CN115286244A - Special gray digital overglaze for ceramic large plate, synthesis method and application - Google Patents
Special gray digital overglaze for ceramic large plate, synthesis method and application Download PDFInfo
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- CN115286244A CN115286244A CN202210837008.8A CN202210837008A CN115286244A CN 115286244 A CN115286244 A CN 115286244A CN 202210837008 A CN202210837008 A CN 202210837008A CN 115286244 A CN115286244 A CN 115286244A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 51
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 239000006229 carbon black Substances 0.000 claims abstract description 97
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001035 drying Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 150
- 239000000243 solution Substances 0.000 claims description 102
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 150000001721 carbon Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 13
- 230000002194 synthesizing effect Effects 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000010669 acid-base reaction Methods 0.000 claims description 4
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 3
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 21
- 239000000049 pigment Substances 0.000 description 16
- 239000007921 spray Substances 0.000 description 10
- 239000003086 colorant Substances 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 230000002572 peristaltic effect Effects 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- -1 octahydrate chlorine zirconium oxide Chemical compound 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002356 laser light scattering Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a special gray digital overglaze for ceramic large plates, a synthesis method and application thereof, comprising the following specific steps: s1: preparing a reaction solution and a carbon black dispersion; s2: dropwise adding the reaction solution into the carbon black dispersion liquid for reaction, and then centrifugally drying to obtain precursor-coated carbon black powder; s3: and (3) calcining the precursor coated carbon black powder, and crushing to obtain a powdery product. The invention has the advantages of simple synthesis process, reasonable design, capability of preparing the gray digital overglaze with stable gray tone and fidelity color and low cost.
Description
Technical Field
The invention relates to the technical field of ceramic digital ink-jet, in particular to a special gray digital overglaze for a ceramic large plate, a synthesis method and application.
Background
With the rise of ceramic ink-jet technology in the ceramic industry in recent years, a plurality of ceramic factories introduce ceramic digital ink-jet printers, and high-end ceramic plates all adopt the digital ink-jet technology to replace the traditional printing process. In 2021, the hot tide of a strand of ceramic large plates and rock plates is raised in the industry, and dozens of large plate production lines are added in China during one year. The definition of the prior industry for the rock plate is not unified, and no matter the blank, the glaze, the toughness, the process or the size, the prior industry has no unified standard, so the prior enterprise is called the rock plate, and the prior enterprise is called the ceramic large plate.
The digital glaze as a solid-liquid mixture replaces pigments, printing oil, printing glaze and other additives, and can directly manufacture the required colors and patterns. The function and effect of the glaze, in contrast, determines that most glazes need to be covered with sufficient area and thickness, and the current glazing process can achieve these requirements precisely and with high adjustability.
However, no digital glaze with stable tone and suitable for ceramic slabs or rock plates has been released in the market. Thus, for the traditional glaze, the gray level and the covering power are difficult to have, and the problems of low coloring quality and distorted pattern gray effect are caused.
Disclosure of Invention
The invention aims to solve the technical problem of providing a special gray digital overglaze for ceramic large plates, a synthesis method and application, and aims to solve the problems in the prior art.
The technical scheme for solving the technical problems is as follows:
a method for synthesizing special gray digital overglaze for ceramic large plates comprises the following steps:
s1: preparing a reaction solution and a carbon black dispersion;
s2: dropwise adding the reaction solution into the carbon black dispersion liquid for reaction, and then centrifugally drying to obtain precursor-coated carbon black powder;
s3: and (3) calcining the precursor coated carbon black powder, and crushing to obtain a powdery product.
On the basis of the technical scheme, the invention can be further improved as follows.
Further: the reaction solution in the step S1 comprises an octahydrate chlorine zirconium oxide solution and a sodium hydroxide solution, and the molar concentration of the sodium hydroxide solution is twice of that of the octahydrate chlorine zirconium oxide solution.
Further, the preparation of the zirconium oxychloride octahydrate solution specifically comprises: weighing the zirconium oxychloride octahydrate according to the mass percentage of 1: (4-10) dissolving in deionized water and stirring to completely dissolve the zirconium oxychloride octahydrate to obtain the zirconium oxychloride octahydrate solution.
