CN108359270A - Ultra-fine Preen nono ceramic paint of spinel-type and preparation method thereof - Google Patents
Ultra-fine Preen nono ceramic paint of spinel-type and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003973 paint Substances 0.000 title description 2
- 229910010069 TiCo Inorganic materials 0.000 claims abstract description 41
- 239000000049 pigment Substances 0.000 claims abstract description 41
- 239000000243 solution Substances 0.000 claims abstract description 26
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052596 spinel Inorganic materials 0.000 claims description 21
- 239000011029 spinel Substances 0.000 claims description 21
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical group CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 239000001384 succinic acid Substances 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical group [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 8
- 238000002310 reflectometry Methods 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical group C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 12
- 235000013772 propylene glycol Nutrition 0.000 description 12
- 238000001035 drying Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- SNLCFABCUVHNSN-UHFFFAOYSA-J Cl[Co](Cl)(Cl)Cl Chemical compound Cl[Co](Cl)(Cl)Cl SNLCFABCUVHNSN-UHFFFAOYSA-J 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 239000001056 green pigment Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical group O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C09C1/0009—Pigments for ceramics
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/40—Complex oxides containing cobalt and at least one other metal element
-
- 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
- C01P2006/32—Thermal properties
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
一种尖晶石型超细绿色纳米陶瓷颜料及其制备方法，包括如下步骤：1）将钴盐和钛源溶解在蒸馏水中，并用玻璃棒适当搅拌，待其完全溶解；2）加入稳定剂；3）调节pH至5.0‑7.0；4)将一定量的交联剂加入混合溶液中形成凝胶状溶液；5）以上钴盐和钛源分别以钴和钛计，则稳定剂：交联剂：钛：钴的物质的量为3.95‑4.05：0.95‑1.05：0.95‑1.05：1.95‑2.05；6）使凝胶状溶液蒸发；7）热处理，研磨后得到的产物即绿色TiCo2O4陶瓷颜料。该陶瓷颜料具有粒度小、分散性好、色泽鲜艳、稳定性好、近红外反射率高的优点。A spinel-type ultra-fine green nano-ceramic pigment and a preparation method thereof, comprising the following steps: 1) dissolving cobalt salt and titanium source in distilled water, stirring properly with a glass rod until they are completely dissolved; 2) adding a stabilizer ;3) Adjust the pH to 5.0-7.0; 4) Add a certain amount of cross-linking agent to the mixed solution to form a gel-like solution; 5) The above cobalt salt and titanium source are calculated as cobalt and titanium respectively, then the stabilizer: cross-linking Agent: Titanium: The amount of cobalt substance is 3.95‑4.05: 0.95‑1.05: 0.95‑1.05: 1.95‑2.05; 6) Evaporate the gel-like solution; 7) Heat treatment, the product obtained after grinding is green TiCo 2 O 4 ceramic pigments. The ceramic pigment has the advantages of small particle size, good dispersibility, bright color, good stability and high near-infrared reflectivity.
Description
技术领域technical field
本发明属于高近红外反射功能颜料技术领域，具体是涉及一种尖晶石型超细绿色陶瓷颜料的制备方法。The invention belongs to the technical field of high near-infrared reflective functional pigments, and in particular relates to a preparation method of spinel-type ultrafine green ceramic pigments.
