CN114620937B - Titanium sphene-coated cadmium sulfoselenide pigment and preparation method and application thereof - Google Patents
Titanium sphene-coated cadmium sulfoselenide pigment and preparation method and application thereof Download PDFInfo
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- CN114620937B CN114620937B CN202210314363.7A CN202210314363A CN114620937B CN 114620937 B CN114620937 B CN 114620937B CN 202210314363 A CN202210314363 A CN 202210314363A CN 114620937 B CN114620937 B CN 114620937B
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- PGWFQHBXMJMAPN-UHFFFAOYSA-N ctk4b5078 Chemical compound [Cd].OS(=O)(=O)[Se]S(O)(=O)=O PGWFQHBXMJMAPN-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000000049 pigment Substances 0.000 title claims abstract description 54
- 239000010936 titanium Substances 0.000 title claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002002 slurry Substances 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000000292 calcium oxide Substances 0.000 claims abstract description 33
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 33
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 30
- 239000011521 glass Substances 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000006229 carbon black Substances 0.000 claims abstract description 26
- 210000003298 dental enamel Anatomy 0.000 claims abstract description 25
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 23
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 238000007641 inkjet printing Methods 0.000 claims abstract description 19
- 239000000084 colloidal system Substances 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 239000011669 selenium Substances 0.000 claims abstract description 16
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims abstract description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 8
- JLATXDOZXBEBJX-UHFFFAOYSA-N cadmium(2+);selenium(2-);sulfide Chemical compound [S-2].[Se-2].[Cd+2].[Cd+2] JLATXDOZXBEBJX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 25
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 22
- 239000011268 mixed slurry Substances 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 16
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 14
- 239000001099 ammonium carbonate Substances 0.000 claims description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 14
- 239000011265 semifinished product Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 229910052793 cadmium Inorganic materials 0.000 claims description 11
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 9
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011164 primary particle Substances 0.000 claims description 8
- 230000000903 blocking effect Effects 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- 229910052861 titanite Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- -1 calcium hydroxide Chemical compound 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940009662 edetate Drugs 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 2
- 230000009466 transformation Effects 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 abstract 2
- 239000011247 coating layer Substances 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 238000009283 thermal hydrolysis Methods 0.000 abstract 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001054 red pigment Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
-
- 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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
Abstract
The invention discloses a titanium sphene-coated cadmium sulfoselenide pigment, and a preparation method and application thereof. Firstly, mixing the prepared cadmium chloride solution with the mixed solution of selenium, ammonium sulfide, ammonium fluoride, white carbon black and a dispersing agent according to steps, utilizing the porous structure of the white carbon black to enable the original cadmium selenide particles synthesized by reaction to be adsorbed on the mixed solution to form mixed colloid slurry, then adding quicklime and titanyl sulfate solution into the slurry according to steps, utilizing the exothermic reaction of the quicklime and water and the thermal hydrolysis reaction of the titanyl sulfate solution to form a calcium hydroxide and titanium hydroxide coating layer covering the cadmium selenide sulfide, enabling the cadmium selenide to be transformed into crystals for stabilization by reaction heat, and finally placing the colloid at 600-700 ℃ for further heating to form the titanium sphenite coated cadmium selenide sulfide pigment with 300-600nm. The invention realizes a new technical system of titanium sphene coated cadmium sulfoselenide scarlet pigment for the first time, and widens the application of the cadmium sulfoselenide pigment to the fields of enamel and glass inkjet printing.
Description
Technical Field
The invention belongs to the field of enamel or glass pigment, and in particular relates to a titanium-sphene-coated cadmium selenide sulfide pigment and a preparation method thereof, and the application of the titanium-sphene-coated cadmium selenide pigment is widened to the field of enamel and glass inkjet printing.
