquid phase method, and the process is simple and the reaction is easy to control; by introducing alumina, the vulcanization process is relatively stable, and impurity phases are not easy to appear, making the preparation process and product performance It is more stable and reliable, and is conducive to the promotion and application of industrialization.
(3)本发明制得的色料产品红度值a*≥32。在600℃下仍呈现红色外观，红度值a*≥30，极大地拓展了其应用领域。(3) The redness value of the pigment product prepared by the present invention is a*≥32. It still has a red appearance at 600°C, and the redness value a*≥30, which greatly expands its application field.
附图说明Description of drawings
下面将结合实施例和附图对本发明作进一步的详细描述：The present invention will be described in further detail below in conjunction with embodiment and accompanying drawing:
图1是本发明实施例一所制得的氧化铝包裹型γ～Ce2S3红色色料的X射线衍射谱图(XRD)；Fig. 1 is the X-ray diffraction spectrum (XRD) of the alumina-wrapped γ-Ce 2 S 3 red pigment prepared in Example 1 of the present invention;
图2是本发明实施例二所制备的氧化铝包裹型γ～Ce2S3红色色料的透射电镜图片(TEM)；Fig. 2 is a transmission electron microscope picture (TEM) of the aluminum oxide-wrapped γ-Ce 2 S 3 red colorant prepared in Example 2 of the present invention;
图3是本发明实施例三所制备的氧化铝包裹型γ～Ce2S3红色色料的透射电镜图片(TEM)。Fig. 3 is a transmission electron microscope picture (TEM) of the alumina-wrapped γ-Ce 2 S 3 red colorant prepared in Example 3 of the present invention.
具体实施方式Detailed ways
实施例一：Embodiment one:
本实施例一种氧化铝包裹型γ～Ce2S3红色色料的制备方法，其步骤如下：In this embodiment, a method for preparing an alumina-wrapped γ-Ce 2 S 3 red colorant, the steps are as follows:
(1)液相法制备包裹型CeO2前驱体沉淀(1) Preparation of encapsulated CeO 2 precursor precipitation by liquid phase method
(1-1)将5.5g Ce(NO3)3·6H2O、4.5gAl(NO3)3·9H2O溶于5ml水中，然后滴入由10ml曲拉通、30ml环己烷和8ml正己醇组成的溶剂A中，室温下搅拌4h，制得微乳液A；(1-1) Dissolve 5.5g Ce(NO 3 ) 3 ·6H 2 O, 4.5g Al(NO 3 ) 3 ·9H 2 O in 5ml of water, and then drop into a mixture of 10ml Triton, 30ml cyclohexane and 8ml In solvent A composed of n-hexanol, stir at room temperature for 4 hours to prepare microemulsion A;
(1-2)将4.5ml浓氨水滴入由10ml曲拉通、30ml环己烷和8ml正己醇组成的溶剂B中，室温下搅拌4h，制得微乳液B；(1-2) 4.5ml of concentrated ammonia water was dropped into a solvent B composed of 10ml of triton, 30ml of cyclohexane and 8ml of n-hexanol, and stirred at room temperature for 4h to obtain a microemulsion B;
(1-3)按照体积比溶剂A∶溶剂B＝1∶1，将微乳液A与微乳液B混合后，室温下继续搅拌5h，加入丙酮破乳，获得氢氧化铝包裹的CeO2前驱体沉淀；(1-3) According to the volume ratio of solvent A:solvent B=1:1, after mixing microemulsion A and microemulsion B, continue to stir at room temperature for 5h, add acetone to break the emulsion, and obtain the CeO2 precursor wrapped in aluminum hydroxide precipitation;
(2)制备包裹型CeO2前驱体粉料(2) Preparation of encapsulated CeO 2 precursor powder
上述氢氧化铝包裹的CeO2前驱体沉淀，经水洗、醇洗、干燥后，制得包裹型 CeO2前驱体粉料；The above-mentioned aluminum hydroxide-wrapped CeO Precipitation , washing with water, alcohol washing, and drying to obtain wrapped CeO Precursor powder;
(3)硫化热处理制备γ～Ce2S3红色色料(3) Preparation of γ～Ce 2 S 3 red pigment by vulcanization heat treatment
将上述包裹型CeO2前驱体粉料置于瓷舟中，将瓷舟放入气氛炉，通入按照体积比CS2∶N2＝1∶10的混合气体，以5℃/min升温至1050℃，保温250min，冷却至室温，即制得氧化铝包裹型γ～Ce2S3红色色料。Put the above-mentioned encapsulated CeO 2 precursor powder in a porcelain boat, put the porcelain boat into the atmosphere furnace, pass in the mixed gas according to the volume ratio CS 2 :N 2 =1:10, and raise the temperature to 1050 at 5°C/min. ℃, keep warm for 250min, and cool down to room temperature to prepare alumina-wrapped γ-Ce 2 S 3 red pigment.