背景技术Background technique
绿色是自然界中常见的颜色，是在光谱中介于蓝与黄之间的颜色，光波长约550nm。绿色陶瓷颜料用处很多，像用于陶瓷装饰艺术，或用于墙体涂料。但传统的绿色颜料通常以氧化铬为发色剂并在其中加入一定数量的天然矿物原料和Ca、Mg等配制而成。这种颜料一是有毒；二是色差，气氛中的氧分压和温度对铬的氧化物都是敏感的，如Cr2O3在不同的气氛中以不同的形式存在，这种特性使产品难以达到色调均匀一致的目的。二是颜色暗绿，且传统铬绿颜料使用过程中常伴有釉面针眼和剥釉等现象。众所周知，当颜料尺寸降到纳米级时，材料就有着常规材料无可比拟的优越性能，因此我们的目标就是致力于用一种节能、环保的方式制备出一种尺寸小且分散性好、具有高红外反射率的尖晶石型TiCo2O4绿色纳米陶瓷颜料。Green is a common color in nature, it is a color between blue and yellow in the spectrum, and the wavelength of light is about 550nm. Green ceramic pigments are used in many ways, such as for ceramic decorative art, or for wall paint. However, traditional green pigments are usually prepared by using chromium oxide as a coloring agent and adding a certain amount of natural mineral raw materials and Ca, Mg, etc. to it. This kind of pigment is poisonous; the second is color difference. The oxygen partial pressure and temperature in the atmosphere are sensitive to chromium oxides. For example, Cr 2 O 3 exists in different forms in different atmospheres. This characteristic makes the product It is difficult to achieve the purpose of uniform tone. Second, the color is dark green, and the use of traditional chrome green pigments is often accompanied by phenomena such as glaze pinholes and glaze peeling. As we all know, when the size of the pigment is reduced to the nanometer level, the material has unparalleled superior performance compared to conventional materials, so our goal is to prepare a small size and good dispersion in an energy-saving and environmentally friendly way. A spinel-type TiCo 2 O 4 green nano-ceramic pigment with high infrared reflectivity.
申请号为201210342748.0的专利申请公开了一种多元掺杂的三氧化二铬绿色高近红外反射颜料。与常规的市售颜料相比，既具有低可见光明度，又具有近红外高反射特性的绿色，并在 680nm-700nm 波段内具有明显的反射率突变特性，可以满足彩色高反射节能涂层、目标伪装涂层等对颜料光谱反射特性的应用要求。但是其制备过程采用了固相法，需要的温度很高（1200℃），且湿法研磨后再烘干，需要很大的能量且不利于节能减排，成本较高且粒度较大会有一定的成分偏析。The patent application with application number 201210342748.0 discloses a multi-component doped chromium trioxide green high near-infrared reflective pigment. Compared with conventional commercially available pigments, it is green with low visible lightness and high near-infrared reflection characteristics, and has obvious mutation characteristics of reflectivity in the 680nm-700nm band, which can meet the requirements of color high-reflection energy-saving coatings, targets Application requirements for camouflage coatings on the spectral reflectance characteristics of pigments. However, the solid-phase method is used in its preparation process, which requires a high temperature (1200°C), and it needs a lot of energy and is not conducive to energy saving and emission reduction. The cost is high and the particle size is large. composition segregation.
发明内容Contents of the invention
为了克服上述技术问题，本发明提供一种尖晶石型超细绿色纳米陶瓷颜料及其制备方法，该陶瓷颜料具有粒度小、分散性好、色泽鲜艳、稳定性好、近红外反射率高的优点。In order to overcome the above-mentioned technical problems, the present invention provides a spinel-type ultrafine green nano-ceramic pigment and a preparation method thereof. The ceramic pigment has small particle size, good dispersibility, bright color, good stability and high near-infrared reflectivity. advantage.