Technical Field
The vessels such as ceramics, enamel, glass and the like used in the life of the people are colorful and gorgeous in color, and various high-temperature-resistant inorganic pigments are used for coloring, wherein the bright red pigment is an important ring. Cadmium sulfoselenide is an inorganic pigment with scarlet color, the color vividness and saturation of which can be compared with those of organic pigment, but the cadmium sulfoselenide can be used after being completely wrapped by a thermally stable crystal substance due to the defects of heavy metal cadmium and easy oxidation at the temperature of more than 300-400 ℃. The zirconium silicate crystal coated cadmium sulfoselenide is the only coated red pigment produced industrially at present, and zirconium silicate is a high-temperature-resistant corrosion-resistant crystal substance which can be kept stable at the high temperature of more than 1300 ℃, so that the zirconium silicate coated cadmium sulfoselenide pigment is mainly applied to the traditional ceramic glaze or ceramic with the temperature of more than 1000 DEG CThe field of ink-jet printing, but for the field of enamel or glass at 550-900 ℃, zirconium silicate coated cadmium sulfoselenide pigment is not suitable. The reason is that in enamel or glass products, the requirements on the vividness and saturation of the color are far greater than those of ceramics, so that the use amount of pigment is 50-200% higher than that of ceramics, and a large amount of high-temperature resistant zirconium silicate crystals are added into low-temperature enamel glaze or glass glaze, so that the performance of the low-temperature glaze can be seriously changed, and the glaze cannot be vitrified at 550-900 ℃, so that the glaze has the problems of cracking, chalking, opacifying and the like. Therefore, finding a non-zirconium silicate crystal substance matched with enamel or glass glaze to wrap cadmium sulfoselenide is a key to widening the application field of the wrapped cadmium sulfoselenide bright red pigment. Screening to find titanic sphene (CaTiSiO) 5 ) The crystal is suitable for enamel or glass glaze, has good stability in the glaze at 500-1000 ℃ only, does not influence the basic performance of the glaze, has excellent wrapping effect, and is often used for wrapping and solidifying nuclear waste.
The ink jet printing technology is applied to the surface decoration of the plate enamel and the glass, which is a new technology only appearing in recent years, the performance of the ink jet printing technology on the decoration of the plate enamel and the glass is far superior to that of the traditional screen printing and decal, the ink jet printing technology has the characteristics of high resolution, wide color gamut and high automation, and various designed patterns can be printed on the plate enamel or the glass through a special ink jet printer under the control of a computer program. The ink jet printing technology is to spray special ink drops from a precise spray nozzle densely covered with 10-20 microns of spray holes to color the plate enamel and glass, and the main components of the ink are organic solvent, dispersant, inorganic pigment and glaze. In order to meet the performance requirement of the inkjet printer nozzle and the requirement of long-term storage of ink, the maximum granularity of the glaze and the pigment is required to be smaller than 1 micron, so that the titanium sphene used for enamel or ceramic inkjet printing is coated with cadmium sulfoselenide pigment, the coating is required to be complete, the coating rate is high, and the granularity of the crystal shell is required to be small enough to avoid the problem of precipitation or nozzle blockage in the process of ink preparation. However, the energy required for the formation of such crystals of titanite is inherently much lower than that of zirconium silicate crystals, which provides a precondition for their synthesis of fine grains at low temperatures.
Disclosure of Invention
In order to solve the technical problems, the invention provides a titanium sphene-coated cadmium sulfoselenide bright red pigment, a preparation method and application thereof, wherein a double precipitation coating process is adopted according to the synthesis conditions of each component of the pigment and the chemical properties of raw materials, the synthesis of the titanium sphene-coated cadmium sulfoselenide pigment is realized for the first time, the high activity characteristic of a semi-finished product and the characteristic that the formation temperature of the titanium sphene is lower per se are obtained by utilizing the process, the pigment is synthesized at the low temperature of 600-700 ℃ calcination, the average grain size of crystals is ensured to be 300-600nm, and thus the use requirement of enamel or glass ink-jet printing is met.
The technical scheme of the invention is as follows:
a titanium sphene-coated cadmium sulfoselenide pigment having an average particle size of 300-600nm and a reddish color, comprises titanium sphene (CaTiSiO 5 ) A housing.
