WO2022142124A1 - Green pigment based on ca3teo6 structure, preparation method therefor and use thereof - Google Patents
Green pigment based on ca3teo6 structure, preparation method therefor and use thereof Download PDFInfo
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- WO2022142124A1 WO2022142124A1 PCT/CN2021/097637 CN2021097637W WO2022142124A1 WO 2022142124 A1 WO2022142124 A1 WO 2022142124A1 CN 2021097637 W CN2021097637 W CN 2021097637W WO 2022142124 A1 WO2022142124 A1 WO 2022142124A1
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- green pigment
- green
- pigment
- containing compound
- teo
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- 239000001056 green pigment Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011575 calcium Substances 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011656 manganese carbonate Substances 0.000 claims description 2
- 235000006748 manganese carbonate Nutrition 0.000 claims description 2
- 229940093474 manganese carbonate Drugs 0.000 claims description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(iii) oxide Chemical compound O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 abstract description 14
- 239000002253 acid Substances 0.000 abstract description 11
- 239000003513 alkali Substances 0.000 abstract description 11
- 238000000227 grinding Methods 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 4
- 241001464837 Viridiplantae Species 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000985 reflectance spectrum Methods 0.000 description 11
- 239000000843 powder Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 239000001023 inorganic pigment Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- -1 TeO 2 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000005274 electronic transitions Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- FPSFKBGHBCHTOE-UHFFFAOYSA-N sodium 3-hydroxy-4-[(3-methyl-5-oxo-1-phenyl-4H-pyrazol-4-yl)diazenyl]naphthalene-1-sulfonic acid Chemical compound [Na+].O=C1C(N=NC=2C3=CC=CC=C3C(=CC=2O)S(O)(=O)=O)C(C)=NN1C1=CC=CC=C1 FPSFKBGHBCHTOE-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- 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
- C09C1/02—Compounds of alkaline earth metals or magnesium
-
- 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
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- 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
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
-
- 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
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/30—Camouflage paints
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/62—L* (lightness axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/63—Optical properties, e.g. expressed in CIELAB-values a* (red-green axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
- C01P2006/66—Hue (H*)
Definitions
- the invention relates to the field of preparation of inorganic pigments, and more particularly, to a green pigment based on the structure of Ca 3 TeO 6 and a preparation method and application thereof.
- Inorganic pigments are widely used in building materials, coatings and paints, plastics, inks, military camouflage and other industries because of their stable properties, bright colors, complete and pure varieties of chromatograms.
- the existing commercial inorganic pigments still suffer from various problems.
- traditional commercial pigments such as chrome yellow (PbCrO 3 ), cadmium yellow (CdS), antimony yellow (Sb 2 O 3 2PbO) and molybdenum chrome red [Pb(Cr, Mo, S)O 4 ] contain lead, Toxic heavy metal elements such as chromium and cadmium can harm human health and pollute the environment, and their application fields are also more and more restricted.
- the pigment production process is complex and produces toxic by-products, which do not meet the requirements of energy conservation and environmental protection.
- Chinese invention patent CN111978775A discloses (published on August 29, 2020) a military infrared reflective green inorganic pigment and its preparation method.
- the inorganic pigment has good weather resistance, high temperature resistance, and light resistance, but its synthesis High temperature and acid and alkali resistance.
- Chinese invention patent CN111154295A discloses (published on May 15, 2020) an environmentally friendly green inorganic pigment and its preparation method. The invention reduces the firing temperature of the pigment by adding highly active cobalt carbonate, but the invention describes Green pigments still have the problem of acid and alkali resistance.
- the primary purpose of the present invention is to overcome the problems of poor acid and alkali resistance and high temperature resistance of green pigments in the prior art, and to provide a green pigment based on the Ca 3 TeO 6 structure, which is non-toxic, acid and alkali resistant, and high temperature resistant. .
- Another object of the present invention is to provide the application of the above-mentioned green pigment.
- a green pigment based on the structure of Ca 3 TeO 6 the molecular formula of the green inorganic pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.1 ⁇ x ⁇ 0.4.
- the molecular formula of the green pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.2 ⁇ x ⁇ 0.3.
- the element molar ratio Ca:Te:Mn:Li (3-2x):1:x:x, wherein 0.1 ⁇ x ⁇ 0.4.
- the element molar ratio Ca:Te:Mn:Li (3-2x):1:x:x, wherein 0.2 ⁇ x ⁇ 0.3.
- the calcium-containing compound is one or both of calcium carbonate and calcium oxide.
- the manganese-containing compound is one or more of manganese carbonate, manganese monoxide, manganese dioxide and manganese trioxide.
- the calcination is to raise the temperature to 900-1200°C at a heating rate of 4°C/min-10°C/min, and keep the temperature for 4-12 hours.