为解决上述技术问题，本发明的技术方案是：In order to solve the problems of the technologies described above, the technical solution of the present invention is:
一种尖晶石型超细绿色纳米陶瓷颜料的制备方法，包括如下步骤：A preparation method of spinel type ultrafine green nano-ceramic pigment, comprising the steps of:
1）将钴盐和钛源溶解在蒸馏水中，并用玻璃棒适当搅拌，待其完全溶解；1) Dissolve the cobalt salt and titanium source in distilled water, and stir properly with a glass rod until they are completely dissolved;
2）加入稳定剂；2) Add stabilizer;
3）调节pH至5.0-7.0；3) Adjust the pH to 5.0-7.0;
4) 将一定量的交联剂加入混合溶液中形成凝胶状溶液；4) A certain amount of cross-linking agent is added to the mixed solution to form a gel-like solution;
5）以上钴盐和钛源分别以钴和钛计，则稳定剂：交联剂：钛：钴的物质的量为3.95-4.05：0.95-1.05：0.95-1.05：1.95-2.05；5) The above cobalt salt and titanium source are calculated as cobalt and titanium respectively, then the amount of stabilizer: crosslinking agent: titanium: cobalt is 3.95-4.05: 0.95-1.05: 0.95-1.05: 1.95-2.05;
6）使凝胶状溶液蒸发；6) Evaporate the gel-like solution;
7）热处理，研磨后得到的产物即绿色TiCo2O4陶瓷颜料。7) Heat treatment, the product obtained after grinding is green TiCo 2 O 4 ceramic pigment.
进一步地，在上述方案中，所述步骤3）逐滴滴加氨水或碳酸氢钠或碳酸钠或氢氧化钠溶液调节pH。Further, in the above scheme, step 3) adding ammonia water or sodium bicarbonate or sodium carbonate or sodium hydroxide solution drop by drop to adjust the pH.
进一步地，在上述方案中，：所述步骤1）中钴盐为硝酸钴、氯化钴或醋酸钴的中任一种；钛源为钛酸丁酯或四氯化钛，稳定剂：交联剂：钛：钴的物质的量为4：1：1：2。Further, in the above scheme,: the cobalt salt in step 1) is any one of cobalt nitrate, cobalt chloride or cobalt acetate; the titanium source is butyl titanate or titanium tetrachloride, and the stabilizer: alternating Joint agent: the amount of titanium: cobalt substance is 4:1:1:2.
进一步地，在上述方案中，所述稳定剂为丁二酸,所述交联剂为1，2-丙二醇。Further, in the above scheme, the stabilizer is succinic acid, and the crosslinking agent is 1,2-propanediol.
进一步地，在上述方案中，步骤4）在温室下下搅拌为2-4h，步骤6）所述的蒸发过程温度为75-85℃，蒸发过程在磁力搅拌器上边搅拌边蒸发或者在烘箱里烘干进行。Further, in the above scheme, step 4) is stirred under the greenhouse for 2-4 hours, the temperature of the evaporation process described in step 6) is 75-85°C, and the evaporation process is evaporated while stirring on a magnetic stirrer or in an oven Drying is carried out.
进一步地，在上述方案中，步骤7）所述的热处理温度为200-400℃烘干1.5-3h，600-800℃烘干3.5-4.5h。Further, in the above scheme, the heat treatment temperature in step 7) is 200-400°C for 1.5-3 hours, and 600-800°C for 3.5-4.5 hours.
更进一步地，在上述方案中，步骤6）所述的蒸发过程中温度为80℃，蒸发过程是在磁力搅拌器上边搅拌边蒸发或在烘箱里烘干进行。Furthermore, in the above solution, the temperature in the evaporation process described in step 6) is 80°C, and the evaporation process is performed on a magnetic stirrer while evaporating or drying in an oven.
更进一步地，在上述方案中，步骤7）所述的热处理温度为300-400℃烘干2h，600-800℃烘干4h；Furthermore, in the above scheme, the heat treatment temperature in step 7) is 300-400°C for 2 hours, and 600-800°C for 4 hours;
更进一步地，在上述方案中，步骤7）所述的热处理温度300-400℃烘干2h，650-750℃烘干4h。Furthermore, in the above solution, the heat treatment temperature in step 7) is 300-400°C for 2 hours, and 650-750°C for 4 hours.
一种采用上述任一项所述方法制备得到的尖晶石型TiCo2O4超细绿色纳米陶瓷颜料。A spinel type TiCo 2 O 4 ultrafine green nano-ceramic pigment prepared by any one of the methods described above.