Further, the preparation of the sodium hydroxide solution specifically comprises: weighing sodium hydroxide, dissolving the sodium hydroxide in deionized water, and cooling to room temperature after dissolving to obtain a sodium hydroxide solution.
Further, the step S2 includes the following specific steps:
s21: placing the carbon black dispersion liquid into a stirrer to be stirred;
s22: respectively and simultaneously dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid according to the molar ratio of 1 to 2 for reaction, controlling the pH to 8.5-9.5 by virtue of acid-base reaction, stopping dripping the zirconium oxychloride octahydrate solution, continuing dripping the sodium hydroxide solution and stirring for 20-40 minutes, stopping dripping the sodium hydroxide solution, continuing to react until the pH is 9.0, and stopping stirring to obtain a mixed solution;
s23: and stirring the mixed solution to react for 2-8 hours, then centrifugally drying to obtain dispersion liquid with the water content of 5% -10%, and then centrifugally drying to obtain precursor-coated carbon black powder.
Further, the preparation of the carbon black dispersion in S1 comprises the following specific steps:
s11: carrying out modification treatment on carbon black to obtain modified carbon black;
s12: firstly, mixing the modified carbon black according to the mass percent of 1: (20-100) dissolving in deionized water to obtain a carbon black solution, adding a dispersing agent, wherein the dispersing agent accounts for 1-5% of the mass of the carbon black solution, stirring and carrying out ultrasonic treatment for 5-10 minutes; then the mixture is placed in a mixer to react for 2 to 4 hours, and the pH value is adjusted to 3, so that carbon black dispersion liquid is obtained.
Further, the step S3 includes the following specific steps:
s31: mixing the precursor-coated carbon black powder with a mineralizer according to the mass percentage of 1-10%, and placing the mixture in a calcinator, wherein the calcinator is filled with protective gas;
s32: the calcinator is placed at 950-1100 ℃ for calcination for 5-60 minutes;
s33: taking out and crushing to 320-400 meshes to obtain a powdery product.
Further, the mineralizer in S31 is one or more of lithium fluoride, sodium fluoride, potassium fluoride and magnesium fluoride.
The invention also relates to a gray digital overglaze prepared by adopting the synthesis method of the special gray digital overglaze for the ceramic large plate.
The invention also relates to an application of the gray digital overglaze, which is applied to the technical field of ceramics.
The invention has simple synthesis process and reasonable design, can prepare the gray digital overglaze with stable gray tone and fidelity color and has low cost.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a schematic view of a black digital overglaze prepared in the present invention;
FIG. 3 is a schematic view of a black digital overglaze spray plate prepared in the present invention;
FIG. 4 is an electron microscope image of the microstructure of the black digital overglaze prepared in the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings, which are based on the orientations and positional relationships indicated in the drawings, and are used for convenience in describing the present invention and for simplicity in description, but do not indicate or imply that the device or element so referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
As shown in fig. 1 to 4, the present embodiment provides a method for synthesizing a special gray digital overglaze for a ceramic large panel, which includes the following specific steps:
s1: preparing a reaction solution and a carbon black dispersion;
s2: dropwise adding the reaction solution into the carbon black dispersion liquid for reaction, and then centrifugally drying to obtain precursor-coated carbon black powder (coating reaction);
s3: and (3) calcining the precursor coated carbon black powder, and crushing to obtain a powdery product.
The synthesis process of the embodiment is simple, the design is reasonable, the gray digital overglaze with stable gray tone and fidelity color can be prepared, and the cost is low.
Example 2
On the basis of example 1, in this example, the reaction solution in S1 includes a zirconium oxychloride octahydrate solution and a sodium hydroxide solution, and the molar concentration of the sodium hydroxide solution is twice of the molar concentration of the zirconium oxychloride octahydrate solution.
Example 3
In this embodiment, on the basis of embodiment 2, the preparation of the zirconium oxychloride octahydrate solution specifically includes: weighing the zirconium oxychloride octahydrate according to the mass percentage of 1: (4-10) dissolving in deionized water and stirring to completely dissolve the zirconium oxychloride octahydrate, wherein the solution is clear and transparent and has no suspension, and thus the zirconium oxychloride octahydrate solution is obtained.