实施例二：Embodiment two:
本实施例一种氧化铝包裹型γ～Ce2S3红色色料的制备方法，其步骤如下：In this embodiment, a method for preparing an alumina-wrapped γ-Ce 2 S 3 red colorant, the steps are as follows:
(1)液相法制备包裹型CeO2前驱体沉淀(1) Preparation of encapsulated CeO 2 precursor precipitation by liquid phase method
(1-1)将5g CeCl3·7H2O、4gAlCl3·6H2O溶于6ml水中，然后滴入由12ml曲拉通、35ml环己烷和9ml正己醇组成的溶剂A中，室温下搅拌4.5h，制得微乳液A；(1-1) Dissolve 5g CeCl 3 ·7H 2 O and 4g AlCl 3 ·6H 2 O in 6ml of water, and then drop them into solvent A consisting of 12ml of triton, 35ml of cyclohexane and 9ml of n-hexanol. Stir for 4.5h to prepare microemulsion A;
(1-2)将3.5ml浓氨水滴入由12ml曲拉通、35ml环己烷和9ml正己醇组成的溶剂B中，室温下搅拌4.5h，制得微乳液B；(1-2) 3.5ml of concentrated ammonia water was dropped into a solvent B consisting of 12ml of triton, 35ml of cyclohexane and 9ml of n-hexanol, and stirred at room temperature for 4.5h to obtain microemulsion B;
(1-3)按照体积比溶剂A∶溶剂B＝1∶1，将微乳液A与微乳液B混合后，室温下继续搅拌4.5h，加入乙醇破乳，获得氢氧化铝包裹的CeO2前驱体沉淀；(1-3) According to the volume ratio of solvent A:solvent B=1:1, after mixing microemulsion A and microemulsion B, continue to stir at room temperature for 4.5h, add ethanol to break the emulsion, and obtain the CeO2 precursor wrapped in aluminum hydroxide Body precipitation;
(2)制备包裹型CeO2前驱体粉料(2) Preparation of encapsulated CeO 2 precursor powder
上述氢氧化铝包裹的CeO2前驱体沉淀，经水洗、醇洗、干燥后，制得包裹型 CeO2前驱体粉料；The above-mentioned aluminum hydroxide-wrapped CeO Precipitation , washing with water, alcohol washing, and drying to obtain wrapped CeO Precursor powder;
(3)硫化热处理制备γ～Ce2S3红色色料(3) Preparation of γ～Ce 2 S 3 red pigment by vulcanization heat treatment
将上述包裹型CeO2前驱体粉料置于瓷舟中，将瓷舟放入气氛炉，通入按照体积比CS2∶Ar＝1∶8的混合气体，以5℃/min升温至1000℃，保温360min，冷却至室温，即制得氧化铝包裹型γ～Ce2S3红色色料。Put the above-mentioned encapsulated CeO 2 precursor powder in a porcelain boat, put the porcelain boat into the atmosphere furnace, pass in the mixed gas according to the volume ratio CS 2 :Ar=1:8, and raise the temperature to 1000°C at 5°C/min , keep warm for 360min, and cool down to room temperature to obtain alumina-wrapped γ-Ce 2 S 3 red pigment.