The preparation method of the titanite-coated cadmium sulfoselenide pigment adopts a double precipitation coating process, and specifically comprises the following steps:
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 0.5-2 mol/L;
(2) In a molar ratio of SiO 2 :Se:NH 4 S:NH 4 F, mixing and dissolving white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and dispersing agent to form mixed slurry, wherein Cd= (2-5): (0.05-0.25): (1.0-1.1): (0.1-0.25): 1;
(3) Dripping the cadmium chloride solution obtained in the step (1) into the mixed slurry obtained in the step (2) to react cadmium, sulfur and selenium to generate 10-40 nm cadmium sulfoselenide primary particles, adsorbing the cadmium sulfoselenide primary particles by white carbon black, and utilizing the porous property of the white carbon black to enable the cadmium sulfoselenide primary particles to be adsorbed on the white carbon black to form the mixed slurry of the cadmium sulfoselenide and the white carbon black, wherein in the dripping process, the mixed slurry obtained in the step (2) is required to be kept in a stirring state, and the dripping speed is controlled to be 0.4-0.8 m 3 /h；
(4) According to the mole ratio of CaO to SiO 2 Uniformly and slowly scattering quicklime powder, namely calcium oxide, into the mixed slurry obtained in the step (3) and ensuring that the slurry is always in a stirring state, wherein the ratio of the calcium oxide to the mixed slurry is =1:1The calcium hydroxide reacts with water to form slaked lime, namely calcium hydroxide, and reacts with ammonium fluoride to form calcium fluoride, the calcium hydroxide is crosslinked with white carbon black adsorbed with cadmium sulfoselenide in the forming process, so that the cadmium sulfoselenide has cladding and blocking effects, the calcium fluoride is used as a mineralizer to promote titanium sphene crystallization during subsequent calcination, the heat generated by the reaction can promote the original cadmium sulfoselenide to be crystallized, the cadmium sulfoselenide is not easy to grow during high-temperature crystallization due to the blocking effect of the calcium hydroxide, and the adding speed of the calcium hydroxide is controlled to be 1-5 g/s;
(5) In a molar ratio of Ti to SiO 2 Preparing titanyl sulfate solution with the concentration of 0.5-2.0 mol/L by the ratio of (1:1);
(6) Preparing ammonium carbonate solution with the concentration of 0.1-0.5 mol/L;
(7) Dripping the titanyl sulfate solution obtained in the step (5) into the slurry obtained in the step (4), wherein in the dripping process, the slurry is required to be in a stirring state, the temperature is not lower than 90 ℃, stirring and heating are continued for 2-4 hours after the titanyl sulfate solution is dripped, in the process, the titanyl sulfate is automatically hydrolyzed in hot water to form titanium hydroxide which is attached to the surface of calcium hydroxide in the slurry, cadmium selenide is secondarily coated, acid is generated during the hydrolysis of the titanyl sulfate, and meanwhile, the ammonium carbonate solution prepared in the step (6) is dripped into the slurry to maintain the pH value of the whole slurry to be more than 7;
(8) Continuously baking the slurry obtained in the step (7) for 24-48 h at 150-200 ℃ by using an oven to drain the water content in the slurry to below 0.5%, so as to form high-activity amorphous colloidal semi-finished product dry material, and removing most of ammonium salt in the colloid under long-time high-temperature baking;
(9) Continuously calcining the colloid semi-finished product obtained in the step (8) for 2-4 hours at 600-700 ℃ by using a kiln, gradually forming titanium sphene crystals by using amorphous calcium hydroxide, titanium hydroxide and white carbon black mixed colloid under the action of calcium fluoride, solidifying the cadmium sulfoselenide color-forming core coated in the colloid, and finally forming the titanium sphene-coated cadmium sulfoselenide pigment.
Further, in the step (2), the concentration of the ammonium sulfide is 0.5-2.0 mol/L, the dispersing agent is one or more than two of thioglycollic acid, mercaptopropionic acid, diethanolamine, triethanolamine, ammonium citrate, ammonium oxalate and ammonium edetate, and the use amount of the dispersing agent is 10-100% of the mass of selenium.
Further, in the steps (3), (4) and (7), the stirring speed is 200-800 r/min, namely, the rapid stirring state is maintained.
The titanite obtained by the preparation method wraps cadmium sulfoselenide pigment, and the average granularity of the powder is 300-600nm.
The titanium sphene-coated cadmium sulfoselenide pigment can be used in enamel or glass inkjet printing.