- the green pigment of the invention is resistant to acid and alkali, high temperature, and has a reflectance value similar to that of green plants, and can be used for painting camouflage materials. Therefore, the application of the green pigment in the field of camouflage materials should also fall within the protection scope of the present invention.
- FIG. 1 is the XRD pattern of the sample described in Example 1.
- FIG. 1 is the XRD pattern of the sample described in Example 1.
- Figure 2 is the appearance diagram of the sample before acid-base treatment (Sample) and after acid-base treatment described in Example 1.
- the temperature was raised from room temperature to 900°C at a heating rate of 4°C/min, calcined in air for 12 hours, cooled down naturally, and a powder sample was obtained after taking out and grinding.
- the powder samples are white because Li + ions are not introduced as activators, and Mn exists mainly in the divalent form.
- the difference between the comparative example 2 and the embodiment 1 is that the calcination temperature in the comparative example 2 is 600°C.
- Figure 1 is the XRD pattern of the sample described in Example 1. It can be seen from the figure that the phase of the sample described in Example 1 matches the XRD pattern of Ca 3 TeO 6 , indicating that the green pigment was successfully prepared in Example 1.
- the XRD patterns of the samples described in Examples 2 to 5 are basically the same as those in Example 1.
- the CIE (Commission on Illumination) standard 1976 is used to describe the color of pigments, that is, the perception of color stimuli and color quality received by the eye is converted into color coordinates L*, a*, b* representation.
- the color coordinate values of the samples described in Examples 1 to 5 measured by a colorimeter and the calculated hue angle value h° are shown in Table 1.
- Example 1 46.40 1.40 19.90 85.97
- Example 2 55.23 0.64 22.62 88.38
- Example 3 71.52 0.56 31.11 88.95
- Example 4 30.76 0.63 9.67 86.27
- Example 5 52.18 1.86 18.22 84.17
- Examples 1 to 5 are close to the a* axis in the chromaticity space, and are biased towards the b* axis (yellow), and the hue angle values h° are 85.97°, 88.38, 88.95, 86.27, and 84.17, respectively. Because L* Lower values are visually green.
- Example 1 The acid and alkali resistance test was carried out on the sample described in Example 1, that is, HNO 3 with a concentration of 5% and a NaOH solution with a concentration of 5% were prepared, and the pigment was added to the acid or alkali solution prepared above, and mixed and stirred for 10 minutes , filtered, washed with water and ethanol, and air-dried.
- the sample described in Example 1 was subjected to a high temperature test, that is, the sample was calcined at a high temperature.
- Figure 2 is the appearance diagram of the sample before acid-base treatment (Sample) and after acid-base treatment described in Example 1.
- the color coordinate values of the samples before and after high temperature treatment and the calculated color difference ⁇ E * of the sample described in Example 1 are shown in Table 2.
- the color difference ⁇ E * of the samples described in Examples 2 to 5 before and after high temperature treatment is the same as the Example 1 is basically the same.
- Figure 3 is the XRD pattern of the sample described in Comparative Example 2. It can be seen from the figure that the phase of the sample does not match the XRD pattern of Ca 3 TeO 6 , that is, the green pigment cannot be prepared in Comparative Example 2.
Abstract
Disclosed are a green pigment based on Ca3TeO6 structure, a preparation method therefor and use thereof. The molecular formula of the green pigment is Ca3-2xMnxLixTeO6, wherein 0.1≤x≤0.4. The preparation method for the green pigment comprises the following steps: weighing raw materials of a calcium-containing compound, a tellurium-containing compound, a manganese-containing compound, and Li2CO3 according to an element molar ratio, mixing and grinding same uniformly, calcining same at 900-1200 °C, and cooling same so as to obtain the green pigment. The preparation method of the present invention is simple and environmentally friendly, the raw materials are inexpensive and non-toxic, the prepared green pigment is acid-resistant and alkali-resistant, the pigment can maintain the color unchanged below 1100 °C, and the pigment has a reflectance value similar to that of green plants and can be used for coating of camouflage materials.
Description
本发明涉及无机颜料制备领域，更具体地，涉及一种基于Ca
3TeO
6结构的绿色颜料及其制备方法和应用。
The invention relates to the field of preparation of inorganic pigments, and more particularly, to a green pigment based on the structure of Ca 3 TeO 6 and a preparation method and application thereof.