更进一步地，在上述方案中，步骤4）在室温下搅拌约4h，搅拌时间低于4h，则反应不充分，产物相不均匀；经检测得知当步骤3）中的pH为6时产物分散性较好，呈色性较好，因此pH为6为较优；步骤6）所述的蒸发过程中在磁力搅拌器上约80℃烘干较为简单省时，效果也较为理想。Furthermore, in the above scheme, step 4) is stirred at room temperature for about 4 hours, and if the stirring time is less than 4 hours, the reaction is insufficient and the product phase is uneven; it is found that when the pH in step 3) is 6, the product It has better dispersibility and better coloration, so pH 6 is better; drying on a magnetic stirrer at about 80°C during the evaporation process in step 6) is simpler and time-saving, and the effect is also more ideal.
更进一步地，在上述方案中，步骤7）所述的热处理温度为200-400℃烘干2h，600-800℃烘干4h时产物颗粒分散性一般，呈色性一般；当热处理温度为300-400℃烘干2h，600-800℃烘干4h时，分散性较好，呈色性较好；当热处理温度为350℃烘干2h，700℃烘干4h，分散性最好，呈色性也最好。Furthermore, in the above scheme, the heat treatment temperature in step 7) is 200-400°C for 2 hours and 600-800°C for 4 hours. When drying at -400°C for 2 hours, and drying at 600-800°C for 4 hours, the dispersibility and coloration are better; when the heat treatment temperature is 350°C for 2 hours, and 700°C for 4 hours, the dispersibility and coloration are the best. Sex is also the best.
本发明的有益效果是：本发明合成的尖晶石型TiCo2O4陶瓷颜料呈色性好、具有高化学稳定性、分散性好、且具有高的近红外反射率。且合成方法简单、原料易得，需要的温度相对较低，且工艺简单可控，能够大规模工业化生产；并且制得的产物低毒甚至无毒，绿色环保，具有非常好的耐热性、耐光性、耐化学品性，易分散，呈色性好，是一种具有高的红外反射率的绿色功能颜料。The beneficial effects of the invention are: the spinel type TiCo 2 O 4 ceramic pigment synthesized by the invention has good color rendering, high chemical stability, good dispersibility and high near-infrared reflectivity. Moreover, the synthesis method is simple, the raw materials are easy to obtain, the required temperature is relatively low, and the process is simple and controllable, which can be industrialized on a large scale; and the obtained product is low-toxic or even non-toxic, green and environmentally friendly, and has very good heat resistance. Light resistance, chemical resistance, easy dispersion, good color rendering, is a green functional pigment with high infrared reflectivity.
附图说明Description of drawings
图1为TiCo2O4的X射线衍射谱图。Figure 1 is the X-ray diffraction spectrum of TiCo 2 O 4 .
图2为TiCo2O4的SEM图。Figure 2 is the SEM image of TiCo 2 O 4 .
图3为TiCo2O4的EDS点扫描图。Figure 3 is the EDS point scan diagram of TiCo 2 O 4 .
图4为TiCo2O4的EDS面扫描图。Fig. 4 is an EDS surface scan diagram of TiCo 2 O 4 .
具体实施方案specific implementation plan
以下结合实施例对本发明的技术方案作进一步地详细介绍，但本发明的保护范围并不局限于此。The technical solutions of the present invention will be further described in detail below in conjunction with the examples, but the protection scope of the present invention is not limited thereto.