The invention has the beneficial effects that:
the invention adopts a double precipitation coating process, realizes a new technical system of coating cadmium selenide red pigment with titanium trabecite for the first time, and widens the application of the cadmium selenide pigment to the fields of enamel and glass inkjet printing. In the invention, in the stage of synthesizing cadmium sulfoselenide, the dispersing agent blocking function is utilized to keep the cadmium sulfoselenide in the state of original particles of 10-40 nm without growing up, meanwhile, the white carbon black porous adsorption function is utilized to fix the cadmium sulfoselenide original particles to prevent subsequent agglomeration, then calcium hydroxide formed by the reaction of quicklime and water is utilized to carry out first coating on the cadmium sulfoselenide, and then titanium oxysulfate hydrolysis reaction is utilized to carry out second coating, so that the raw materials form a coating structure in the stage of semi-finished products, and finally, the titanium sphene-coated cadmium sulfoselenide scarlet pigment is prepared by low-temperature calcination below 700 ℃. The semi-finished product synthesized by the process has the characteristics of high activity and low requirement on the crystallization energy of the titanite, and the average granularity of the pigment synthesized by low-temperature calcination is 300-600nm, and the maximum granularity can be less than 900nm, so that the process completely meets the requirements of enamel and glass ink-jet printing. In addition, in the preparation method of the invention, cadmium sulfoselenide is coated by calcium hydroxide and titanium hydroxide colloid in the semi-finished product stage, so that the coating rate of the cadmium sulfoselenide is close to 100% when the titanium sphene is finally crystallized and formed, the high content of the color development core (cadmium sulfoselenide) of the coating pigment is ensured, and the cadmium sulfoselenide has stronger red saturation and coloring capability than the cadmium sulfoselenide pigment coated by zirconium silicate in low-temperature glaze such as enamel or glass glaze.
Drawings
FIG. 1 is a particle size distribution diagram of the product obtained in example 1.
FIG. 2 is a particle size distribution diagram of the product obtained in example 2.
FIG. 3 is a particle size distribution diagram of the product obtained in example 3.
FIG. 4 is a particle size distribution diagram of the product obtained in example 4.
FIG. 5 is a particle size distribution diagram of the product obtained in the comparative example.
FIG. 6 is a transmission electron microscope image of the product obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited thereto.
Example 1
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 1mol/L;
(2) In a molar ratio of SiO 2 :Se:NH 4 S:NH 4 Mixing and dissolving white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and a dispersing agent in a ratio of Cd=2:0.2:1:0.2:1 to form mixed slurry, wherein the concentration of the ammonium sulfide is 1mol/L, the dispersing agent is mercaptopropionic acid, and the dosage is 10% of the mass of selenium;
(3) Dripping the cadmium chloride solution obtained in the step (1) into the mixed slurry obtained in the step (2), and keeping the solution obtained in the step (2) in a rapid stirring state in the dripping process, wherein the dripping speed is controlled to be 0.4m 3 /h；
(4) According to the mole ratio of CaO to SiO 2 Uniformly and slowly scattering quicklime powder, namely calcium oxide, into the slurry obtained in the step (3), and ensuring that the slurry is always in a rapid stirring state, wherein the adding speed of quicklime is controlled to be 1g/s;
(5) In a molar ratio of Ti to SiO 2 Preparing an aqueous titanyl sulfate solution with the concentration of 1mol/L by the ratio of 1:1;
(6) Preparing an ammonium carbonate aqueous solution with the concentration of 0.5mol/L;
(8) Dripping the titanyl sulfate solution prepared in the step (5) into the slurry obtained in the step (4), wherein the slurry is in a rapid stirring state in the dripping process, the temperature is higher than 90 ℃, after the titanyl sulfate solution is completely dripped, stirring and heating are continued for 2 hours, and meanwhile, the ammonium carbonate solution prepared in the step (7) is dripped into the slurry, so that the pH of the whole slurry is maintained to be more than 7;
(9) Continuously baking the slurry obtained in the step (8) for 24 hours at 150 ℃ by using an oven;
(10) Continuously calcining the colloid semi-finished product obtained in the step (9) for 2 hours at 700 ℃ by using a kiln to finally prepare the titanium sphene-coated cadmium sulfoselenide scarlet pigment for enamel or glass ink-jet printing.