Example 4
In this embodiment, on the basis of any one of embodiments 2 to 3, the preparation of the sodium hydroxide solution specifically includes: weighing sodium hydroxide, dissolving the sodium hydroxide in deionized water, and cooling to room temperature after dissolving to obtain a sodium hydroxide solution.
Example 5
On the basis of any one of embodiment 2 to embodiment 4, in this embodiment, the step S2 includes the following specific steps:
s21: stirring the carbon black dispersion liquid in a stirrer at the stirring speed of 60-80 revolutions per minute;
s22: respectively and simultaneously dropwise adding the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid according to the molar ratio of 1;
respectively dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid through two peristaltic pumps for reaction, wherein the two solutions of the zirconium oxychloride octahydrate solution and the sodium hydroxide solution are respectively dripped in a droplet shape;
s23: stirring the mixed solution for reaction for 2-8 hours, wherein the stirring speed is 30-60 revolutions per minute; and then centrifugally drying to obtain a dispersion liquid with the water content of 5% -10%, and then centrifugally drying to obtain precursor coated carbon black powder.
Example 6
On the basis of the above embodiments, in this embodiment, the preparation of the carbon black dispersion in S1 includes the following specific steps:
s11: carrying out modification treatment on carbon black to obtain modified carbon black;
s12: firstly, mixing the modified carbon black according to the mass percent of 1: (20-100) dissolving in deionized water to obtain a carbon black solution, adding a dispersing agent, wherein the dispersing agent accounts for 1-5% of the mass of the carbon black solution, stirring and carrying out ultrasonic treatment for 5-10 minutes; then the mixture is placed in a mixer to react for 2 to 4 hours, and the pH value is adjusted to 3, so that carbon black dispersion liquid is obtained.
In the present embodiment, the carbon black is preferably modified carbon black.
Preferably, in this embodiment, the specific steps of modifying the carbon black are as follows:
(1) The concentrated nitric acid and the concentrated sulfuric acid are mixed according to the mass percentage of 1: (20-100) to obtain a mixed modified solution, then adding a proper amount of carbon black into the mixed modified solution, and heating for 10-20 minutes in a water bath at 60-80 ℃ to obtain a mixture of the carbon black and the mixed modified solution with the mass percentage of 1: (2-7), preferably 1;
(2) Filtering, then washing many times, the preface can use running water to wash many times, consequently uses deionized water to wash at last, and the index of washing clean is: the modified carbon black has an electrical conductivity of 300 or less;
(3) And finally, drying in an oven at the temperature of 100-120 ℃ for 30-40 minutes.
Preferably, in the present embodiment, the dispersant is preferably an aqueous dispersant, preferably one of PVP and polyethylene glycol and a mixture thereof.
Preferably, in this embodiment, the particle size D50 of the carbon black after dispersion and ultrasonic treatment should be less than 300nm, preferably less than 150nm. The reason is as follows: the coating reaction in S2 requires that the microscopic particle size of the carbon black is sufficiently small, and the yield of the coating reaction is high.
The carbon black dispersion liquid needs to be prepared as it is.
Example 7
On the basis of the foregoing embodiments, in this embodiment, the S3 includes the following specific steps:
s31: mixing the precursor-coated carbon black powder with a mineralizer according to the mass percentage of 1-10%, preferably 3-5%, and placing the mixture in a calcinator, wherein the calcinator is filled with a protective gas;
s32: calcining the calciner at 950-1100 ℃ for 5-60 minutes, preferably 10-15 minutes;
s33: taking out, pulverizing, preferably ball-milling to 320-400 meshes to obtain a powdery product.
Example 8
In this embodiment, on the basis of embodiment 7, the mineralizer in S31 is one or more of lithium fluoride, sodium fluoride, potassium fluoride, and magnesium fluoride.
Example 9
On the basis of the above embodiments, the present embodiment further provides a gray digital overglaze prepared by the above method for synthesizing a special gray digital overglaze for a ceramic large panel.