无机颜料因其性质稳定、色泽鲜艳、品种色谱齐全且纯正，而被广泛应用于建筑建材、涂料油漆，塑料、油墨、军事伪装等行业领域。然而，现有的商用无机颜料还存在各种各样的问题。其一，传统的商用颜料铬黄(PbCrO
3)、镉黄(CdS)、锑黄(Sb
2O
3·2PbO)和钼铬红[Pb(Cr,Mo,S)O
4]等含铅、铬、镉等有毒重金属元素，会危害人类健康和污染环境，其应用领域也受到越来越多的限制。其二，颜料生产过程复杂，并产生有毒副产物，不符合节能环保的要求。
Inorganic pigments are widely used in building materials, coatings and paints, plastics, inks, military camouflage and other industries because of their stable properties, bright colors, complete and pure varieties of chromatograms. However, the existing commercial inorganic pigments still suffer from various problems. First, traditional commercial pigments such as chrome yellow (PbCrO 3 ), cadmium yellow (CdS), antimony yellow (Sb 2 O 3 2PbO) and molybdenum chrome red [Pb(Cr, Mo, S)O 4 ] contain lead, Toxic heavy metal elements such as chromium and cadmium can harm human health and pollute the environment, and their application fields are also more and more restricted. Second, the pigment production process is complex and produces toxic by-products, which do not meet the requirements of energy conservation and environmental protection.
中国发明专利CN111978775A公开了(公开时间2020年08月29日)一种军用红外反射绿色无机颜料及其制备方法，所述无机颜料具有很好的耐候性、耐高温性、耐光性，但其合成温度高且不耐酸碱。中国发明专利CN111154295A公开了(公开时间2020年05月15日)一种环保型绿色无机颜料及其制备方法，该发明通过添加活性高的碳酸钴降低了颜料的烧成温度，但该发明所述绿色颜料仍然存在不耐酸碱的问题。Chinese invention patent CN111978775A discloses (published on August 29, 2020) a military infrared reflective green inorganic pigment and its preparation method. The inorganic pigment has good weather resistance, high temperature resistance, and light resistance, but its synthesis High temperature and acid and alkali resistance. Chinese invention patent CN111154295A discloses (published on May 15, 2020) an environmentally friendly green inorganic pigment and its preparation method. The invention reduces the firing temperature of the pigment by adding highly active cobalt carbonate, but the invention describes Green pigments still have the problem of acid and alkali resistance.
发明内容SUMMARY OF THE INVENTION
本发明的首要目的是克服现有技术中绿色颜料耐酸碱、耐高温性能差的问题，提供一种基于Ca
3TeO
6结构的绿色颜料，所述绿色颜料无毒、耐酸碱、耐高温。
The primary purpose of the present invention is to overcome the problems of poor acid and alkali resistance and high temperature resistance of green pigments in the prior art, and to provide a green pigment based on the Ca 3 TeO 6 structure, which is non-toxic, acid and alkali resistant, and high temperature resistant. .
本发明的进一步目的是提供上述绿色颜料的制备方法。A further object of the present invention is to provide a method for preparing the above green pigment.
本发明的另一个目的是提供上述绿色颜料的应用。Another object of the present invention is to provide the application of the above-mentioned green pigment.
本发明的上述目的通过以下技术方案实现：The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种基于Ca
3TeO
6结构的绿色颜料，所述绿色无机颜料的分子式为Ca
3-2xMn
xLi
xTeO
6，其中0.1≤x≤0.4。
A green pigment based on the structure of Ca 3 TeO 6 , the molecular formula of the green inorganic pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.1≤x≤0.4.
基质Ca
3TeO
6为Mn离子提供了合适的配位环境，即CaO6，Ca和距离最近的6个O构成四棱双锥的八面体空间几何构型；TeO6，Te和距离最近的6个O 构成四棱双锥的八面体空间几何构型。Mn离子进入晶格后，占据Ca或Te的位置，在引入Li
+之前体系中主要是二价Mn，Mn
2+在八面体中没有特殊的电子跃迁在可见区，即粉体不会有颜色。引入Li
+后产生空穴，诱导体系中Mn的价态升高，此时体系中Mn的价态主要为四价，八面体配位环境中的Mn
4+在可见区产生特殊的跃迁使粉体颜色为绿色。
The matrix Ca 3 TeO 6 provides a suitable coordination environment for Mn ions, namely CaO 6, Ca and the nearest 6 Os form the octahedral space geometry of a quadrangular bipyramid; TeO6, Te and the 6 nearest Os The octahedral space geometry that constitutes a quadrangular bipyramid. After the Mn ion enters the lattice, it occupies the position of Ca or Te. Before the introduction of Li + , the system is mainly divalent Mn, and Mn 2+ has no special electronic transition in the octahedron in the visible region, that is, the powder will not have color. . Holes are generated after the introduction of Li + , which induces the increase of the valence state of Mn in the system. At this time, the valence state of Mn in the system is mainly tetravalent, and Mn 4+ in the octahedral coordination environment produces a special transition in the visible region to make the powder Body color is green.
优选地，所述绿色颜料的分子式为Ca
3-2xMn
xLi
xTeO
6，其中0.2≤x≤0.3。
Preferably, the molecular formula of the green pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.2≤x≤0.3.
