CN111039300B - Simple, green and safe method for hydro-thermal synthesis of Chinese purple pigment - Google Patents
Simple, green and safe method for hydro-thermal synthesis of Chinese purple pigment Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 17
- 239000001057 purple pigment Substances 0.000 title claims abstract description 15
- 240000006688 Telosma cordata Species 0.000 claims abstract description 35
- 235000017352 Telosma cordata Nutrition 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000049 pigment Substances 0.000 claims abstract description 26
- 239000005751 Copper oxide Substances 0.000 claims abstract description 25
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 21
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 159000000009 barium salts Chemical class 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims description 31
- 239000000725 suspension Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000011049 filling Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000004111 Potassium silicate Substances 0.000 claims description 4
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 4
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical group [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 3
- 229910001626 barium chloride Inorganic materials 0.000 claims description 3
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 229910052788 barium Inorganic materials 0.000 abstract description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 239000010703 silicon Substances 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 abstract description 4
- 239000006184 cosolvent Substances 0.000 abstract description 2
- 150000002611 lead compounds Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 19
- -1 polytetrafluoroethylene Polymers 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 239000000843 powder Substances 0.000 description 10
- IGDGIZKERQBUNG-UHFFFAOYSA-N [Cu].[Ba] Chemical compound [Cu].[Ba] IGDGIZKERQBUNG-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000002745 absorbent Effects 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000013049 sediment Substances 0.000 description 8
- 238000010583 slow cooling Methods 0.000 description 8
- 239000006228 supernatant Substances 0.000 description 8
- 239000012856 weighed raw material Substances 0.000 description 8
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- PWHCIQQGOQTFAE-UHFFFAOYSA-L barium chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Ba+2] PWHCIQQGOQTFAE-UHFFFAOYSA-L 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 238000005245 sintering Methods 0.000 description 5
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 description 5
- 229910052916 barium silicate Inorganic materials 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910020451 K2SiO3 Inorganic materials 0.000 description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 description 2
- 241000530268 Lycaena heteronea Species 0.000 description 2
- 229910003243 Na2SiO3·9H2O Inorganic materials 0.000 description 2
- 241000907663 Siproeta stelenes Species 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- MFEVGQHCNVXMER-UHFFFAOYSA-L 1,3,2$l^{2}-dioxaplumbetan-4-one Chemical compound [Pb+2].[O-]C([O-])=O MFEVGQHCNVXMER-UHFFFAOYSA-L 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910016064 BaSi2 Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910000003 Lead carbonate Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
Images
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- 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
- C09C1/28—Compounds of silicon
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the technical field of Chinese violet preparation, and particularly relates to a simple, green and safe method for hydro-thermally synthesizing Chinese violet pigment, which comprises the steps of adding water-soluble barium salt, copper oxide, water-soluble silicate and deionized water into a closed container, carrying out hydro-thermal reaction at 150-190 ℃, and cooling to 40-60 ℃ after the reaction to obtain a target product. The method adopts cheap and easily available silicon source, barium source and copper source, magnetically stirs at normal temperature, and can prepare the Chinese purple pigment with bright color, high purity and good crystallinity at a lower temperature of below 190 ℃ and especially at 160 ℃ by one step by using a reaction kettle, and the Chinese purple pigment can be used as a text repair material. XRD tests show that the pigment characteristic peak has good crystallinity and high strength. The method for preparing the Chinese violet has low reaction temperature, does not need to add lead compounds and other cosolvents, does not need to adjust the pH value (pH value), and has simpler and more environment-friendly process.
Description
Technical Field
The invention belongs to the technical field of Chinese violet preparation, and particularly relates to a simple, green and safe method for hydro-thermally synthesizing Chinese violet pigment.