The black digital overglaze provided by the embodiment has the advantages of simple synthesis process and reasonable design, can be used for preparing the gray digital overglaze with stable gray tone and fidelity color, and is low in cost.
Example 10
On the basis of the above embodiments, the present embodiment further provides an application of the gray digital overglaze, which is applied to the technical field of ceramics.
The grey digital overglaze provided by the embodiment has the advantages of simple synthesis process and reasonable design, can be used for preparing the grey digital overglaze with stable grey tone and fidelity color, is low in cost, and can be applied to the technical field of ceramics.
The specific embodiment of the invention is as follows:
example 11
(1) Weighing the zirconium oxychloride octahydrate according to the mass percentage of 1:4, dissolving in deionized water and stirring to completely dissolve the zirconium oxychloride octahydrate, wherein the solution is clear, transparent and free of suspension, and thus obtaining a zirconium oxychloride octahydrate solution;
(2) Weighing sodium hydroxide, dissolving the sodium hydroxide in deionized water, and cooling to room temperature after dissolving to obtain a sodium hydroxide solution;
(3) Carrying out modification treatment on carbon black to obtain modified carbon black;
(4) Firstly, mixing the modified carbon black according to the mass percent of 1:20, dissolving the carbon black into deionized water to obtain a carbon black solution, adding a dispersing agent, wherein the dispersing agent accounts for 1% of the mass of the carbon black solution, stirring and carrying out ultrasonic treatment for 5 minutes; then placing the mixture in a mixer to react for 2 hours, and adjusting the pH value to 3 to obtain carbon black dispersion liquid;
(5) Stirring the carbon black dispersion liquid in a stirrer at the stirring speed of 60 revolutions per minute;
(6) Respectively and simultaneously dropwise adding the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid according to the molar ratio of 1 to 2 for reaction, controlling the pH to 8.5 by virtue of acid-base reaction (monitoring by using a high-precision portable pH meter in the prior art), stopping dropwise adding the zirconium oxychloride octahydrate solution, continuing dropwise adding the sodium hydroxide solution and stirring for 20 minutes, then stopping dropwise adding the sodium hydroxide solution, continuing to react until the pH is 9.0, and stopping stirring to obtain a mixed solution;
respectively dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid through two peristaltic pumps for reaction, wherein the two solutions of the zirconium oxychloride octahydrate solution and the sodium hydroxide solution are respectively dripped in a droplet shape;
(7) Stirring the mixed solution for reaction for 2 hours, wherein the stirring speed is 30 revolutions per minute; then, carrying out centrifugal drying to obtain a dispersion liquid with the water content of 5 percent, and then carrying out centrifugal drying to obtain precursor coated carbon black powder;
(8) Mixing the precursor-coated carbon black powder with a mineralizer according to the mass percent of 1-10%, preferably 3-5%, and placing the mixture in a calcinator, wherein the calcinator is filled with a protective gas;
(9) The calcinator is placed at 950 ℃ for calcination for 5 minutes;
(10) Taking out, crushing, preferably ball milling to obtain 320-mesh powder product.