上述绿色颜料的制备方法，包括如下步骤：The preparation method of above-mentioned green pigment, comprises the steps:
将原料含钙的化合物、含碲的化合物、含锰的化合物、Li
2CO
3按元素摩尔比称取后混合并研磨均匀在900～1200℃条件下煅烧，冷却后所得即为绿色颜料。
The raw materials calcium-containing compound, tellurium-containing compound, manganese-containing compound, Li 2 CO 3 are weighed according to the element molar ratio, mixed, ground and evenly calcined at 900-1200 ℃, and the green pigment is obtained after cooling.
优选地，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.1≤x≤0.4。Preferably, the element molar ratio Ca:Te:Mn:Li=(3-2x):1:x:x, wherein 0.1≤x≤0.4.
更优选地，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.2≤x≤0.3。More preferably, the element molar ratio Ca:Te:Mn:Li=(3-2x):1:x:x, wherein 0.2≤x≤0.3.
优选地，所述含钙的化合物为碳酸钙、氧化钙中的一种或两种。Preferably, the calcium-containing compound is one or both of calcium carbonate and calcium oxide.
优选地，所述含锰的化合物为碳酸锰、一氧化锰、二氧化锰和三氧化二锰中的一种或多种。Preferably, the manganese-containing compound is one or more of manganese carbonate, manganese monoxide, manganese dioxide and manganese trioxide.
优选地，所述煅烧为以4℃/min～10℃/min的升温速率将温度升至900～1200℃，保温4～12h。Preferably, the calcination is to raise the temperature to 900-1200°C at a heating rate of 4°C/min-10°C/min, and keep the temperature for 4-12 hours.
更优选地，所述煅烧为以4℃/min～6℃/min的升温速率将温度升至1000～1100℃，保温4～8h。More preferably, the calcination is to raise the temperature to 1000-1100°C at a heating rate of 4°C/min-6°C/min, and keep the temperature for 4-8 hours.
本发明所述绿色颜料耐酸碱、耐高温，且反射率值与绿色植物的反射率相似，可用于伪装材料的涂装。因此，所述绿色颜料在伪装材料领域中的应用也应该在本发明的保护范围内。The green pigment of the invention is resistant to acid and alkali, high temperature, and has a reflectance value similar to that of green plants, and can be used for painting camouflage materials. Therefore, the application of the green pigment in the field of camouflage materials should also fall within the protection scope of the present invention.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明所述制备方法环保，原料平价且无毒性，制备得到的绿色无机颜料耐酸碱，1100℃以下颜料可保持颜色不变，且所述颜料反射率值与绿色植物的反射率相似，可用于伪装材料的涂装。The preparation method of the invention is environmentally friendly, the raw materials are cheap and non-toxic, the prepared green inorganic pigment is resistant to acid and alkali, the color of the pigment below 1100°C can remain unchanged, and the reflectance value of the pigment is similar to that of green plants, and can be used Coating with camouflage materials.
图1为实施例1所述样品的XRD图。FIG. 1 is the XRD pattern of the sample described in Example 1. FIG.
图2为实施例1所述样品酸碱处理前(Sample)和酸碱处理后的外观图。Figure 2 is the appearance diagram of the sample before acid-base treatment (Sample) and after acid-base treatment described in Example 1.
图3为对比例2所述样品的XRD图。FIG. 3 is an XRD pattern of the sample described in Comparative Example 2. FIG.
图4中(a)为实施例1所述样品的反射率光谱图，(b)为实施例3所述样 品的反射率光谱图，(c)为黄色叶片的反射率光谱图，(d)为绿色叶片的反射率光谱图。In Figure 4 (a) is the reflectance spectrum of the sample described in Example 1, (b) is the reflectance spectrum of the sample described in Example 3, (c) is the reflectance spectrum of the yellow leaf, (d) is the reflectance spectrum of green leaves.
为了更清楚、完整的描述本发明的技术方案，以下通过具体实施例进一步详细说明本发明，应当理解，此处所描述的具体实施例仅用于解释本发明，并不用于限定本发明，可以在本发明权利限定的范围内进行各种改变。In order to describe the technical solution of the present invention more clearly and completely, the present invention is further described in detail below through specific embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the Various changes can be made within the scope defined by the claims of the present invention.
实施例1Example 1
将原料CaCO
3，TeO
2，MnCO
3，Li
2CO
3按元素摩尔比Ca:Te:Mn:Li＝2.4：1：0.3：0.3称取后混合并研磨均匀放入马弗炉中，从室温以4℃/min的升温速率升温至1000℃，在空气中煅烧6小时，自然降温，取出研磨后即得到粉末样品。
The raw materials CaCO 3 , TeO 2 , MnCO 3 , Li 2 CO 3 were weighed according to the element molar ratio Ca:Te:Mn:Li=2.4:1:0.3:0.3, mixed and ground into a muffle furnace, from room temperature The temperature was raised to 1000°C at a heating rate of 4°C/min, calcined in air for 6 hours, cooled naturally, and a powder sample was obtained after taking out and grinding.