Background
Chinese violet (BaCuSi)2O6) Is one of copper barium silicate pigments, is one of the great creations of Chinese ancestors, is a representative of ancient scientific and technical level of China, and in 1983 and 1992, blue copper barium silicate and purple copper barium silicate are found on colored drawing pottery and octahedral rods in Han dynasty by Elisabeth West FitzHugh in UK, and are named as Han blue and Han purple respectively. The scholars of China also found the barium copper silicate pigment in the cultural relics samples from spring, autumn and Han dynasties such as color-painted pottery, glassware, octagonal prism, wall painting and pottery figurines which come out of earth in provinces such as Gansu, Shaanxi, Shandong, Henan and Jiangsu, and most scholars call Chinese purple (BaCuSi)2O6) Chinese blue (BaCuSi)4O10) Chinese dark blue (BaCu)2Si2O7). Foreign scholars found corresponding natural minerals of Chinese blue and Chinese violet in mineral deposits of south Africa in 1985 and 2015, respectively, but artificially synthesized barium copper silicate was found only in China, and most of the barium copper silicate was found in Chinese violet. The preparation of the Chinese purple pigment not only can provide help for the repair and academic research of related ancient cultural relics, but also finds that the Chinese purple pigment is a near-infrared luminescent material and hasThe property of converting visible light into near infrared light (aged rock, von gecko) and the near infrared luminescent material are widely applied to a plurality of fields of medical diagnosis, information storage, laser communication, anti-counterfeiting identification and the like (in 2017, Zhang Wen, manganese-doped near infrared luminescent material is designed and synthesized and the spectral performance is researched), so that the Chinese purple pigment has good application prospect.
For the simulation preparation research, the scholars combine the cultural relic analysis information and the chemical formula of the barium copper silicate to propose different simulation preparation methods, most of which mainly use solid-phase sintering, such as Heinz Berke proposes using copper sulfide, blue copper ore and malachite as mineral sources, silica (quartz or sand) as silicon sources, barium sulfate or barium carbonate as barium sources, adding lead carbonate or lead oxide to reduce the melting temperature of the barium sulfate, and sintering at 1000 ℃; in the Zhang Guogong in 2012, barium oxide, barium carbonate or barium sulfate is used as a barium source, lime or copper oxide is used as a copper source, silicon dioxide is used as a silicon source, lead oxide is added as a fluxing agent, and Chinese violet is fired at the temperature of 900-; the Qinying uses natural quartz, black copper ore or malachite, witherite as raw material, and prepares Chinese purple at 1050 deg.C. Although the copper barium silicate is prepared by the preparation schemes, the used barium source and fluxing agent lead oxide are harmful to the environment or human body, the final calcining temperature is high, the energy consumption is high, and the final product contains Cu2O、BaSi2O5、SiO2And the like, so that the Chinese violet with higher purity cannot be prepared.
With the development and application of hydrothermal synthesis technology, BaCl is obtained by aged rock and the like2·4H2O、Na2SiO3·9H2Mixing O and CuO powder with distilled water, adjusting pH to 11 with HCl, placing into a reaction kettle, heating to 250 deg.C, reacting for 48 hr, cooling to room temperature, at which pH is 11.5, adding NH4Cl was reacted at 60 ℃ for 24 hours to remove impurities from the reaction product, and finally the product was collected by drying. Zhang Chawu et al combines hydrothermal synthesis with solid phase sintering, called coprecipitation hydrothermal method, and carries out hydrothermal autoclave reaction at 160-180 ℃ to prepare barium copper silicate prepolymer, and finally sintering at 650-750 DEG C. The two preparation schemes can obtain Chinese violet with bright color and high purity, however, the first scheme has high preparation temperature, long experimental period and high requirement on experimental equipment, and although the method of Zhang-Chawu et al reduces the experimental temperature, the experimental process is more complex and is not beneficial to operation, so that a more economic, safe, green and simple and convenient Chinese violet preparation method needs to be found.
Disclosure of Invention
The invention aims to provide a simple, green and safe method for hydrothermally synthesizing a Chinese purple pigment, and solves the technical problem of synthesizing the Chinese purple pigment with high purity and high crystallinity by using an analytically pure oxide and inorganic salt safely, economically and greenly and easily.
The realization process of the invention is as follows:
a simple, green and safe method for hydro-thermally synthesizing Chinese violet pigment is characterized by adding water-soluble barium salt, copper oxide, water-soluble silicate and deionized water into a closed container, carrying out hydro-thermal reaction at 150-190 ℃, and cooling to 40-60 ℃ after the reaction to obtain a target product.
The method for hydrothermally synthesizing the Chinese violet pigment comprises the following steps:
(1) weighing water-soluble barium salt, copper oxide and water-soluble silicate;
(2) under the condition of stirring, adding the raw materials weighed in the step (1) into deionized water, and mixing to obtain a suspension;
(3) and (3) placing the suspension obtained in the step (2) into a closed reaction kettle, carrying out hydrothermal reaction at 160-180 ℃ for 12-72 hours, cooling to 45-55 ℃ after reaction, standing, washing and drying to obtain a target product.
