CN107384027B - Chalk for low-temperature ceramic colored drawing/marking and preparation method thereof - Google Patents
Chalk for low-temperature ceramic colored drawing/marking and preparation method thereof Download PDFInfo
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- CN107384027B CN107384027B CN201710612508.0A CN201710612508A CN107384027B CN 107384027 B CN107384027 B CN 107384027B CN 201710612508 A CN201710612508 A CN 201710612508A CN 107384027 B CN107384027 B CN 107384027B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09D13/00—Pencil-leads; Crayon compositions; Chalk compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
- B43K—IMPLEMENTS FOR WRITING OR DRAWING
- B43K19/00—Non-propelling pencils; Styles; Crayons; Chalks
- B43K19/003—Chalks
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Abstract
The invention relates to a low-temperature chalk for ceramic painting/marking and a preparation method thereof, wherein the chalk is a body material which contains a pigment for ceramic and/or a glaze for ceramic and has a certain shape and has the use temperature of 700-850 ℃, and the chalk can be used for painting or marking on a substrate.
Description
Technical Field
The invention relates to a chalk for low-temperature ceramic painting/marking and a preparation method thereof, and the chalk suitable for low-temperature ceramic painting can be prepared by the method, and can participate in the heat treatment process of materials in a suitable temperature range to be used as a marking pen for marking and recording.
Background
From pottery to porcelain, from unglazed ceramic to glazed ceramic, from single-color glazed ceramic to multi-color or colored painted ceramic, from the moment when the ceramic is born in the real sense to ceramic establishment in the modern scientific sense, the colors are accompanied with each stage of ceramic development, and the aesthetic and technological connotations of the ceramic are continuously enriched. Therefore, the variety and quality of ceramic color glaze are indispensable components of the ceramic industry and are also important indexes for measuring the development level of the national ceramic industry.
Therefore, the development of new products of ceramic color glaze has never been stopped, and especially the invention patent of ceramic color glaze in recent years shows the increase of well spraying type. However, although there are many reports on the preparation of ceramic colored glaze materials, no ceramic colored drawing chalk has been reported.
Disclosure of Invention
In the ceramic industry, the successful application of colored glazes plays a crucial role. The invention aims to provide chalk meeting the professional ceramic painting artistic effect, mark chalk capable of participating in the heat treatment process of materials and being used as identification recording, and a preparation method thereof.
On one hand, the invention provides a low-temperature chalk for ceramic painting/marking, the chalk is a body material which contains a pigment and/or a glaze for ceramic with the use temperature of 700-850 ℃ and has a certain shape, and the chalk can paint or mark on a ceramic substrate.
The invention provides a chalk for low-temperature ceramic colored drawing and marking for the first time, which forms a body material with a certain shape by using a colored glaze material for low-temperature ceramic, and can simply and conveniently draw or mark on material matrixes such as biscuit, pottery, porcelain, glass, carbon-nitrogen compound, carbon-silicon compound, aluminum-silicon compound and the like.
Preferably, the content of the ceramic coloring material and/or the ceramic glaze in the chalk is 70% or more.
Preferably, the pigment for ceramics is at least one of glaze pigment, blank pigment and ceramic pigment, preferably at least one of west carmine, agate red, zirconium iron red, white flux, zirconium praseodymium yellow, green grass, zirconium ash, ruddle and brilliant black.
Preferably, the glaze for ceramics is at least one selected from transparent glaze, translucent glaze and opaque glaze.
Preferably, the shape of the chalk is selected from any one of a column shape, a block shape, a ball shape and a sheet shape.
Preferably, the color of the chalk is white or colored, preferably at least one of white, red, green, blue, yellow and black.
In another aspect, the present invention provides a method for preparing the above chalk for low-temperature ceramic painting/marking, comprising the steps of:
(1) mixing a pigment and/or glaze for ceramics with the use temperature of 700-850 ℃ with an auxiliary reagent, and preparing a pre-treatment material capable of being formed;
(2) and forming the pre-treated material into a formed object with a certain shape.
Preferably, in the step (1), the pretreatment material is any one of dry powder, wet powder, slurry and pug.
Preferably, the method of preparing a dry powder comprises: respectively weighing 80.0-99.0% of colored glaze, 0.1-3.0% of solid dispersing agent, 0-5.0% of fixing agent and 0-2.0% of foaming agent by mass percent, filling the materials into a ball milling tank, mixing for 1.5-5 hours, taking out the mixed materials, and repeatedly sieving the materials for a plurality of times by using a 40-mesh sieve.