实施例2Example 2
将原料CaO，TeO
2，MnO，Li
2CO
3按元素摩尔比Ca:Te:Mn:Li＝2.6：1：0.2：0.2称取后混合并研磨均匀放入马弗炉中，从室温以6℃/min的升温速率升温至1100℃，在空气中煅烧4小时，自然降温，取出研磨后即得到粉末样品。
The raw materials CaO, TeO 2 , MnO, Li 2 CO 3 were weighed according to the elemental molar ratio Ca:Te:Mn:Li=2.6:1:0.2:0.2, mixed and ground into a muffle furnace, from room temperature to 6 The temperature was raised to 1100°C at a heating rate of ℃/min, calcined in air for 4 hours, cooled naturally, and a powder sample was obtained after taking out and grinding.
实施例3Example 3
将原料CaCO
3，TeO
2，Mn
2O
3，Li
2CO
3按元素摩尔比Ca:Te:Mn:Li＝2.8：1：0.1：0.1称取后混合并研磨均匀放入马弗炉中，从室温以4℃/min的升温速率升温至900℃，在空气中煅烧12小时，自然降温，取出研磨后即得到粉末样品。
The raw materials CaCO 3 , TeO 2 , Mn 2 O 3 , Li 2 CO 3 were weighed according to the element molar ratio Ca:Te:Mn:Li=2.8:1:0.1:0.1, mixed and ground into a muffle furnace. The temperature was raised from room temperature to 900°C at a heating rate of 4°C/min, calcined in air for 12 hours, cooled down naturally, and a powder sample was obtained after taking out and grinding.
实施例4Example 4
将原料CaCO
3，TeO
2，MnO
2，Li
2CO
3按元素摩尔比Ca:Te:Mn:Li＝2.2：1：0.4：0.4称取后混合并研磨均匀放入马弗炉中，从室温以8℃/min的升温速率升温至1150℃，在空气中煅烧10小时，自然降温，取出研磨后即得到粉末样品。
The raw materials CaCO 3 , TeO 2 , MnO 2 , Li 2 CO 3 were weighed according to the element molar ratio Ca:Te:Mn:Li=2.2:1:0.4:0.4, mixed and ground into a muffle furnace, from room temperature The temperature was raised to 1150°C at a heating rate of 8°C/min, calcined in air for 10 hours, cooled naturally, and a powder sample was obtained after taking out and grinding.
实施例5Example 5
将原料CaCO
3，TeO
2，MnO
2，Li
2CO
3按元素摩尔比Ca:Te:Mn:Li＝2.4：1：0.3：0.3称取后混合并研磨均匀放入马弗炉中，从室温以10℃/min的升温速率升温至1200℃，在空气中煅烧8小时，自然降温，取出研磨后即得到粉末样品。
The raw materials CaCO 3 , TeO 2 , MnO 2 , Li 2 CO 3 were weighed in the element molar ratio Ca:Te:Mn:Li=2.4:1:0.3:0.3, mixed and ground into a muffle furnace, from room temperature The temperature was raised to 1200°C at a heating rate of 10°C/min, calcined in air for 8 hours, cooled down naturally, and a powder sample was obtained after taking out and grinding.
对比例1Comparative Example 1
将原料CaCO
3，TeO
2，MnCO
3按元素摩尔比Ca:Te:Mn＝2.4：1：0.3称取后混合并研磨均匀放入马弗炉中，从室温以4℃/min的升温速率升温至1000℃，在空气中煅烧6小时，自然降温，取出研磨后即得到粉末样品。粉末样品为白色，原因在于没有引入Li
+离子作为激活剂，Mn主要以二价形式存在。
The raw materials CaCO 3 , TeO 2 , MnCO 3 were weighed according to the element molar ratio Ca:Te:Mn=2.4:1:0.3, mixed and ground evenly, put them into a muffle furnace, and heated at a heating rate of 4°C/min from room temperature To 1000 ° C, calcined in the air for 6 hours, naturally cooled, take out and grind to obtain a powder sample. The powder samples are white because Li + ions are not introduced as activators, and Mn exists mainly in the divalent form.
对比例2Comparative Example 2
本对比例2与实施例1的区别在于，本对比例2中煅烧温度为600℃。The difference between the comparative example 2 and the embodiment 1 is that the calcination temperature in the comparative example 2 is 600°C.