Further, the degree of filling of the closed reaction kettle is more than 81%.
Further, the water-soluble barium salt is barium chloride or barium nitrate; the water-soluble silicate is any one of sodium silicate, lithium silicate and potassium silicate.
Further, the water-soluble barium salt: copper oxide: water-soluble silicate: the deionized water is prepared from (1-1.2): 1: 2: (1000-1110).
Further, the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110.
further, the stirring process in the step (2) is performed at room temperature.
Further, the temperature of the hydrothermal reaction in the step (3) is 160 ℃, and the reaction time is 72 hours; the temperature after the temperature reduction in the step (3) is 50 ℃.
Further, the solvent used for washing in the step (3) is absolute ethyl alcohol or deionized water.
Further, the drying in step (3) may be natural drying or vacuum drying.
The mechanism of the invention is analyzed as follows:
the invention belongs to the technical field of hydrothermal synthesis, and particularly relates to an effective method for material synthesis and treatment, which is carried out in a reaction kettle by taking water as a solvent, heating a reaction system and utilizing the self vapor pressure of the water to create a relatively high-temperature high-pressure reaction environment. In the exploration experiment, a polytetrafluoroethylene inner container of 23mL is used, after raw materials and deionized water of 20mL are added, the filling degree of a reaction kettle reaches more than 81%, according to an ideal gas state equation, namely PV ═ nRT, P is gas pressure, V is gas volume, n is the amount of a gas substance, R is an ideal gas constant, and T is the thermodynamic temperature of gas, compared with the prior art, the amount and the temperature of the gas substance are the same, and R is a constant, so that P is relatively enhanced under the condition that V is reduced, and the reaction temperature is relatively reduced, therefore, the high-purity Chinese purple pigment can be obtained by using the reaction temperature of 190 ℃ (especially 160 ℃ -180 ℃).
The invention has the following positive effects:
(1) the method adopts cheap and easily available silicon source, barium source and copper source, magnetically stirs at normal temperature, and can prepare the Chinese purple pigment with bright color, high purity and good crystallinity at a lower temperature of below 190 ℃ and especially at 160 ℃ by one step by using a reaction kettle, and the Chinese purple pigment can be used as a text repair material. XRD tests show that the pigment characteristic peak has good crystallinity and high strength.
(2) In the method, the raw materials for preparing the Chinese violet are selected economically and easily. With Na2SiO3·9H2O、K2SiO3Or Li2SiO3As silicon source, CuO as copper source, and BaCl2·2H2O or Ba (NO)3)2Is a barium source, adopts a convenient and practical hydrothermal synthesis method to prepare the Chinese purple pigment, has green and environment-friendly reaction, low energy and high efficiency, and Na2SiO3·9H2O、K2SiO3Or Li2SiO3Provides ideal alkaline reaction conditions for the solution, and is more beneficial to the preparation of Chinese violet.
(3) Compared with the lowest reaction temperature of more than 250 ℃ required by the prior art, the method disclosed by the invention can be used for reacting for a plurality of hours in a hydrothermal kettle at a lower temperature of only 190 ℃ (especially 160-180 ℃), and the Chinese purple pigment can be obtained after cleaning and drying. The prepared product is bright in color, relatively pure and can be directly used without further impurity removal process, so that the energy consumption is greatly reduced, and the labor and material cost is saved.
(4) Compared with the traditional high-temperature solid phase sintering, the method for preparing the Chinese violet has low reaction temperature, does not need to add lead compounds and other cosolvents, does not need to adjust the pH value (pH value), and has simpler and more environment-friendly process.
Drawings
FIG. 1 shows the hydrothermal synthesis of BaCuSi in example 12O6Scanning electron microscope image of Chinese violet pigment magnified 300 times;
FIG. 2 shows the hydrothermal synthesis of BaCuSi in example 12O6Scanning electron microscope images of Chinese violet pigment magnified 100 times;
FIG. 3 shows the hydrothermal synthesis of BaCuSi in examples 1, 2 and 32O6Macroscopic pictures and XRD test results of the Chinese violet pigment;
FIG. 4 shows the hydrothermal synthesis of BaCuSi in examples 4, 5, 6 and 72O6Macroscopic picture and XRD test result of Chinese violet pigment.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110 g, 0.24428g of barium chloride dihydrate, 0.07960g of copper oxide and 0.56810g of sodium silicate nonahydrate are weighed respectively, the weighed raw material powder is poured into a polytetrafluoroethylene inner container (the volume is 23mL) of a hydrothermal kettle, 20mL of deionized water is added, the filling degree is about 89%, and the mixture is stirred for 30 minutes by magnetic force to be fully mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 72 hours at 160 ℃ by using an air-blast drying oven, and then slowly cooling to 50 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard pattern is relatively consistent, the yield is 83.1%, the scanning electron micrograph of the product is shown in figures 1 and 2, and the XRD map is shown in figure 3.