Example 2
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 1mol/L;
(2) In a molar ratio of SiO 2 :Se:NH 4 S:NH 4 Mixing and dissolving white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and a dispersing agent in a ratio of Cd=2:0.2:1:0.2:1 to form mixed slurry, wherein the concentration of the ammonium sulfide is 1mol/L, and the dispersing agent is triethanolamine and ammonium citrate, and the dosage of the dispersing agent is 5% of the mass of selenium respectively;
(3) Dripping the cadmium chloride solution obtained in the step (1) into the mixed slurry obtained in the step (2), and keeping the solution obtained in the step (2) in a rapid stirring state in the dripping process, wherein the dripping speed is controlled to be 0.4m 3 /h；
(4) According to the mole ratio of CaO to SiO 2 Uniformly and slowly scattering quicklime powder, namely calcium oxide, into the slurry obtained in the step (3), and ensuring that the slurry is always in a rapid stirring state, wherein the adding speed of quicklime is controlled to be 1g/s;
(5) In a molar ratio of Ti to SiO 2 Preparing an aqueous titanyl sulfate solution with the concentration of 1mol/L by the ratio of 1:1;
(6) Preparing an ammonium carbonate aqueous solution with the concentration of 0.5mol/L;
(8) Dripping the titanyl sulfate solution prepared in the step (5) into the slurry obtained in the step (4), wherein the slurry is in a rapid stirring state in the dripping process, the temperature is higher than 90 ℃, after the titanyl sulfate solution is completely dripped, stirring and heating are continued for 2 hours, and meanwhile, the ammonium carbonate solution prepared in the step (7) is dripped into the slurry, so that the pH of the whole slurry is maintained to be more than 7;
(9) Continuously baking the slurry obtained in the step (8) for 24 hours at 150 ℃ by using an oven;
(10) Continuously calcining the colloid semi-finished product obtained in the step (9) for 2 hours at 700 ℃ by using a kiln to finally prepare the titanium sphene-coated cadmium sulfoselenide scarlet pigment for enamel or glass ink-jet printing.
Example 3
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 1mol/L;
(2) In a molar ratio of SiO 2 :Se:NH 4 S:NH 4 Mixing white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and a dispersing agent in a ratio of Cd=2:0.2:1:0.2:1 to form mixed slurry, wherein the concentration of the ammonium sulfide is 1mol/L, the dispersing agent is triethanolamine and ammonium citrate, and the dosage is 10% of the mass of selenium;
(3) Dripping the cadmium chloride solution obtained in the step (1) into the mixed slurry obtained in the step (2), and keeping the solution obtained in the step (2) in a rapid stirring state in the dripping process, wherein the dripping speed is controlled to be 0.4m 3 /h；
(4) According to the mole ratio of CaO to SiO 2 Uniformly and slowly scattering quicklime powder, namely calcium oxide, into the slurry obtained in the step (3), and ensuring that the slurry is always in a rapid stirring state, wherein the adding speed of quicklime is controlled to be 1g/s;
(5) In a molar ratio of Ti to SiO 2 Preparing an aqueous titanyl sulfate solution with the concentration of 1mol/L by the ratio of 1:1;
(6) Preparing an ammonium carbonate aqueous solution with the concentration of 0.5mol/L;
(8) Dripping the titanyl sulfate solution prepared in the step (5) into the slurry obtained in the step (4), wherein the slurry is in a rapid stirring state in the dripping process, the temperature is higher than 90 ℃, after the titanyl sulfate solution is completely dripped, stirring and heating are continued for 2 hours, and meanwhile, the ammonium carbonate solution prepared in the step (7) is dripped into the slurry, so that the pH of the whole slurry is maintained to be more than 7;
(9) Continuously baking the slurry obtained in the step (8) for 24 hours at 150 ℃ by using an oven;
(10) Continuously calcining the colloid semi-finished product obtained in the step (9) for 4 hours at 600 ℃ by using a kiln to finally prepare the titanium sphene-coated cadmium sulfoselenide scarlet pigment for enamel or glass ink-jet printing.