对比例3Comparative Example 3
本对比例3与实施例1的区别在于，本对比例3中煅烧温度为1250℃。本对比例3未能制备绿色伪装颜料，原因在于1250℃条件下，样品褪色且部分融化。The difference between this comparative example 3 and example 1 is that the calcination temperature in this comparative example 3 is 1250°C. The green camouflage pigment could not be prepared in this Comparative Example 3 because the sample faded and partially melted under the condition of 1250°C.
表征representation
图1为实施例1所述样品的XRD图，从图中可以看出，实施例1所述样品的物相与Ca
3TeO
6的XRD图谱匹配，说明实施例1成功制备了绿色颜料。实施例2～5所述样品的XRD图与实施例1基本一致。
Figure 1 is the XRD pattern of the sample described in Example 1. It can be seen from the figure that the phase of the sample described in Example 1 matches the XRD pattern of Ca 3 TeO 6 , indicating that the green pigment was successfully prepared in Example 1. The XRD patterns of the samples described in Examples 2 to 5 are basically the same as those in Example 1.
采用CIE(国际照明委员会)标准1976来描述颜料的颜色，即将眼睛接收到的颜色刺激和颜色质量的感知转换为颜色坐标L*、a*、b*表示。通过色度计测量的实施例1～5所述样品的颜色坐标值及计算得到的色相角度值h°如表1所示。The CIE (Commission on Illumination) standard 1976 is used to describe the color of pigments, that is, the perception of color stimuli and color quality received by the eye is converted into color coordinates L*, a*, b* representation. The color coordinate values of the samples described in Examples 1 to 5 measured by a colorimeter and the calculated hue angle value h° are shown in Table 1.
表1Table 1
| L * L * | a * a * | b * b * | h°h° | |
| 实施例1Example 1 | 46.4046.40 | 1.401.40 | 19.9019.90 | 85.9785.97 |
| 实施例2Example 2 | 55.2355.23 | 0.640.64 | 22.6222.62 | 88.3888.38 |
| 实施例3Example 3 | 71.5271.52 | 0.560.56 | 31.1131.11 | 88.9588.95 |
| 实施例4Example 4 | 30.7630.76 | 0.630.63 | 9.679.67 | 86.2786.27 |
| 实施例5Example 5 | 52.1852.18 | 1.861.86 | 18.2218.22 | 84.1784.17 |
如表1所示，实施例1～5在色度空间中靠近a*轴，偏向b*轴(黄)，色相角度值h°分别为85.97°、88.38、88.95、86.27、84.17，由于L*值较低，视觉上为绿色。As shown in Table 1, Examples 1 to 5 are close to the a* axis in the chromaticity space, and are biased towards the b* axis (yellow), and the hue angle values h° are 85.97°, 88.38, 88.95, 86.27, and 84.17, respectively. Because L* Lower values are visually green.
对实施例1所述样品进行耐酸碱测试，即配置浓度为5％的HNO
3，浓度为5％的NaOH溶液，分别将颜料加入至上述配好的酸或碱溶液中，混合搅拌10分钟，过滤，再用水和乙醇洗涤，自然风干。另对实施例1所述样品进行高温测试，即将样品置于高温中煅烧。图2为实施例1所述样品酸碱处理前(Sample)和酸碱处理后的外观图，从图中可以看到，经过酸碱处理后，颜料颜色没有强烈变化，说明颜料耐酸碱。实施例2～5所述样品的酸碱测试结果与实施例1一致，酸碱及高温处理后颜色基本不变。
The acid and alkali resistance test was carried out on the sample described in Example 1, that is, HNO 3 with a concentration of 5% and a NaOH solution with a concentration of 5% were prepared, and the pigment was added to the acid or alkali solution prepared above, and mixed and stirred for 10 minutes , filtered, washed with water and ethanol, and air-dried. In addition, the sample described in Example 1 was subjected to a high temperature test, that is, the sample was calcined at a high temperature. Figure 2 is the appearance diagram of the sample before acid-base treatment (Sample) and after acid-base treatment described in Example 1. It can be seen from the figure that after acid-base treatment, the color of the pigment does not change strongly, indicating that the pigment is resistant to acid and alkali. The acid-base test results of the samples described in Examples 2 to 5 are consistent with those of Example 1, and the color is basically unchanged after acid-base and high-temperature treatment.
实施例1所述样品酸碱及高温处理前后样品的颜色坐标值及计算得到的色差ΔE
*如表2所示，实施例2～5所述样品酸碱及高温处理前后样品的色差ΔE
*与实施例1基本一致。
The color coordinate values of the samples before and after high temperature treatment and the calculated color difference ΔE * of the sample described in Example 1 are shown in Table 2. The color difference ΔE * of the samples described in Examples 2 to 5 before and after high temperature treatment is the same as the Example 1 is basically the same.