Example 2
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: weighing 0.26144g of barium nitrate, 0.07974g of copper oxide and 0.56803g of sodium silicate nonahydrate respectively according to the molar ratio of 1000, pouring the weighed raw material powder into a 23mL polytetrafluoroethylene liner (the volume is 23mL) of a hydrothermal kettle, adding 18 mL of deionized water to reach the filling degree of about 81%, and performing magnetic stirring for 40 minutes to fully mix.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 36 hours at 180 ℃ by using an air-blast drying oven, and then slowly cooling to 40 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard pattern is relatively consistent, and the yield is 84.3%. The XRD pattern of the product is shown in FIG. 3.
Example 3
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110 g, 0.24458g of barium chloride dihydrate, 0.07954g of copper oxide and 0.56814g of sodium silicate nonahydrate are weighed respectively, the weighed raw material powder is poured into a polytetrafluoroethylene inner container (the volume is 23mL) of a hydrothermal kettle, 20mL of deionized water is added, the filling degree is about 89%, and the mixture is stirred for 35 minutes by magnetic force to be fully mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 72 hours at 150 ℃ by using an air-blast drying oven, and then slowly cooling to 60 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard pattern is relatively consistent, and the yield is 84.8%. The XRD pattern of the product is shown in FIG. 3.
Example 4
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110 g, 0.24428g of barium chloride dihydrate, 0.07962g of copper oxide and 0.30849g of potassium silicate were weighed, the weighed raw material powders were poured into a polytetrafluoroethylene inner container (23 mL in volume) of a hydrothermal kettle, 20mL of deionized water was added to a degree of filling of about 89%, and the mixture was magnetically stirred for 30 minutes to be sufficiently mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 12 hours at 170 ℃ by using an air-blast drying oven, and then slowly cooling to 45 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard pattern is relatively consistent, and the yield is 85.6%. The XRD pattern of the product is shown in FIG. 4.
Example 5
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110 g, 0.24455g of barium chloride dihydrate, 0.07962g of copper oxide and 0.18051g of lithium silicate were weighed, the weighed raw material powders were poured into a polytetrafluoroethylene inner container (23 mL in volume) of a hydrothermal kettle, 20mL of deionized water was added to a degree of filling of about 88%, and the mixture was magnetically stirred for 30 minutes to be sufficiently mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 24 hours at 160 ℃ by using an air-blast drying oven, and then slowly cooling to 50 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard pattern is relatively consistent, and the yield is 85.3%. The XRD pattern of the product is shown in FIG. 4.
Example 6
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110 g, 0.24427g of raw material powder barium chloride dihydrate, 0.07958g of copper oxide and 0.56833g of sodium silicate nonahydrate are respectively weighed, the weighed raw material powder is poured into a polytetrafluoroethylene inner container (the volume is 23mL) of a hydrothermal kettle, 20mL of deionized water is added, the filling degree is about 90%, and the mixture is magnetically stirred for 30 minutes to be fully mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 48 hours at 170 ℃ by using an air-blast drying oven, and then slowly cooling to 55 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard map is relatively consistent, and the yield is 85.1%. The XRD pattern of the product is shown in FIG. 4.
Example 7
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of deionized water is 1.2: 1: 2: 1000, 0.31361g of barium nitrate, 0.07958g of copper oxide and 0.30867g of potassium silicate are weighed respectively, the weighed raw material powder is poured into a polytetrafluoroethylene inner container (the volume is 23mL) of a hydrothermal kettle, 18 mL of deionized water is added, the filling degree is about 81 percent, and the mixture is stirred for 30 minutes by magnetic force to be fully mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 24 hours at 190 ℃ by using an air-blast drying oven, and then slowly cooling to 55 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with deionized water for several times, naturally drying on absorbent paper, and collecting.