Preferably, the process for preparing the wet powder comprises: respectively weighing 75.0-97.9% by mass of colored glaze, 0.1-3.0% by mass of solid dispersing agent, 0-5.0% by mass of fixing agent and 0-2.0% by mass of foaming agent, filling the materials into a ball milling tank, mixing for 1.5-5 hours, taking out the mixed materials, then weighing 2.0-10.0% by mass of water, and atomizing and spraying the water on the mixture; the atomized water treated mixture was sieved several times through a 40 mesh sieve.
Preferably, the preparation method of the slurry comprises: weighing 70.0-98.9% of color glaze, 0-20% of thickening binder, 1.0-5.0% of fixing agent and 0-2.0% of foaming agent by mass percent respectively, filling the materials into a ball milling tank 314, weighing ball milling stones with a certain particle diameter ratio, putting the ball milling stones into the ball milling tank, adding a proper amount of distilled water as a ball milling medium, weighing 0.1-3.0% of liquid dispersing agent by volume percent, mixing for 5-45 minutes, pouring out the mixed slurry, and sieving with a 200-mesh sieve.
Preferably, the preparation method of the pug comprises the following steps: preparing a thickening binder solution with the volume percentage of 5-20%; respectively weighing 75.0-99.999% by mass of colored glaze, 0.1-3.0% by mass of solid dispersing agent, 0.001-5.0% by mass of fixing agent and 0-2.0% by mass of foaming agent, filling the materials into a ball milling tank, mixing for 1.5-5 hours, taking out the mixed materials, repeatedly sieving the materials for a plurality of times by using a 40-mesh sieve, placing the materials into a container, and then adding 5-20% by volume of thickening binder solution according to a certain proportion to form mud.
Preferably, the pretreatment material is aged for 1-7 days between the step (1) and the step (2).
Preferably, in the step (2), the forming method is dry forming or wet forming; preferably, the dry forming is selected from any one of powder dry pressing method, isostatic pressing method and mould pressing method, and the wet forming is selected from any one of extrusion method, mould pressing method, slurry pouring method and mould pressing method.
Preferably, in the step (2),
pressing the dry powder or the wet powder into a required shape by using powder forming equipment;
injecting the slurry into a mold for forming;
the pug is moulded into various required shapes by manual kneading, extrusion forming or stamping.
Preferably, the step (2) is followed by performing post-treatment on the formed product, and preferably, the post-treatment is one or more of drying treatment at 35-200 ℃, micro-sintering treatment at 200-350 ℃, thermal infrared drying treatment, ultraviolet aging treatment and laser micro-sintering.
The invention has the beneficial effect that chalk/marking pens with different colors and different types and using temperature environments of 700 ℃ and 850 ℃ can be provided according to different actual requirements. Based on the above, firstly, the chalk/marking pen for low-temperature ceramic colored drawing with the use temperature of 700-850 ℃ can be prepared; secondly, the special mark written by the chalk/marking pen can be used in a sintering environment with the temperature of 700 ℃ and 850 ℃, and thirdly, the chalk/marking pen can be used for drawing on substrates with various shapes and materials.
Drawings
FIGS. 1A-1D illustrate a dry powder compaction method for making ceramic chalks in accordance with one embodiment of the present invention;
FIGS. 2A-2E illustrate a wet powder compaction method for making ceramic chalks in accordance with one embodiment of the present invention;
3A-3D illustrate a slurry casting method for making ceramic chalks in accordance with one embodiment of the present invention;
4A-4F illustrate a method of pressing and stamp-forming a mass for making ceramic chalk according to an embodiment of the present invention;
FIG. 5 shows a cylindrical chalk of zirconium ash (Zr-Si-Ni) 10mm in diameter manufactured by a pug extrusion method for manufacturing ceramic chalk according to an embodiment of the present invention;
FIG. 6 shows a cylindrical chalk of zirconium ash (Zr-Si-Ni) 10mm in diameter manufactured by a pug extrusion method for manufacturing ceramic chalk according to an embodiment of the present invention;
FIG. 7 shows a cylindrical chalk having an agate red pigment diameter of 5mm manufactured by a pug extrusion method for manufacturing ceramic chalks according to an embodiment of the present invention;
FIG. 8 shows a columnar chalk manufactured by a clay molding method for manufacturing a ceramic chalk according to an embodiment of the present invention;
fig. 9 shows a photograph of a ceramic green body on which a chalk according to an embodiment of the present invention is drawn.
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting.
One embodiment of the invention is a low-temperature ceramic chalk for painting/marking (the chalk for short), which has the advantages of low cost, rich colors, simplicity in use, convenience in carrying and environmental friendliness. The chalk is formed by molding low-temperature (the use temperature is 700-850 ℃) ceramic color glaze, and can be used for drawing, writing, marking and the like on a substrate. That is, the ceramic colored glaze is applied to the substrate by rubbing the chalk against the substrate. The applicable temperature (using environment temperature) of the chalk is 700-850 ℃, namely, the ceramic color glaze applied on the substrate by the chalk can be sintered at 700-850 ℃.