TiCo2O4实施例1TiCo 2 O 4 Example 1
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为5.0，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在磁力搅拌器上80℃使凝胶状溶液蒸发。再在350℃下煅烧2h，700℃下煅烧4h，研磨后得到的产物即尖晶石型绿色TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 5.0, and add 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 h, and the gel-like solution was evaporated on a magnetic stirrer at 80 °C. Calcining at 350° C. for 2 hours and 700° C. for 4 hours, the product obtained after grinding is spinel green TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例2TiCo 2 O 4 Example 2
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为6.0，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在磁力搅拌器上80℃使凝胶状溶液蒸发。再在350℃下煅烧2h，700℃下煅烧4h，研磨后得到的产物即尖晶石型TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 6.0, and add 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 h, and the gel-like solution was evaporated on a magnetic stirrer at 80 °C. Then calcining at 350° C. for 2 hours and 700° C. for 4 hours, and the product obtained after grinding is spinel type TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例3TiCo 2 O 4 Example 3
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为7.0，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在磁力搅拌器上80℃使凝胶状溶液蒸发。再在350℃下煅烧2h，700℃下煅烧4h，研磨后得到的产物即尖晶石型TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 7.0, and mix 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 h, and the gel-like solution was evaporated on a magnetic stirrer at 80 °C. Then calcining at 350° C. for 2 hours and 700° C. for 4 hours, and the product obtained after grinding is spinel type TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例4TiCo 2 O 4 Example 4
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为6.0，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在烘箱中温度为80℃使凝胶状溶液蒸发。再在350℃下煅烧2h，700℃下煅烧4h，研磨后得到的产物即尖晶石型TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 6.0, and add 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 hours, and the gel-like solution was evaporated in an oven at a temperature of 80°C. Then calcining at 350° C. for 2 hours and 700° C. for 4 hours, and the product obtained after grinding is spinel type TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例5TiCo 2 O 4 Example 5
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为6.0，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在磁力搅拌器上80℃使凝胶状溶液蒸发。再在250℃下煅烧2h，700℃下煅烧4h，研磨后得到的产物即尖晶石型TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 6.0, and add 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 h, and the gel-like solution was evaporated on a magnetic stirrer at 80 °C. Calcining at 250° C. for 2 hours and 700° C. for 4 hours, the product obtained after grinding is spinel type TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例6TiCo 2 O 4 Example 6
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为6，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在磁力搅拌器上80℃使凝胶状溶液蒸发。再在350℃下煅烧2h，600℃下煅烧4h，研磨后得到的产物即尖晶石型TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 6, and mix 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 h, and the gel-like solution was evaporated on a magnetic stirrer at 80 °C. Then calcining at 350° C. for 2 hours and 600° C. for 4 hours, the product obtained after grinding is the spinel type TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例7TiCo 2 O 4 Example 7