Example 4
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 1mol/L;
(2) In a molar ratio of SiO 2 :Se:NH 4 S:NH 4 F:Cd=4:0.2:1:0.1:1, mixing white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and a dispersing agent to form mixed slurry, wherein the concentration of the ammonium sulfide is 1mol/L, the dispersing agent is mercaptopropionic acid, and the dosage is 10% of the mass of selenium;
(3) Dripping the cadmium chloride solution obtained in the step (1) into the mixed slurry obtained in the step (2), and keeping the solution obtained in the step (2) in a rapid stirring state in the dripping process, wherein the dripping speed is controlled to be 0.4m 3 /h；
(4) According to the mole ratio of CaO to SiO 2 Uniformly and slowly scattering quicklime powder, namely calcium oxide, into the slurry obtained in the step (3), and ensuring that the slurry is always in a rapid stirring state, wherein the adding speed of quicklime is controlled to be 1g/s;
(5) In a molar ratio of Ti to SiO 2 Preparing an aqueous titanyl sulfate solution with the concentration of 1mol/L by the ratio of 1:1;
(6) Preparing an ammonium carbonate aqueous solution with the concentration of 0.5mol/L;
(8) Dripping the titanyl sulfate solution prepared in the step (5) into the slurry obtained in the step (4), wherein the slurry is in a rapid stirring state in the dripping process, the temperature is higher than 90 ℃, after the titanyl sulfate solution is completely dripped, stirring and heating are continued for 2 hours, and meanwhile, the ammonium carbonate solution prepared in the step (7) is dripped into the slurry, so that the pH of the whole slurry is maintained to be more than 7;
(9) Continuously baking the slurry obtained in the step (8) for 24 hours at 150 ℃ by using an oven;
(10) Continuously calcining the colloid semi-finished product obtained in the step (9) for 4 hours at 600 ℃ by using a kiln to finally prepare the titanium sphene-coated cadmium sulfoselenide scarlet pigment for enamel or glass ink-jet printing.
Comparative example
The comparative example used a ceramic inkjet zirconium silicate coated cadmium sulfoselenide pigment commercially available from Jiangxi gold ring pigment Inc.
The pigments obtained in examples 1 to 4 and the comparative example pigment were subjected to particle size detection by a laser particle sizer, and then prepared into a red ink for glass inkjet printing, which was printed onto tempered glass by a special glass inkjet machine, calcined and cured, and the color effect was detected by a color difference meter, and the coating state of individual particles of the pigment of example 3 was scanned by a transmission electron microscope. The following are test results:
test Performance data summary of the package pigments obtained in the examples
| Particle size D50 | Particle size D97 | L* | a* | b* | Glass surface state | |
| Example 1 | 625nm | 659nm | 41.5 | 57.0 | 26.6 | Transparent and transparent |
| Example 2 | 574nm | 773nm | 39.5 | 56.8 | 22.3 | Transparent and transparent |
| Example 3 | 468nm | 651nm | 40.1 | 55.6 | 24.8 | Transparent and transparent |
| Example 4 | 362nm | 516nm | 45.5 | 39.2 | 23.6 | Transparent and transparent |
| Comparative example | 682nm | 1641nm | 71.0 | 21.7 | 13.2 | Opacifying |
As can be seen from the test results of examples 1 to 4 and comparative examples, the enamel and glass ink-jet printing titanium sphene coated cadmium sulfoselenide scarlet pigment prepared by the invention has great advantages in the aspects of granularity, color and glass surface state compared with the comparative example zirconium silicate coated cadmium sulfoselenide scarlet pigment: the maximum particle size D97 of the four example pigments is less than 1000nm, the comparative example pigments reach 1641nm, the redness value a of the four example pigments exceeds 35 in color, the appearance is bright red and transparent, the comparative example pigments a are only 21.7, the appearance is opalescent pink, which is caused by mismatching of the melting points of zirconium silicate and glass glaze, and the titanite has no such defects. Furthermore, it is known from the differences of the pigments of examples 1 to 4 that by adjusting the dispersant combinations, the initial conditions of the formulation, the calcination temperature, products having different particle sizes and color development can be obtained to meet the needs of different customers.