The color of the chalk may be white or colored, such as white, red, green, blue, yellow, black, and the like. The invention is suitable for the fields of ceramic arts and crafts and heat treatment processing and manufacturing. The chalk may have various shapes such as a columnar shape, a block shape, a spherical shape, and a sheet shape.
The chalk mainly contains ceramic color glaze with the use temperature of 700-850 ℃. The content of the ceramic glaze in the chalk may be, for example, 70% or more. In addition, the chalk can also contain a small amount of auxiliary materials which are beneficial to forming, such as a binding agent, a dispersing agent, a foaming agent, a shaping agent and the like.
The ceramic color glaze refers to a pigment for ceramics and/or a glaze for ceramics. In the invention, the ceramic color glaze can be used at the use temperature of 700-850 ℃. For example, colorants include: various commercially available glaze pigments and blank pigments, pigments for ceramic gold water and pigments for ceramic ink, etc., such as magenta, agate red, zircaloy red, white flux, zircaloy yellow, green grass, zircaloy ash, red ochre, brilliant black, etc. The glaze material comprises: transparent, semitransparent and opaque glaze.
In one embodiment of the invention, industrial pigments and glazes with mature processes and stable color development are used as basic raw materials, certain water-soluble and oily dispersing agents, foaming agents, binders, forming agents and the like are added, and the marking pens used in a low-temperature sintering environment and ceramic colored drawings with series strength, series density, various shapes and various colors are respectively prepared by different processes and different post-treatments according to a certain mixture ratio of the materials. The method for producing the chalk of the present invention will be specifically described below as an example.
Pretreatment of
The raw materials are low-temperature colored glaze (low-temperature pigment and/or low-temperature glaze) with the temperature of 700-850 ℃. The particle size of the powder is 160-350 mesh. The granularity is too large to facilitate painting and firing; the particle size is too small, the preparation energy consumption is high, and the relative cost is high. The low-temperature colored glaze can be commercially available colored glaze with stable performance and mature process as described above. The raw materials and part of the auxiliary reagent are pretreated to prepare certain pretreated materials, such as powder, slurry, mud and the like. The auxiliary agent comprises a binder, a dispersing agent, a foaming agent, a solidifying agent and the like. The auxiliary reagent can be food grade, so that the prepared chalk is safer and more environment-friendly. The partial premixing treatment is carried out in a roller ball mill. A portion of the auxiliary reagent may be formulated as a solution (e.g., an aqueous solution) of a certain concentration.
In one example, the starting material and auxiliary agent are made into a dry powder. FIGS. 1A-1B illustrate a process flow for making a dry powder material. Referring to FIGS. 1A-1B, the dry powder process is as follows: firstly, 80.0-99.0% by mass of a colored glaze 102, 0.1-3.0% by mass of a dispersant (such as a solid dispersant) 104, 0-5.0% by mass of a curing agent 106 and 0-2.0% by mass of a foaming agent 108 are respectively weighed and put into a resin ball milling tank 110. Then mixing for 1.5-5 hours. The ball milling speed can be 150-200 r/min. The mixed material 112 is removed and sieved several times (e.g., 3-5 times) through a 40 mesh sieve for further use.
In one example, the starting material and auxiliary agent are made as a wet powder. FIGS. 2A to 2C schematically show the flow of the preparation of the wet powder. Referring to FIGS. 2A-2C, the wet powder process is as follows: firstly, 75.0-97.9% by mass of a colored glaze 202, 0.1-3.0% by mass of a dispersant (such as a solid dispersant) 204, 0-5.0% by mass of a solid forming agent 206 and 0-2.0% by mass of a foaming agent 208 are respectively weighed and put into a resin ball milling tank 210. Then mixing for 1.5-5 hours. The ball milling speed can be 150-200 r/min. The mixed material 212 is taken out. Then measuring water with the mass percent of 2.0-10.0%, and atomizing and spraying the water on the mixture; the atomized water-treated mixture 214 is repeatedly screened through a 40 mesh screen several times (e.g., 3-5 times) for use.