将2.9g的硝酸钴和1.7g的钛酸丁酯溶解在室温下蒸馏水中，加入2.36g的丁二酸作为稳定剂，逐滴滴加氨水调节pH为6，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌4h，在磁力搅拌器上80℃使凝胶状溶液蒸发。再在350℃下煅烧2h，800℃下煅烧4h，研磨后得到的产物即尖晶石型TiCo2O4纳米陶瓷颜料。Dissolve 2.9 g of cobalt nitrate and 1.7 g of butyl titanate in distilled water at room temperature, add 2.36 g of succinic acid as a stabilizer, add ammonia water drop by drop to adjust the pH to 6, and mix 0.38 g of crosslinking agent ( 1,2-propanediol) was added to the mixed solution, stirred for 4 h, and the gel-like solution was evaporated on a magnetic stirrer at 80 °C. Calcining at 350° C. for 2 hours and 800° C. for 4 hours, the product obtained after grinding is spinel type TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例8TiCo 2 O 4 Example 8
将1.27g的四氯化钴和1.66g的钛酸丁酯溶解在室温下蒸馏水中，加入2.33g的丁二酸作为稳定剂，逐滴滴加碳酸氢钠溶液调节pH为5.5，将0.33g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌2h，在磁力搅拌器上75℃使凝胶状溶液蒸发。再在200℃下煅烧3.5h，600℃下煅烧4.5h，研磨后得到的产物即尖晶石型绿色TiCo2O4纳米陶瓷颜料。1.27g of cobalt tetrachloride and 1.66g of butyl titanate were dissolved in distilled water at room temperature, 2.33g of succinic acid was added as a stabilizer, and sodium bicarbonate solution was added dropwise to adjust the pH to 5.5, and 0.33g The cross-linking agent (1,2-propanediol) was added to the mixed solution, stirred for 2 h, and the gel-like solution was evaporated on a magnetic stirrer at 75 °C. Calcining at 200° C. for 3.5 hours and 600° C. for 4.5 hours, the product obtained after grinding is spinel green TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例9TiCo 2 O 4 Example 9
将1.74g的醋酸钴和0.93g的四氯化钛溶解在室温下蒸馏水中，加入2.34g的丁二酸作为稳定剂，逐滴滴加氢氧化钠溶液调节pH为6.5，将0.34g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌2.5h，在磁力搅拌器上78℃使凝胶状溶液蒸发。再在250℃下煅烧2.5h，650℃下煅烧4.2h，研磨后得到的产物即尖晶石型绿色TiCo2O4纳米陶瓷颜料。1.74g of cobalt acetate and 0.93g of titanium tetrachloride were dissolved in distilled water at room temperature, 2.34g of succinic acid was added as a stabilizer, and sodium hydroxide solution was added dropwise to adjust the pH to 6.5. The coupling agent (1,2-propanediol) was added to the mixed solution, stirred for 2.5h, and the gel-like solution was evaporated on a magnetic stirrer at 78°C. Then calcined at 250° C. for 2.5 hours, and then calcined at 650° C. for 4.2 hours. The product obtained after grinding is spinel green TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例10TiCo 2 O 4 Example 10
将1.33g的四氯化钴和1.74g的钛酸丁酯溶解在室温下蒸馏水中，加入2.37g的丁二酸作为稳定剂，逐滴滴加碳酸钠溶液调节pH为5，将0.38g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌3h，在磁力搅拌器上82℃使凝胶状溶液蒸发。再在350℃下煅烧1.8h，750℃下煅烧4h，研磨后得到的产物即尖晶石型绿色TiCo2O4纳米陶瓷颜料。1.33g of cobalt tetrachloride and 1.74g of butyl titanate were dissolved in distilled water at room temperature, 2.37g of succinic acid was added as a stabilizer, and sodium carbonate solution was added dropwise to adjust the pH to 5. 0.38g of A cross-linking agent (1,2-propanediol) was added to the mixed solution, stirred for 3 h, and the gel-like solution was evaporated on a magnetic stirrer at 82 °C. Calcining at 350° C. for 1.8 hours and 750° C. for 4 hours, the product obtained after grinding is spinel green TiCo 2 O 4 nano ceramic pigment.
TiCo2O4实施例11TiCo 2 O 4 Example 11
将1.81g的醋酸钴和0.97g的四氯化钛溶解在室温下蒸馏水中，加入2.38g的丁二酸作为稳定剂，逐滴滴加碳酸氢钠调节pH为7，将0.381g的交联剂（1,2-丙二醇）加入混合溶液中，搅拌3.5h，在磁力搅拌器上85℃使凝胶状溶液蒸发。再在400℃下煅烧1.5h，800℃下煅烧3.5h，研磨后得到的产物即尖晶石型绿色TiCo2O4纳米陶瓷颜料。Dissolve 1.81 g of cobalt acetate and 0.97 g of titanium tetrachloride in distilled water at room temperature, add 2.38 g of succinic acid as a stabilizer, add sodium bicarbonate drop by drop to adjust the pH to 7, and 0.381 g of crosslinked Agent (1,2-propanediol) was added to the mixed solution, stirred for 3.5h, and the gel-like solution was evaporated on a magnetic stirrer at 85°C. Then calcined at 400°C for 1.5h, and at 800°C for 3.5h, and the product obtained after grinding was spinel-type green TiCo 2 O 4 nano-ceramic pigment.