实施例三：Embodiment three:
本实施例一种氧化铝包裹型γ～Ce2S3红色色料的制备方法，其步骤如下：In this embodiment, a method for preparing an alumina-wrapped γ-Ce 2 S 3 red colorant, the steps are as follows:
(1)液相法制备包裹型CeO2前驱体沉淀(1) Preparation of encapsulated CeO 2 precursor precipitation by liquid phase method
(1-1)将5g CeCl3·7H2O、5gAl(NO3)3·9H2O溶于6ml水中，然后滴入由9.5ml 曲拉通、32ml环己烷和8ml正己醇组成的溶剂A中，室温下搅拌7h，制得微乳液 A；(1-1) Dissolve 5g CeCl 3 7H 2 O, 5g Al(NO 3 ) 3 9H 2 O in 6ml of water, then drop into a solvent consisting of 9.5ml Triton, 32ml cyclohexane and 8ml n-hexanol In A, stir at room temperature for 7 hours to prepare microemulsion A;
(1-2)将4ml浓氨水滴入由9.5ml曲拉通、32ml环己烷和8ml正己醇组成的溶剂B中，室温下搅拌7h，制得微乳液B；(1-2) 4 ml of concentrated ammonia water was dropped into a solvent B composed of 9.5 ml of triton, 32 ml of cyclohexane and 8 ml of n-hexanol, and stirred at room temperature for 7 hours to obtain a microemulsion B;
(1-3)按照体积比溶剂A∶溶剂B＝1∶1，将微乳液A与微乳液B混合后，室温下继续搅拌5h，加入异丙醇破乳，获得氢氧化铝包裹的CeO2前驱体沉淀；(1-3) According to the volume ratio of solvent A:solvent B=1:1, after mixing microemulsion A and microemulsion B, continue to stir at room temperature for 5h, add isopropanol to break the emulsion, and obtain CeO2 wrapped in aluminum hydroxide precursor precipitation;
(2)制备包裹型CeO2前驱体粉料(2) Preparation of encapsulated CeO 2 precursor powder
上述氢氧化铝包裹的CeO2前驱体沉淀，经水洗、醇洗、干燥后，制得包裹型 CeO2前驱体粉料；The above-mentioned aluminum hydroxide-wrapped CeO Precipitation , washing with water, alcohol washing, and drying to obtain wrapped CeO Precursor powder;
(3)硫化热处理制备γ～Ce2S3红色色料(3) Preparation of γ～Ce 2 S 3 red pigment by vulcanization heat treatment
将上述包裹型CeO2前驱体粉料置于瓷舟中，将瓷舟放入气氛炉，通入按照体积比CS2∶N2＝1∶9的混合气体，以2℃/min升温至950℃，保温400min，冷却至室温，即制得氧化铝包裹型γ～Ce2S3红色色料。Put the above-mentioned encapsulated CeO 2 precursor powder in a porcelain boat, put the porcelain boat into the atmosphere furnace, pass in the mixed gas according to the volume ratio CS 2 :N 2 =1:9, and raise the temperature to 950 °C at 2°C/min. ℃, keep it warm for 400min, and cool to room temperature to prepare alumina-wrapped γ-Ce 2 S 3 red pigment.
如图1所示，本发明实施例制得的包裹型γ～Ce2S3红色色料由γ～Ce2S3和氧化铝组成。As shown in FIG. 1 , the encapsulated γ-Ce 2 S 3 red coloring material prepared in the embodiment of the present invention is composed of γ-Ce 2 S 3 and alumina.
图2和图3表明，本发明实施例制得的包裹型γ～Ce2S3红色色料，由γ～Ce2S3和其表面包覆的透明、致密氧化铝包裹层组成。Figure 2 and Figure 3 show that the encapsulated γ-Ce 2 S 3 red pigment prepared in the embodiment of the present invention is composed of γ-Ce 2 S 3 and its surface-coated transparent and dense alumina coating layer.
本发明各实施例所制得的氧化铝包裹型γ～Ce2S3红色色料，其色度值如表1所示。Table 1 shows the chromaticity values of alumina-wrapped γ-Ce 2 S 3 red pigments prepared in various embodiments of the present invention.
表1本发明各实施例氧化铝包裹型γ～Ce2S3红色色料的色度值Table 1 Chromaticity values of alumina-wrapped γ-Ce 2 S 3 red pigments in various embodiments of the present invention
以未包裹的商用γ～Ce2S3色料作为对比例，本发明实施例一所制得的氧化铝包裹型γ～Ce2S3红色色料，在空气气氛中煅烧后的色度值如表2所示。Taking the unwrapped commercial γ-Ce 2 S 3 colorant as a comparative example, the chromaticity value of the alumina-wrapped γ-Ce 2 S 3 red colorant prepared in Example 1 of the present invention after being calcined in an air atmosphere As shown in table 2.
表2本发明实施例一和对比例在空气气氛中煅烧后的色度值Table 2 Chromaticity values of Example 1 of the present invention and comparative examples after being calcined in an air atmosphere
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