In one example, the feedstock and auxiliary agents are formed into a slurry. FIGS. 3A-3B illustrate the preparation of the slurry. Referring to fig. 3A-3B, the process for the slurry is as follows: firstly, 70.0-98.9% of colored glaze 302, 0-20% (preferably 5-15%) of thickening binder 304, 1.0-5.0% of curing agent 306 and 0-2.0% of foaming agent 308 are respectively weighed by mass and filled into a resin ball milling tank 314. Then, a ball mill stone 310 having a certain particle diameter ratio (for example, a large particle diameter ratio: a medium particle diameter: a small particle diameter: 4:3) is weighed and placed in a ball mill pot. Then adding proper amount of distilled water as ball milling medium. The mass ratio of the materials, the balls and the water can be 1: (2.0-3.0): (0.6-1.0). Then, 0.1-3.0% by volume of liquid dispersant 312 is measured. Mixing for 5-45 minutes. The rotation speed of the ball mill can be 180-250 r/min. The mixed slurry 316 is then poured out and sieved through a 200 mesh sieve for later use.
In one example, the raw materials and auxiliary agents are formed into a paste/paste. FIGS. 4A to 4D schematically show the preparation process of the pug. Referring to fig. 4A-4D, the process for the pug/paste is as follows: firstly, preparing a thickening binder 408 solution 410 with the volume percentage of 5-20% for later use. Meanwhile, 90.0-99.999% by mass of the colored glaze 402, 0.1-3.0% by mass of the solid dispersing agent 404, 0.001-5.0% by mass of the solid forming agent 406 and 0-2.0% by mass of the foaming agent 412 are respectively weighed and filled into a resin ball-milling tank 414. Then mixing for 1.5-5 hours. The ball milling speed can be 150-200 r/min. The mixed material 416 is taken out and sieved repeatedly with a 40-mesh sieve for several times (e.g., 3-5 times). And then placed in an enamel tray 418. And then adding a thickening binder solution 410 with the volume percentage of 5-20% and the formed mud 420 for later use, wherein the mass percentage of the thickening binder solution is 10-50% relative to the total amount of the colored glaze, the solid dispersing agent, the solidifying agent and the foaming agent.
The thickening binder is used for adjusting the viscosity of a liquid agent and a slurry and improving the adhesive force for product molding, and may be aqueous or oily. The purity can be food grade and can be selected from: starch, agar, vegetable gum, animal gum, etc.
The starch may be selected from: various kinds of plant starches such as amylose and amylopectin, for example, water-soluble starch, soluble starch and the like.
The vegetable gum can be selected from: fir adhesive, peach gum, sodium alginate, sesbania gum, peach gum, flax gum, fenugreek gum and the like.
The glue can be selected from: fish gelatin, donkey gelatin, bovine gelatin, and the like.
The dispersant is used to uniformly disperse solid particles in a liquid, and may be a liquid dispersant and/or a solid dispersant. When preparing dry powder and wet powder, solid dispersant is preferred; when preparing slurry or slurry, a liquid dispersant is preferable.
The liquid dispersant may be selected from: sodium polyacrylate, sodium methyl cellulose, and the like.
The solid dispersant may be selected from: polyethylene glycol alkyl ethers, such as: polyethylene glycol dimethyl ether, etc., and polyethylene wax, polyethylene glycol 200 or 400, etc.
The above blowing agent, which is used to increase the porosity of the product, can be selected from: carbonates, such as: ammonium bicarbonate, calcium carbonate, sodium bicarbonate, and the like, and carbon black, animal and vegetable protein foaming agents, sodium dodecyl benzene sulfonate, and the like.
The solidifying agent is used for adjusting the material forming performance and can be selected from the following components: artemisia glue, calcium sulfate, paraffin, beeswax, rosin, etc.
Stale flavor
And (3) sealing the pretreated raw materials 112, 214, 316 and 420 and placing the raw materials in a shady and shady place for ageing for 1 to 7 days.
Shaping of
The pre-treated material or the aged pre-treated material is formed into a desired shape, such as a column, a block, a sphere, a sheet, etc. The molding method may be a dry method or a wet method. The dry method may be selected from: dry powder pressing, isostatic pressing, die pressing, and the like. The wet process may be selected from: extrusion, compression molding, slurry casting, impression molding, and the like. For dry and wet powders, dry processes are preferred. For slurry and sludge, the wet method is preferred. Fig. 8 shows a columnar chalk manufactured by a clay molding method for manufacturing a ceramic chalk.
In one example, as shown in fig. 1C-1D, 2D-2E, a powder forming device (e.g., a press) 114, 216 is used to compact the powder into a desired shape 116, 218. The pressing pressure can be 0.5-10 MPa.
In one example, as shown in fig. 3C-3D, the slurry 316 is injected into a mold 318 to form a desired shape 320. The material of the mould can be plaster, plastic, metal and the like.
In one example, as shown in FIGS. 4E-4F, the pug is molded into the desired shapes 424 by manual miskneading, extrusion 422, and/or stamping. Wherein the pressure is 0.5-10 MPa.