表2Table 2
| L * L * | a*a* | b*b* | ΔE * ΔE * | |
| 未处理not processed | 46.4046.40 | 1.401.40 | 19.9019.90 | -- |
| 5％NaOH5%NaOH | 46.0346.03 | 1.561.56 | 19.4119.41 | 0.630.63 |
| 5％HNO 3 5% HNO3 | 47.1047.10 | 1.351.35 | 19.6819.68 | 0.730.73 |
| 1100℃1100℃ | 46.9846.98 | 1.671.67 | 19.7519.75 | 0.660.66 |
从表2可看到，酸碱及高温处理后色差ΔE
*小于1，进一步证明本发明所述颜料耐酸碱、耐高温。
It can be seen from Table 2 that the color difference ΔE * after acid-base and high-temperature treatment is less than 1, which further proves that the pigment of the present invention is resistant to acid, alkali and high temperature.
图3为对比例2所述样品的XRD图，从图中可以看出，样品的物相与Ca
3TeO
6的XRD图谱不匹配，即对比例2未能制备得到所述绿色颜料。
Figure 3 is the XRD pattern of the sample described in Comparative Example 2. It can be seen from the figure that the phase of the sample does not match the XRD pattern of Ca 3 TeO 6 , that is, the green pigment cannot be prepared in Comparative Example 2.
图4中(a)为实施例1所述样品的反射率光谱图，(b)为实施例3所述样品的反射率光谱图，(c)为黄色叶片的反射率光谱图，(d)为绿色叶片的反射率光谱图，从图中可以看出，实施例1和实施例3所述样品在紫外-可见-近红外区(200-1200nm)内的反射率光谱与(黄色、绿色)树叶的反射率光谱类似，表明本发明所述颜料可用于伪装材料的涂装。实施例2、实施例4和实施例5的紫外-可见-近红外区(200-1200nm)内的反射率光谱与实施例1基本一致。In Figure 4 (a) is the reflectance spectrum of the sample described in Example 1, (b) is the reflectance spectrum of the sample described in Example 3, (c) is the reflectance spectrum of the yellow leaf, (d) It is the reflectance spectrum of green leaves. It can be seen from the figure that the reflectance spectrum of the samples described in Example 1 and Example 3 in the ultraviolet-visible-near-infrared region (200-1200nm) is the same as (yellow, green) The reflectance spectra of leaves are similar, indicating that the pigments of the present invention can be used in the coating of camouflage materials. The reflectance spectra in the ultraviolet-visible-near-infrared region (200-1200 nm) of Example 2, Example 4 and Example 5 are basically the same as Example 1.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进 等，均应包含在本发明权利要求的保护范围之内。Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.
Claims (10)
- 一种基于Ca 3TeO 6结构的绿色颜料，其特征在于，所述绿色颜料的分子式为Ca 3-2xMn xLi xTeO 6，其中0.1≤x≤0.4。 A green pigment based on the structure of Ca 3 TeO 6 , characterized in that, the molecular formula of the green pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.1≤x≤0.4.
- 如权利要求1所述绿色颜料，其特征在于，所述绿色颜料的分子式为Ca 3-2xMn xLi xTeO 6，其中0.2≤x≤0.3。 The green pigment according to claim 1, wherein the molecular formula of the green pigment is Ca 3-2x Mn x Li x TeO 6 , wherein 0.2≤x≤0.3.
- 如权利要求1或2所述绿色颜料的制备方法，其特征在于，包括如下步骤：The preparation method of green pigment as claimed in claim 1 or 2, is characterized in that, comprises the steps:将原料含钙的化合物、含碲的化合物、含锰的化合物、Li 2CO 3按元素摩尔比称取后混合并研磨均匀在900～1200℃条件下煅烧，冷却后所得即为绿色颜料。 The raw materials calcium-containing compound, tellurium-containing compound, manganese-containing compound, Li 2 CO 3 are weighed according to the element molar ratio, mixed, ground and evenly calcined at 900-1200 ℃, and the green pigment is obtained after cooling.
- 如权利要求3所述绿色颜料的制备方法，其特征在于，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.1≤x≤0.4。The method for preparing a green pigment according to claim 3, wherein the element molar ratio Ca:Te:Mn:Li=(3-2x):1:x:x, wherein 0.1≤x≤0.4.
- 如权利要求4所述绿色颜料的制备方法，其特征在于，所述元素摩尔比Ca:Te:Mn:Li＝(3-2x)：1：x：x，其中0.2≤x≤0.3。The method for preparing a green pigment according to claim 4, wherein the element molar ratio Ca:Te:Mn:Li=(3-2x):1:x:x, wherein 0.2≤x≤0.3.