Example 12
(1) Weighing the zirconium oxychloride octahydrate according to the mass percentage of 1:10, dissolving in deionized water and stirring to ensure that the zirconium oxychloride octahydrate is completely dissolved, wherein the solution is clear and transparent without suspension, and thus obtaining a zirconium oxychloride octahydrate solution;
(2) Weighing sodium hydroxide, dissolving the sodium hydroxide in deionized water, and cooling to room temperature after dissolving to obtain a sodium hydroxide solution;
(3) Modifying carbon black to obtain modified carbon black;
(4) Firstly, mixing the modified carbon black according to the mass percent of 1:100, dissolving in deionized water to obtain a carbon black solution, adding a dispersing agent, wherein the dispersing agent accounts for 15% of the mass of the carbon black solution, stirring and performing ultrasonic treatment for 10 minutes; then placing the mixture in a mixer to react for 4 hours, and adjusting the pH value to 3 to obtain carbon black dispersion liquid;
(5) Stirring the carbon black dispersion liquid in a stirrer at the stirring speed of 80 revolutions per minute;
(6) Respectively and simultaneously dropwise adding the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid according to the molar ratio of 1 to 2 for reaction, controlling the pH to 9.5 by virtue of acid-base reaction (monitoring by using a high-precision portable pH meter in the prior art), stopping dropwise adding the zirconium oxychloride octahydrate solution, continuing dropwise adding the sodium hydroxide solution and stirring for 40 minutes, then stopping dropwise adding the sodium hydroxide solution, continuing to react until the pH is 9.0, and stopping stirring to obtain a mixed solution;
respectively dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid through two peristaltic pumps for reaction, wherein the two solutions of the zirconium oxychloride octahydrate solution and the sodium hydroxide solution are respectively dripped in a droplet shape;
(7) Stirring the mixed solution to react for 8 hours, wherein the stirring speed is 60 revolutions per minute; then centrifugally drying to obtain dispersion liquid with the water content of 10%, and then centrifugally drying to obtain precursor coated carbon black powder;
(8) Mixing the precursor-coated carbon black powder with a mineralizer according to the mass percentage of 10%, and placing the mixture in a calcinator, wherein the calcinator is filled with protective gas;
(9) The calcinator is placed at 1100 ℃ for calcination for 60 minutes;
(10) Taking out, crushing, preferably ball milling to obtain 320-400 mesh powder product.
Example 13
(1) Weighing the zirconium oxychloride octahydrate according to the mass percentage of 1:7, dissolving in deionized water and stirring to completely dissolve the zirconium oxychloride octahydrate, wherein the solution is clear, transparent and free of suspension, and thus obtaining a zirconium oxychloride octahydrate solution;
(2) Weighing sodium hydroxide, dissolving the sodium hydroxide in deionized water, and cooling to room temperature after dissolving to obtain a sodium hydroxide solution;
(3) Modifying carbon black to obtain modified carbon black;
(4) Firstly, mixing the modified carbon black according to the mass percent of 1:60, dissolving the carbon black into deionized water to obtain a carbon black solution, adding a dispersing agent, stirring and carrying out ultrasonic treatment for 6 minutes, wherein the dispersing agent accounts for 3 mass percent of the carbon black solution; then placing the mixture into a mixer to react for 2 to 4 hours, and adjusting the pH value to 3 to obtain carbon black dispersion liquid;
(5) Stirring the carbon black dispersion liquid in a stirrer at the stirring speed of 70 revolutions per minute;
(6) Respectively and simultaneously dropwise adding the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid according to the molar ratio of 1;
respectively dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid through two peristaltic pumps for reaction, and respectively dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution in a droplet shape;
(7) Stirring the mixed solution for reaction for 5 hours, wherein the stirring speed is 45 revolutions per minute; then, carrying out centrifugal drying to obtain a dispersion liquid with the water content of 7, and then carrying out centrifugal drying to obtain precursor coated carbon black powder;
(8) Mixing the precursor-coated carbon black powder with a mineralizer according to the mass percentage of 6%, and placing the mixture in a calcinator, wherein the calcinator is filled with protective gas;
(9) The calcinator is placed at 1050 ℃ for calcinations for 30 minutes;
(10) Taking out, crushing, preferably ball milling to obtain 320-400 mesh powder product.
Comparative example
Mixing iron oxide and chromium oxide according to the mass percentage of 1. The digital overglaze prepared by the method has dark color, and the gray digital overglaze provided by the invention cannot be obtained.
The digital overglaze obtained by the invention is subjected to various detections, and the specific detection analysis results are shown in the following table:
TABLE 1 Effect of digital overglaze spray plates obtained with carbon black dispersions of different particle sizes and different mineralizers
From the data in the above table, it is clear that the control of the conditions such as the carbon black modification, the proper particle size selection of the carbon black dispersant, the selection of the mineralizer, the calcination temperature, etc. can effectively improve the color tone and quality of the digital overglaze.