Claims (5)
1. The titanium sphene coated cadmium sulfoselenide pigment is characterized in that: the average particle size of the powder of the pigment is 300-600nm, and the pigment has a bright red color and a titanite shell;
the preparation method of the titanium sphene coated cadmium sulfoselenide pigment adopts a double precipitation coating process, and specifically comprises the following steps:
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 0.5-2 mol/L;
(2) Mixing white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and a dispersing agent to form mixed slurry;
(3) Under the condition of rapid stirring, the cadmium chloride solution obtained in the step (1) is dripped into the mixed slurry obtained in the step (2), and the molar ratio of SiO is calculated 2 :Se:NH 4 S:NH 4 F, cd= (2-5): 0.05-0.25): 1.0-1.1): 0.1-0.25): 1, and drop acceleration is controlled to be 0.4-0.8 m 3 Reacting cadmium, sulfur and selenium to generate 10-40 nm cadmium sulfoselenide primary particles, and adsorbing the cadmium sulfoselenide primary particles by using white carbon black to enable the cadmium sulfoselenide primary particles to be adsorbed on the white carbon black to form mixed slurry of the cadmium sulfoselenide and the white carbon black;
(4) According to the mole ratio of CaO to SiO 2 Under the condition of rapid stirring, uniformly and slowly scattering quicklime powder, namely calcium oxide, into the mixed slurry obtained in the step (3), reacting quicklime with water to form slaked lime, namely calcium hydroxide, reacting with ammonium fluoride to form calcium fluoride, wherein the calcium hydroxide is crosslinked with white carbon black adsorbed with cadmium sulfoselenide in the forming process, so that the cadmium sulfoselenide has coating and blocking effects, the calcium fluoride is used as a mineralizer to promote titanium sphene crystallization during subsequent calcination, the heat generated by the reaction can promote the original cadmium sulfoselenide to turn into red, the cadmium sulfoselenide is not easy to grow during high-temperature crystal transformation due to the blocking effect of the calcium hydroxide, and the adding speed of the quicklime is controlled to be 1-5 g/s;
(5) In a molar ratio of Ti to SiO 2 The =1:1 formulation concentration was 0.5 to 2.0mol/L of titanyl sulfate solution;
(6) Preparing ammonium carbonate aqueous solution with the concentration of 0.1-0.5 mol/L;
(7) Dripping the titanyl sulfate solution obtained in the step (5) into the slurry obtained in the step (4), wherein the slurry is in a rapid stirring state and the temperature is not lower than 90 ℃ in the dripping process, and after the titanyl sulfate solution is completely dripped, continuously stirring and heating for 2-4 hours, wherein in the process, the titanyl sulfate is automatically hydrolyzed in hot water to form titanium hydroxide which is attached to the surface of calcium hydroxide in the slurry, and cadmium selenide is secondarily coated, acid is generated during the hydrolysis of the titanyl sulfate, and meanwhile, the ammonium carbonate solution prepared in the step (6) is dripped into the slurry to maintain the pH value of the whole slurry to be more than 7;
(8) Continuously baking the slurry obtained in the step (7) for 24-48 h at 150-200 ℃ by using an oven to drain the water in the slurry to below 0.5% to form high-activity amorphous colloidal semi-finished product dry material;
(9) Continuously calcining the colloid semi-finished product obtained in the step (8) for 2-4 hours at 600-700 ℃ by using a kiln, gradually forming titanium sphene crystals by using amorphous calcium hydroxide, titanium hydroxide and white carbon black mixed colloid under the action of calcium fluoride, solidifying the cadmium sulfoselenide color-forming core coated in the colloid, and finally forming the titanium sphene-coated cadmium sulfoselenide pigment.