X-ray diffraction pattern and BaCuSi of the product of this example2O6The standard pattern is relatively consistent, and the yield is 85.7%. The XRD pattern of the product is shown in FIG. 4.
Example 8
The simple, green and safe method for hydro-thermally synthesizing the Chinese violet pigment comprises the following steps:
(1) according to the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of deionized water is 1.1: 1: 2: 0.26871g of barium chloride dihydrate, 0.07958g of copper oxide and 0.56823g of sodium silicate nonahydrate are weighed respectively according to the molar ratio of 1050, the weighed raw material powder is poured into a polytetrafluoroethylene inner container (the volume is 23mL) of a hydrothermal kettle, 19 mL of deionized water is added, the filling degree is about 85%, and the mixture is stirred for 30 minutes by magnetic force to be fully mixed.
(2) And (3) putting the fully stirred suspension into a hydrothermal kettle, reacting for 12 hours at 160 ℃ by using an air-blast drying oven, and then slowly cooling to 50 ℃ in the air-blast drying oven.
(3) After the slow cooling is finished, pouring the contents in the polytetrafluoroethylene inner container into a clean beaker, standing and pouring out the supernatant, and leaving the bottom sediment; washing with anhydrous ethanol for several times, placing on absorbent paper, vacuum drying, and collecting. The yield of the product of this example was 84.9%.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the invention to the particular forms disclosed. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (7)
1. A simple, green and safe method for hydro-thermally synthesizing Chinese purple pigment is characterized by comprising the following steps:
(1) weighing water-soluble barium salt, copper oxide and water-soluble silicate;
(2) under the condition of stirring, adding the raw materials weighed in the step (1) into deionized water, and mixing to obtain a suspension;
(3) putting the suspension obtained in the step (2) into a closed reaction kettle, carrying out hydrothermal reaction at 160-180 ℃ for 12-72 hours, cooling to 45-55 ℃ after reaction, standing, washing and drying to obtain a target product;
wherein the water-soluble barium salt is barium chloride or barium nitrate; the water-soluble silicate is any one of sodium silicate, lithium silicate or potassium silicate; the water-soluble barium salt: copper oxide: water-soluble silicate: the deionized water is prepared from (1-1.2): 1: 2: (1000-1110).
2. The method for hydrothermally synthesizing a chinese violet pigment according to claim 1, wherein: the filling degree of the closed reaction kettle is more than 81%.
3. The method for hydrothermally synthesizing a chinese violet pigment according to claim 1, wherein: the water-soluble barium salt: copper oxide: water-soluble silicate: the optimal molar ratio of the deionized water is 1: 1: 2: 1110.
4. the method for hydrothermally synthesizing a chinese violet pigment according to claim 1, wherein: the stirring process in the step (2) is carried out at room temperature.
5. The method for hydrothermally synthesizing a chinese violet pigment according to claim 1, wherein: the temperature of the hydrothermal reaction in the step (3) is 160 ℃, and the reaction time is 72 hours; the temperature after the temperature reduction in the step (3) is 50 ℃.
6. The method for hydrothermally synthesizing a chinese violet pigment according to claim 1, wherein: and (4) the solvent used for washing in the step (3) is absolute ethyl alcohol or deionized water.
7. The method for hydrothermally synthesizing a chinese violet pigment according to claim 1, wherein: the drying in the step (3) may be natural drying or vacuum drying.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103570031A (en) * | 2013-11-14 | 2014-02-12 | 吉林大学 | Method for preparing BaCuSi2O6 and BaCu2Si2O7 pigments through hydrothermal technology |
| CN103601202A (en) * | 2013-11-14 | 2014-02-26 | 吉林大学 | Method for preparing SrCuSi4O10 and BaCuSi4O10 blue pigments through hydrothermal technique |
| CN106379907A (en) * | 2016-08-12 | 2017-02-08 | 陕西科技大学 | Preparation method for purple archaistic ceramic pigment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570031A (en) * | 2013-11-14 | 2014-02-12 | 吉林大学 | Method for preparing BaCuSi2O6 and BaCu2Si2O7 pigments through hydrothermal technology |
| CN103601202A (en) * | 2013-11-14 | 2014-02-26 | 吉林大学 | Method for preparing SrCuSi4O10 and BaCuSi4O10 blue pigments through hydrothermal technique |
| CN106379907A (en) * | 2016-08-12 | 2017-02-08 | 陕西科技大学 | Preparation method for purple archaistic ceramic pigment |
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