Table 2 the microstructure analysis method and apparatus of the obtained digital overglaze powder particles
The microstructure analysis flow of the ceramic pigment particles comprises the following steps:
(1) Pretreating the ceramic pigment, drying the solvent, spraying the dried solvent on the conductive adhesive, and placing the conductive adhesive in a gold plating box for gold plating;
(2) Sequentially starting a computer, starting a scanning electron microscope SEM-4500M and software, and then loading a processed sample;
(3) Vacuumizing, and then primarily adjusting the directions X, Y and R of the test bench to find the position of the sample;
(4) Finely adjusting the directions X and Y of the test table on software to find a specific sub-microscopic structure to be observed;
(5) Photographing and storing the image in a designated folder, and then recording data;
(6) And shutting down the machine and taking out the sample.
The test results are shown in fig. 4.
From the above, the obtained digital overglaze powder has good shape regularity and is ellipsoid-shaped, and the average particle size after drying is about 2um, which meets the requirement of particle size (below 5 um).
Table 3 obtained method and instrument for testing particle size of digital overglaze powder particles
| Test items | Test method | Testing instrument |
| Pigment particle size | Dynamic laser light scattering method | Laser particle size analyzer |
The ceramic pigment particle size testing process comprises the following steps:
(1) Starting up and starting up the computer, and cleaning the equipment by using deionized water;
(2) Selecting the types and names of the test particles (red material, yellow material and black material);
(3) Adding deionized water into a ceramic pigment sample, and performing ultrasonic pre-dispersion for later use;
(4) Clicking to start the test, and when the computer appears 'please drop the sample', dropping a proper amount of diluted ceramic pigment until the indication strip is in a green area;
(5) Wait for 30s and read the result.
Table 4 results of particle size measurement of the digital overglaze powder particles
| Test item | Unit of | As a result, the | Limit value | Conclusion |
| Ceramic colorant particle size (D50, first time) | um | 2.054 | X<3.0 | Conform to |
| Ceramic colorant particle size (D50, second) | um | 1.867 | X<3.0 | Conform to |
| Ceramic colorant particle size (D50, third) | um | 1.941 | X<3.0 | Meet with |
| Mean value of | um | 1.954 | X<3.0 | Conform to |
| Ceramic colorant particle size (D90, first time) | um | 3.541 | X<6.0 | Conform to |
| Ceramic colorant particle size (D90, second) | um | 3.762 | X<6.0 | Conform to |
| Ceramic colorant particle size (D90, third time) | um | 3.814 | X<6.0 | Meet with |
| Mean value of | um | 3.706 | X<6.0 | Meet with |
And (4) conclusion: d50, 50 percent of the particle diameter is below the particle diameter; d90: the particle size of 90% of the particles is below this size.
TABLE 5 ceramic pigment moisture test method and apparatus
| Test item | Test method | Test instrument |
| Moisture testing | Drying at 120 deg.C | Multifunctional moisture tester |
TABLE 6 ceramic pigment moisture test results
| Test items | Unit | As a result, the | Limit value | Conclusion |
| Water content of ceramic pigment | wt％ | 1.02 | X<1.5 | Conform to |
TABLE 7 ceramic pigment spray plate testing method and instrument
| Test item | Test method | Testing instrument |
| Ceramic pigment spray plate | Spray plate and high temperature firing | Ball mill, spray gun and shuttle kiln |
The ceramic pigment particle spray plate testing process comprises the following steps:
(1) Sequentially weighing 1.8g of ceramic pigment, 0.15g of dispersing agent STTP, 0.3g of sodium cellulose and 50g of base glaze;
(2) Pouring the mixture into a ball milling tank, adding 30ml of water, and carrying out ball milling for 3min;
(3) Pouring into a spray gun, spraying glaze 3.2g, and drying for 5min;
(4) Putting the mixture into a shuttle kiln with a preset temperature, finishing firing, and closing the kiln;
(5) And performing color difference comparison with a standard plate.
TABLE 8 ceramic pigment spray test results
| Test items | Color tone | Color development intensity | Color difference | High temperature resistance | Conclusion |
| Ceramic pigment spray plate | Pure ash | High strength | Is smaller | 1250℃ | Meet with |
According to the contents of the table, the quality of the gray digital overglaze prepared by the synthesis method provided by the invention is obviously superior to that of the gray digital overglaze prepared by the traditional process, the requirements of related standards are met, the cost is low, and the color tone of the gray digital overglaze is stable.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for synthesizing special gray digital overglaze for ceramic large plates is characterized by comprising the following specific steps:
s1: preparing a reaction solution and a carbon black dispersion;
s2: dropwise adding the reaction solution into the carbon black dispersion liquid for reaction, and then centrifugally drying to obtain precursor-coated carbon black powder;
s3: and calcining the precursor coated carbon black powder, and crushing to obtain a powdery product.