Post-treatment
After molding, post-treatment may also be performed to increase the strength of the molded article and improve the use properties. For example, the shaped product is placed in a ventilated shade or a special post-treatment apparatus for an appropriate treatment time. The post-treatment can be drying treatment, micro-sintering treatment, thermal infrared treatment, ultraviolet aging treatment and the like. For example, the post-processing may be: drying treatment is carried out in a forced air drying oven at 35-200 ℃ (preferably 60-120 ℃) for 60-320 minutes, micro-sintering treatment is carried out in a low-temperature sintering furnace at 200-350 ℃ for 30-60 minutes, drying treatment is carried out in a thermal infrared drying oven for 30-60 minutes, aging treatment is carried out in an ultraviolet aging oven for 30-120 minutes, laser micro-sintering is carried out for 10-30 minutes, and the like, and the method is carried out in one mode or a combination of multiple modes.
Packaging/wrapping
The finished product after treatment is packaged by using various packaging technologies. For example, the film package is made of an organic or inorganic film or a composite film of the two, and various materials are used as a protective or auxiliary casing or sleeve for convenient use.
The chalk of the invention can be used for drawing or marking on material matrixes such as blanks, ceramics, porcelain, glass, carbon-nitrogen compounds, carbon-silicon compounds, aluminum-silicon compounds and the like. Referring to fig. 9, there is shown a photograph of a ceramic green body painted with the chalk of the present invention. Drawing or marking may include in-glaze, over-glaze, under-glaze. After drawing or marking, sintering at 700-850 ℃.
The marking pen used in the environment of ceramic colored drawing and low-temperature sintering with series strength, series density, various shapes and various colors is prepared by different processes and different post-treatments. For example, the chalk of the present invention has a strength of 12N/cm2-15N/cm2And (4) controllable.
The chalk has the specific advantages of easily obtained raw materials, simple control of the manufacturing process and stable performance, can be prepared into various shapes, and is suitable for marking and recording the heat treatment process of materials; meanwhile, the chalk is rich in color and simple to use, so that the artistic creation of professional ceramic colored drawing can be met, and the chalk can be used for ceramic culture experience facing the public; in addition, the ceramic toy has the advantages of convenience in carrying, environmental friendliness and the like, is particularly suitable for children ceramic artistic training, and has good market prospect and large-scale production capacity due to the advantages.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1:
firstly, respectively weighing 99.9 mass percent of zirconium ash (Zr-Si-Ni) low-temperature color glaze with the granularity of 300 meshes, the using temperature of 850 ℃ and stable market performance, and the mature process, and 0.1 mass percent of sodium polyacrylate, putting the materials into a resin ball milling tank, mixing the materials for 1.5h, taking out the materials, sieving the materials for 3 times by a 40-mesh sieve, and sealing and placing the pretreated raw materials in a dark and cool place for later use; pressing the powder into a cylindrical shape by using isostatic pressing equipment; packaging the formed product.
Example 2:
firstly, respectively weighing zirconium praseodymium yellow low-temperature color glaze with the granularity of 300 meshes, the service temperature of 850 ℃, stable market performance and mature process, the mass percent of which is 98.5%, and the mass percent of which is 1.5%, loading the zirconium praseodymium yellow low-temperature color glaze and the sodium polyacrylate into a resin ball milling tank, mixing the materials for 1.5h, taking out, sieving the materials for 3 times by a 40-mesh sieve, and then sealing and placing the pretreated raw materials in a dark and cool place for later use; pressing the powder into a cylindrical shape by using isostatic pressing equipment; packaging the formed product.
Example 3:
firstly, respectively weighing 96.0% mass percent of agate red low-temperature color glaze material with the granularity of 320 meshes, the using temperature of 850 ℃, stable performance and mature process, 3.0% mass percent of sodium polyacrylate and 1.0% mass percent of ammonium bicarbonate, putting the materials into a resin ball milling tank, mixing the materials for 2 hours, taking out the materials, sieving the materials for 3 times by a 40-mesh sieve, and sealing and placing the pretreated raw materials in a dark and cool place for ageing for 1 d; pressing the powder into a cylindrical shape by using isostatic pressing equipment; placing the formed product in laser sintering equipment for processing; the treated shaped product is then packaged.
Example 4:
firstly, respectively weighing 96.4 mass percent of zirconium ash (Zr-Si-Ni) low-temperature color glaze with the granularity of 300 meshes, the using temperature of 850 ℃, stable performance and mature process, 0.1 mass percent of sodium polyacrylate and 1.5 mass percent of food-grade water-soluble starch, putting the materials into a resin ball milling tank, mixing the materials for 2 hours, taking out the materials, then weighing 2.0 mass percent of purified water, and atomizing and spraying the purified water on the mixed amount; repeatedly sieving the mixture subjected to atomized water treatment for 3 times by using a 40-mesh sieve for later use; then, the pretreated raw materials are sealed and placed in a dark and cool place to be aged for 1 d; pressing the powder into a cylindrical shape by using isostatic pressing equipment; placing the formed product in a ventilating shade for several days; and finally packaging the formed product dried in the shade.