- 如权利要求3所述绿色颜料的制备方法，其特征在于，所述含钙的化合物为碳酸钙、氧化钙中的一种或两种。The method for preparing a green pigment according to claim 3, wherein the calcium-containing compound is one or both of calcium carbonate and calcium oxide.
- 如权利要求3所述绿色颜料的制备方法，其特征在于，所述含锰的化合物为碳酸锰、一氧化锰、二氧化锰和三氧化二锰中的一种或多种。The method for preparing a green pigment according to claim 3, wherein the manganese-containing compound is one or more of manganese carbonate, manganese monoxide, manganese dioxide and manganese trioxide.
- 如权利要求3所述绿色颜料的制备方法，其特征在于，所述煅烧为以4℃/min～10℃/min的升温速率将温度升至1000～1100℃，保温4～12h。The method for preparing a green pigment according to claim 3, wherein the calcination is to raise the temperature to 1000-1100°C at a heating rate of 4°C/min-10°C/min, and keep the temperature for 4-12 hours.
- 如权利要求8所述绿色颜料的制备方法，其特征在于，所述煅烧为以4℃/min～6℃/min的升温速率将温度升至1000～1100℃，保温4～8h。The method for preparing a green pigment according to claim 8, wherein the calcination is to raise the temperature to 1000-1100°C at a heating rate of 4°C/min-6°C/min, and keep the temperature for 4-8 hours.
- 权利要求1或2所述绿色颜料在伪装材料领域中的应用。The application of the green pigment of claim 1 or 2 in the field of camouflage materials.
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Non-Patent Citations (6)
| Title |
|---|
| LI KAI, VAN DEUN RIK: "Realizing a novel dazzling far-red-emitting phosphor NaLaCaTeO 6 :Mn 4+ with high quantum yield and luminescence thermal stability via the ionic couple substitution of Na + + La 3+ for 2Ca 2+ in Ca 3 TeO 6 :Mn 4+ for indoor plant cultivation LEDs", CHEMICAL COMMUNICATIONS, ROYAL SOCIETY OF CHEMISTRY, UK, vol. 55, no. 72, 5 September 2019 (2019-09-05), UK , pages 10697 - 10700, XP055947700, ISSN: 1359-7345, DOI: 10.1039/C9CC05465K * |
| NALBANDYAN VLADIMIR B., SHUKAEV IGOR L., RAGANYAN GRIGORY V., SVYAZHIN ARTEM, VASILIEV ALEXANDER N., ZVEREVA ELENA A.: "Preparation, Crystal Chemistry, and Hidden Magnetic Order in the Family of Trigonal Layered Tellurates A 2 Mn(4+)TeO 6 (A = Li, Na, Ag, or Tl)", INORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY, EASTON , US, vol. 58, no. 9, 6 May 2019 (2019-05-06), Easton , US , pages 5524 - 5532, XP055947701, ISSN: 0020-1669, DOI: 10.1021/acs.inorgchem.8b03445 * |
| POLITOVA, E.D. ; VENEVTSEV, Y.N.: "Ferroelectricity and antiferroelectricity in tellurium containing compounds with perovskite structure", MATERIALS RESEARCH BULLETIN, ELSEVIER, KIDLINGTON., GB, vol. 10, no. 4, 1 April 1975 (1975-04-01), GB , pages 319 - 325, XP024078576, ISSN: 0025-5408, DOI: 10.1016/0025-5408(75)90120-8 * |
| RETUERTO MARIA, SKIADOPOULOU STELLA, BORODAVKA FEDIR, KADLEC CHRISTELLE, KADLEC FILIP, PROKLEŠKA JAN, DENG ZHENG, ALONSO JOSE A., : "Structural and Spectroscopic Properties of the Polar Antiferromagnet Ni2MnTeO6", PHYSICAL REVIEW B, vol. 97, no. 14, 23 April 2018 (2018-04-23), pages 144418, XP055947716, ISSN: 2469-9950, DOI: 10.1103/PhysRevB.97.144418 * |
| S. NATANSOHN: "Fluorescence Properties of Alkaline Earth Tellurates", JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol. 120, no. 5, 1 May 1973 (1973-05-01), pages 660 - 664, XP001278667 * |
| ZARAQ A, ORAYECH B, IGARTUA J. M, EL BOUARI A: "Synthesis, Crystal Structure, and Vibrational Studies of the Monoclinically Distorted Double Perovskite, Sr2Mn1−xNixTeO6 with (x=0.25, 0.5, and 0.75)", POWDER DIFFRACTION, JCPDS-INTERNATIONAL CENTRE FOR DIFFRACTION DATA, WSARTHMORE, US, vol. 34, no. S1, 30 September 2019 (2019-09-30), US , pages S48 - S58, XP009537953, ISSN: 0885-7156, DOI: 10.1017/S0885715619000411 * |
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