2. The method for synthesizing the special gray digital overglaze for the ceramic large plate according to claim 1, which is characterized in that: the reaction solution in the step S1 comprises an octa-hydrated zirconium oxychloride solution and a sodium hydroxide solution, and the molar concentration of the sodium hydroxide solution is twice of that of the octa-hydrated zirconium oxychloride solution.
3. The method for synthesizing the special gray digital overglaze for the ceramic large panel according to claim 2, wherein the preparation of the zirconium oxychloride octahydrate solution specifically comprises the following steps: weighing the zirconium oxychloride octahydrate according to the mass percentage of 1: (4-10) dissolving in deionized water and stirring to completely dissolve the zirconium oxychloride octahydrate to obtain the zirconium oxychloride octahydrate solution.
4. The method for synthesizing a special gray digital overglaze for ceramic large plates according to claim 2, wherein the preparation of the sodium hydroxide solution specifically comprises the following steps: weighing sodium hydroxide, dissolving the sodium hydroxide in deionized water, and cooling to room temperature after dissolving to obtain a sodium hydroxide solution.
5. The method for synthesizing special gray digital overglaze for ceramic large panels according to any one of claims 2 to 4, wherein S2 comprises the following specific steps:
s21: placing the carbon black dispersion liquid into a stirrer to be stirred;
s22: respectively and simultaneously dripping the zirconium oxychloride octahydrate solution and the sodium hydroxide solution into the carbon black dispersion liquid according to the molar ratio of 1 to 2 for reaction, controlling the pH to 8.5-9.5 by virtue of acid-base reaction, stopping dripping the zirconium oxychloride octahydrate solution, continuing dripping the sodium hydroxide solution and stirring for 20-40 minutes, stopping dripping the sodium hydroxide solution, continuing to react until the pH is 9.0, and stopping stirring to obtain a mixed solution;
s23: and stirring the mixed solution to react for 2-8 hours, then centrifugally drying to obtain dispersion liquid with the water content of 5% -10%, and then centrifugally drying to obtain precursor-coated carbon black powder.
6. The method for synthesizing the special gray digital overglaze for the ceramic large plates according to any one of claims 1 to 4, wherein the preparation of the carbon black dispersion liquid in S1 comprises the following specific steps:
s11: carrying out modification treatment on carbon black to obtain modified carbon black;
s12: firstly, mixing the modified carbon black according to the mass percent of 1: (20-100) dissolving in deionized water to obtain a carbon black solution, adding a dispersing agent, wherein the dispersing agent accounts for 1-5% of the mass of the carbon black solution, stirring and carrying out ultrasonic treatment for 5-10 minutes; then placed in a mixer to react for 2-4 hours and adjusted to pH 3 using standard sodium hydroxide solution to obtain a carbon black dispersion.
7. The method for synthesizing special gray digital overglaze for ceramic large panels according to any one of claims 1 to 4, wherein S3 comprises the following specific steps:
s31: mixing the precursor-coated carbon black powder with a mineralizer according to the mass percentage of 1-10%, and placing the mixture in a calcinator, wherein the calcinator is filled with protective gas;
s32: the calcinator is placed at 950-1100 ℃ for calcination for 5-60 minutes;
s33: taking out and crushing to 320-400 meshes to obtain a powdery product.
8. The method for synthesizing the special gray digital overglaze for the ceramic large panel according to claim 7, which is characterized in that: the mineralizer in S31 is one or more of lithium fluoride, sodium fluoride, potassium fluoride and magnesium fluoride.
9. A gray digital overglaze prepared by the synthesis method of the special gray digital overglaze for ceramic large panels as claimed in any one of claims 1 to 8.
10. Use of a digital overglaze according to claim 9, characterized in that: is applied to the technical field of ceramics.
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