Example 5:
firstly, 96.4 mass percent of agate red low-temperature color glaze with the granularity of 300 meshes, the using temperature of 850 ℃, stable performance and mature process, 0.1 mass percent of sodium polyacrylate and 1.5 mass percent of food-grade water-soluble starch are respectively weighed, put into a resin ball milling tank, mixed for 2 hours and taken out. Then, pure water with the mass percent of 2.0% is measured, and atomized and sprayed on the mixed amount; repeatedly sieving the mixture subjected to atomized water treatment for 3 times by using a 40-mesh sieve for later use; then, the pretreated raw materials are sealed and placed in a dark and cool place to be aged for 1 d; pressing the powder into a prism shape by using isostatic pressing equipment; placing the formed product in a ventilating shade for several days; and finally packaging the formed product dried in the shade.
Example 6:
the method comprises the steps of weighing a zirconium praseodymium yellow low-temperature color glaze material which has the granularity of 320 meshes, is used at 850 ℃ and is stable in market performance, mature in process, and comprises 89% by mass of zirconium praseodymium yellow low-temperature color glaze material, 1.0% by mass of sodium polyacrylate and 5.0% by mass of food-grade water-soluble starch, putting the materials into a resin ball milling tank, mixing the materials for 3 hours, and taking the materials out. Then 5.0 percent of purified water by mass percent is weighed and atomized and sprayed on the mixed amount; repeatedly sieving the mixture subjected to atomized water treatment for 3 times by using a 40-mesh sieve for later use; then, the pretreated raw materials are sealed and placed in a dark and cool place to be aged for 2 d; pressing the powder into a cylindrical shape by using isostatic pressing equipment; placing the formed product in a ventilating shade for several days; and finally packaging the formed product dried in the shade.
Example 7:
firstly, respectively weighing 96.8% of zirconium ash (Zr-Si-Ni) low-temperature color glaze with the granularity of 200 meshes and the use temperature of 850 ℃, 3% of food-grade water-soluble starch, 0.1% of sodium polyacrylate and 0.1% of polyethylene glycol alkyl ether, putting the materials into a resin ball milling tank, then weighing 250g of ball milling stones with a certain grain diameter ratio, putting the ball milling tanks and 80ml of purified water. The control proportion is as follows: ball: water 1: 2.5: 0.8, putting the mixture into a ball milling tank, ball milling the mixture for 15min at the rotating speed of 120r/min, pouring out the slurry, and sieving the slurry by a 200-mesh sieve. And sealing the slurry and placing the slurry in a shady and cool place to be aged for 2 d. And injecting the slurry into a mold for forming. The cured product was then placed in an infrared drying oven for several days until completely dry. And packaging the dried product.
Example 8:
firstly, respectively weighing 89.8% zirconium ash (Zr-Si-Ni) low-temperature color glaze with the granularity of 200 meshes, the using temperature of 850 ℃, stable performance and mature process, 10% food-grade water-soluble starch, 0.1% sodium polyacrylate and 0.1% polyethylene glycol alkyl ether, filling the glaze into a resin ball milling tank, then weighing 250g of ball milling stone with a certain grain diameter ratio, placing the ball milling stone into the ball milling tank, and 80ml of purified water. The control proportion is as follows: ball: water 1: 2.5: 0.8, putting the mixture into a ball milling tank, ball milling the mixture for 15min at the rotating speed of 120r/min, pouring out the slurry, and sieving the slurry by a 200-mesh sieve. And sealing the slurry and placing the slurry in a shady and cool place to be aged for 2 d. And injecting the slurry into a mold for forming. The cured product was then placed in an infrared drying oven for several days until completely dry. And packaging the dried product.
Example 9:
firstly, weighing 84.8% of zirconium ash (Zr-Si-Ni) low-temperature color glaze with the granularity of 300 meshes and the use temperature of 850 ℃, 15% of food-grade water-soluble starch, 0.1% of sodium polyacrylate and 0.1% of polyethylene glycol alkyl ether, putting the materials into a resin ball milling tank, weighing 250g of ball milling stone with a certain grain diameter ratio, putting the ball milling stone into the ball milling tank, and 80ml of purified water. The control proportion is as follows: ball: water 1: 2.5: 0.8, putting the mixture into a ball milling tank, ball milling the mixture for 15min at the rotating speed of 120r/min, pouring out the slurry, and sieving the slurry by a 200-mesh sieve. And sealing the slurry and placing the slurry in a shady and cool place to be aged for 2 d. And injecting the slurry into a mold for forming. And then the solid product is placed in a thermal infrared drying oven for drying treatment. After the chalk is completely dried, the product is put in an ultraviolet aging oven for aging treatment, and then the aged product is packaged.