2. The method for preparing the titanium sphene-coated cadmium sulfoselenide pigment according to claim 1, which is characterized by adopting a double precipitation coating process, and specifically comprises the following steps:
(1) Preparing a cadmium chloride aqueous solution, wherein the concentration of cadmium is 0.5-2 mol/L;
(2) Mixing white carbon black, selenium powder, ammonium sulfide, ammonium fluoride and a dispersing agent to form mixed slurry;
(3) Under the condition of rapid stirring, the cadmium chloride solution obtained in the step (1) is dripped into the mixed slurry obtained in the step (2), and the molar ratio of SiO is calculated 2 :Se:NH 4 S:NH 4 F, cd= (2-5): 0.05-0.25): 1.0-1.1): 0.1-0.25): 1, and drop acceleration is controlled to be 0.4-0.8 m 3 Reacting cadmium, sulfur and seleniumForming 10-40 nm cadmium selenide sulfide primary particles, and adsorbing the cadmium selenide sulfide primary particles on the white carbon black by using the white carbon black to form mixed slurry of the cadmium selenide sulfide and the white carbon black;
(4) According to the mole ratio of CaO to SiO 2 Under the condition of rapid stirring, uniformly and slowly scattering quicklime powder, namely calcium oxide, into the mixed slurry obtained in the step (3), reacting quicklime with water to form slaked lime, namely calcium hydroxide, reacting with ammonium fluoride to form calcium fluoride, wherein the calcium hydroxide is crosslinked with white carbon black adsorbed with cadmium sulfoselenide in the forming process, so that the cadmium sulfoselenide has coating and blocking effects, the calcium fluoride is used as a mineralizer to promote titanium sphene crystallization during subsequent calcination, the heat generated by the reaction can promote the original cadmium sulfoselenide to turn into red, the cadmium sulfoselenide is not easy to grow during high-temperature crystal transformation due to the blocking effect of the calcium hydroxide, and the adding speed of the quicklime is controlled to be 1-5 g/s;
(5) In a molar ratio of Ti to SiO 2 Preparing titanyl sulfate solution with the concentration of 0.5-2.0 mol/L by the ratio of (1:1);
(6) Preparing ammonium carbonate aqueous solution with the concentration of 0.1-0.5 mol/L;
(7) Dripping the titanyl sulfate solution obtained in the step (5) into the slurry obtained in the step (4), wherein the slurry is in a rapid stirring state and the temperature is not lower than 90 ℃ in the dripping process, and after the titanyl sulfate solution is completely dripped, continuously stirring and heating for 2-4 hours, wherein in the process, the titanyl sulfate is automatically hydrolyzed in hot water to form titanium hydroxide which is attached to the surface of calcium hydroxide in the slurry, and cadmium selenide is secondarily coated, acid is generated during the hydrolysis of the titanyl sulfate, and meanwhile, the ammonium carbonate solution prepared in the step (6) is dripped into the slurry to maintain the pH value of the whole slurry to be more than 7;
(8) Continuously baking the slurry obtained in the step (7) for 24-48 h at 150-200 ℃ by using an oven to drain the water in the slurry to below 0.5% to form high-activity amorphous colloidal semi-finished product dry material;
(9) Continuously calcining the colloid semi-finished product obtained in the step (8) for 2-4 hours at 600-700 ℃ by using a kiln, gradually forming titanium sphene crystals by using amorphous calcium hydroxide, titanium hydroxide and white carbon black mixed colloid under the action of calcium fluoride, solidifying the cadmium sulfoselenide color-forming core coated in the colloid, and finally forming the titanium sphene-coated cadmium sulfoselenide pigment.
3. The method for preparing the titanium sphene-coated cadmium selenide pigment according to claim 2, wherein in the step (2), the dispersing agent is one or more of thioglycollic acid, mercaptopropionic acid, diethanolamine, triethanolamine, ammonium citrate, ammonium oxalate and ammonium edetate, and the dosage is 10-100% of the mass of selenium.
4. The method for preparing a titanium sphene-coated cadmium sulfoselenide pigment according to claim 2, wherein the concentration of the ammonium sulfide in the step (2) is 0.5 to 2.0mol/L.
5. The use of the titanium sphene-coated cadmium sulfoselenide pigment of claim 1 in enamel or glass inkjet printing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US1983151A (en) * | 1934-07-18 | 1934-12-04 | Silverman Alexander | Coloring agents for glass batches and method of employing same |
| CN108276805A (en) * | 2018-01-31 | 2018-07-13 | 江西金环颜料有限公司 | A kind of ceramic ink jet printing or ceramic dry-mixed zirconium silicate package cadmium sulfoselenide pigment and preparation method thereof |
| CN112409823A (en) * | 2020-11-21 | 2021-02-26 | 广东道氏技术股份有限公司 | Hydrothermal preparation method of mullite coated particles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1983151A (en) * | 1934-07-18 | 1934-12-04 | Silverman Alexander | Coloring agents for glass batches and method of employing same |
| CN108276805A (en) * | 2018-01-31 | 2018-07-13 | 江西金环颜料有限公司 | A kind of ceramic ink jet printing or ceramic dry-mixed zirconium silicate package cadmium sulfoselenide pigment and preparation method thereof |
| CN112409823A (en) * | 2020-11-21 | 2021-02-26 | 广东道氏技术股份有限公司 | Hydrothermal preparation method of mullite coated particles |
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