XRD测试XRD test
对产物TiCo2O4进行XRD分析，如图1所示。由图1可知：TiCo2O4峰形尖锐结晶性良好，最强峰约在2θ为33.4547°处，经与标准谱图对照，发现该方法所得产物结晶性很好，至于形态上是否达到了不规则有棱角的尖晶石的预期形状，有待通过SEM进行下一步研究。The product TiCo 2 O 4 was analyzed by XRD, as shown in Fig. 1 . It can be seen from Figure 1 that the peak shape of TiCo 2 O 4 is sharp and the crystallinity is good, and the strongest peak is at 2θ of 33.4547°. After comparing with the standard spectrum, it is found that the crystallinity of the product obtained by this method is very good. As for whether the morphology has reached The expected shape of the irregular and angular spinel is yet to be further studied by SEM.
SEM测试SEM test
对TiCo2O4进行SEM分析，如图2所示：图2（a）、（b）、（c）、（d）分别是TiCo2O4放大50000倍、100000倍、150000倍和300000倍的SEM图。通过图2（a）放大50000倍的SEM图可知TiCo2O4颗粒完整，粒度均匀，颗粒呈现出不规则有棱角的形状，达到了预期的效果，且颗粒整体分布很均匀，无明显团聚现象。同样由图2（b）、（c）、（d）可知颗粒呈现出不规则有棱角的尖晶石的形状，达到了预期的效果。SEM analysis of TiCo 2 O 4 is shown in Figure 2: Figure 2 (a), (b), (c), and (d) are SEM images of TiCo2O4 magnified 50,000 times, 100,000 times, 150,000 times, and 300,000 times, respectively . According to the SEM image enlarged by 50000 times in Figure 2(a), it can be seen that the TiCo 2 O 4 particles are complete, the particle size is uniform, and the particles present an irregular and angular shape, which has achieved the expected effect, and the overall distribution of the particles is very uniform without obvious agglomeration . Also from Figure 2 (b), (c), (d), it can be seen that the particles present an irregular and angular spinel shape, which has achieved the expected effect.
EDS测试EDS test
通过能谱仪对产物进行了能谱测试，可知元素的含量及分布进而知道TiCo2O4的合成情况。图4为TiCo2O4的EDS面扫描图，通过图4可知：试样由Ti、Co、O三种元素组成，且三种元素分布均匀，没有团聚现象，也没有出现化学偏析现象。图3是基体TiCo2O4的EDS点扫描，通过图3可知试样由Ti、Co、O三种元素组成，且Ti的原子百分比近似于化学式中的原子百分比，O的含量偏高，可能是制备过程中不小心引入的杂质。所以基本上已经合成了TiCo2O4。The energy spectrum test was carried out on the product by an energy spectrometer, the content and distribution of the elements can be known, and then the synthesis of TiCo2O4 can be known. Figure 4 is the EDS surface scanning image of TiCo 2 O 4 . It can be seen from Figure 4 that the sample is composed of three elements: Ti, Co, and O, and the three elements are evenly distributed, without agglomeration or chemical segregation. Figure 3 is the EDS point scan of the matrix TiCo 2 O 4 , it can be seen from Figure 3 that the sample is composed of three elements: Ti, Co, and O, and the atomic percentage of Ti is similar to the atomic percentage in the chemical formula, and the content of O is high, which may be It is an impurity accidentally introduced during the preparation process. So basically TiCo 2 O 4 has been synthesized.
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的技术人员来说，在不脱离本发明整体构思前提下，还可以作出若干改变和改进，这些也应该视为本发明的保护范围，这些都不会影响本发明实施的效果和专利的实用性。What has been described above is only the preferred embodiment of the present invention. It should be pointed out that for those skilled in the art, some changes and improvements can be made without departing from the overall concept of the present invention, and these should also be regarded as the present invention. The scope of protection, these will not affect the effect of the implementation of the present invention and the practicability of the patent.
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