Example 10:
firstly, respectively weighing 95.8% of commercially available zirconium praseodymium yellow low-temperature color glaze with the granularity of 200 meshes and the use temperature of 850 ℃, 3% of food-grade water-soluble starch, 0.1% of sodium polyacrylate, 0.1% of polyethylene glycol alkyl ether and 1.0% of ammonium bicarbonate by mass percent, filling the materials into a resin ball milling tank, then weighing 250g of ball milling stone with a certain grain diameter ratio, placing the ball milling stone into the ball milling tank, and 80ml of distilled water. The control proportion is as follows: ball: water 1: 2.5: 0.8, putting the mixture into a ball milling tank, ball milling the mixture for 15min at the rotating speed of 120r/min, pouring out the slurry, and sieving the slurry by a 200-mesh sieve. And sealing the slurry and placing the slurry in a shady and cool place to be aged for 2 d. And injecting the slurry into a mold for forming. Then the product after setting is placed in a forced air drying oven at 100 ℃ for treatment. And packaging the dried product.
Example 11:
firstly, 89.8 percent of commercial agate red material for glaze, 10 percent of food-grade water-soluble starch, 0.1 percent of food-grade artemisia glue and 0.1 percent of polyethylene glycol alkyl ether with the granularity of 320 meshes and the use temperature of 850 ℃ are respectively weighed and put into a resin ball milling pot, then 250g of ball milling stone with a certain grain diameter ratio is weighed and put into the ball milling pot, and 80ml of distilled water. The control proportion is as follows: ball: water 1: 2.5: 0.8, putting the mixture into a ball milling tank, ball milling the mixture for 15min at the rotating speed of 120r/min, pouring out the slurry, and sieving the slurry by a 200-mesh sieve. And sealing the slurry and placing the slurry in a shady and cool place to be aged for 2 d. And injecting the slurry into a mold for forming. Then the product after setting is placed in a forced air drying oven at 100 ℃ for treatment. And packaging the dried product.
Example 12:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of commercial zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 320 meshes and the use temperature of 850 ℃ and 0.01 percent of sodium polyacrylate, putting the glaze and the sodium polyacrylate into a resin ball milling tank, ball milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, then pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and then placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. The pug is molded into a cylindrical chalk with the diameter of 10mm by an extrusion molding method, as shown in figure 5. And finally, placing the formed product in a ventilated and cool place. And packaging and boxing the chalk after the chalk is completely dried.
Example 13:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of commercial zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 320 meshes and the use temperature of 850 ℃ and 0.01 percent of sodium polyacrylate, putting the glaze and the sodium polyacrylate into a resin ball milling tank, ball milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, then pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and then placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. The pug was molded into 10mm diameter cylindrical chalk by extrusion molding, as shown in FIG. 6. Finally, the molded product was treated in a forced air drying oven at 100 ℃. And packaging and boxing the chalk after the chalk is completely dried.
Example 14:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously, respectively weighing 99.99 percent of commercially available agate red pigment with the granularity of 320 meshes and the use temperature of 850 ℃ and 0.01 percent of sodium polyacrylate, putting the materials into a resin ball milling tank, ball milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, pouring out powder materials, sieving the powder materials by a 40-mesh sieve, sieving the powder materials for 3 times, and placing the powder materials in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. The pug was molded into 10mm diameter cylindrical chalk by extrusion molding, as shown in FIG. 7. And finally, placing the formed product in a thermal infrared drying oven for drying treatment. After the chalk is completely dried, the product is put in an ultraviolet aging oven for aging treatment, and then the aged product is packaged.
Example 15:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously weighing 98.99 percent of zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 320 meshes and the use temperature of 850 ℃, 0.01 percent of sodium polyacrylate and 1.0 percent of ammonium bicarbonate by mass percent, putting the materials into a resin ball milling tank, ball milling the mixed materials for 1.5 hours at the rotating speed of 120r/min, pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and putting the powder into an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into columnar chalk with the diameter of 10mm by adopting an extrusion molding method. Finally, the molded product was treated in a forced air drying oven at 100 ℃. And packaging and boxing the chalk after the chalk is completely dried.
Example 16:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 320 meshes and the use temperature of 850 ℃ and 0.01 percent of food-grade artemisia glue, putting the materials into a resin ball-milling tank, ball-milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, then pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and then placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into columnar chalk with the diameter of 10mm by adopting an extrusion molding method. And finally, placing the formed product in a ventilated and cool place. And packaging and boxing the chalk after the chalk is completely dried.
Example 17:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 320 meshes and the use temperature of 850 ℃ and 0.01 percent of food-grade artemisia glue, putting the materials into a resin ball-milling tank, ball-milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, then pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and then placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into columnar chalk with the diameter of 10mm by adopting an extrusion molding method. And finally, placing the formed product in a thermal infrared drying oven for drying treatment. After the chalk is completely dried, the product is put in an ultraviolet aging oven for aging treatment, and then the aged product is packaged.
Example 18:
firstly, weighing 10g of food-grade water-soluble starch, placing the food-grade water-soluble starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 200 meshes and the use temperature of 850 ℃ and 0.01 percent of food-grade artemisia glue, putting the materials into a resin ball-milling tank, ball-milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, then pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and then placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to form a mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into columnar chalk with the diameter of 10mm by adopting an extrusion molding method. And finally, placing the formed product in a ventilated and cool place. And packaging and boxing the chalk after the chalk is completely dried.
Example 19:
firstly, weighing 10g of food-grade water-soluble starch, placing the food-grade water-soluble starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of a commercially available zirconium praseodymium yellow pigment with the granularity of 200 meshes and the use temperature of 850 ℃ and 0.01 percent of food grade artemisia glue, putting the materials into a resin ball milling tank, ball milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, then pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and then placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into columnar chalk with the diameter of 10mm by adopting an extrusion molding method. And finally, placing the formed product in a thermal infrared drying oven for drying treatment. After the chalk is completely dried, the product is put in an ultraviolet aging oven for aging treatment, and then the aged product is packaged.
Example 20:
firstly, weighing 10g of food-grade water-soluble starch, placing the food-grade water-soluble starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously weighing 98.99 percent of commercially available agate red pigment with the granularity of 200 meshes and the use temperature of 850 ℃, 0.01 percent of food-grade artemisia glue and 1.0 percent of ammonium bicarbonate by mass, putting the materials into a resin ball milling tank, ball-milling and mixing the materials at the rotating speed of 120r/min for 1.5 hours, pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and placing the powder in an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into columnar chalk with the diameter of 10mm by adopting an extrusion molding method. Finally, the molded product was treated in a forced air drying oven at 100 ℃. And packaging and boxing the chalk after the chalk is completely dried.
Example 21:
firstly, weighing 5g of food-grade water-soluble starch, placing the starch into a conical flask, weighing 100ml of purified water, adding the purified water into the conical flask, placing the conical flask on a magnetic stirrer, stirring for about 30min until the solution is clear, and sealing the opening of the conical flask for later use;
simultaneously respectively weighing 99.99 percent of zirconium ash (Zr-Si-Ni) low-temperature colored glaze with the granularity of 320 meshes and the use temperature of 850 ℃ and 0.01 percent of sodium polyacrylate, putting the materials into a resin ball milling tank, ball milling the mixed materials at the rotating speed of 120r/min for 1.5 hours, pouring out the powder, sieving the powder by a 40-mesh sieve, sieving the powder for 3 times, and placing the powder into an enamel tray;
then 50ml of water-soluble starch solution is added to be made into mud, and the mud is sealed and placed in a shady and cool place to be aged for 1 day. And (3) molding the pug into a columnar chalk with the diameter of 10mm by adopting a die molding method. And finally, placing the formed product in a ventilated and cool place. And packaging and boxing the chalk after the chalk is completely dried.
Claims (15)
1. The chalk for low-temperature ceramic painting/marking is characterized in that the chalk is a body material which contains a pigment for ceramic and/or a glaze for ceramic and has a certain shape and the use temperature of which is 700-850 ℃; the content of the ceramic pigment and/or the ceramic glaze is more than 70%; the shape of the chalk is selected from any one of column, block, sphere and sheet;
the method for preparing the chalk for low-temperature ceramic colored drawing/marking comprises the following steps:
(1) mixing a ceramic pigment and/or ceramic glaze with the use temperature of 700-850 ℃ with an auxiliary reagent to prepare a formable pretreatment material; the pretreatment material is any one of dry powder, wet powder, slurry and pug;
when the pretreatment material is dry powder or wet powder, the auxiliary agents comprise: 0.1-3.0% by mass of a solid dispersing agent, 0-5.0% by mass of a solid forming agent and 0-2.0% by mass of a foaming agent;
when the pretreatment slurry is a slurry, the auxiliary reagents include: 0-20% of thickening binder, 1.0-5.0% of solidifying agent, 0-2.0% of foaming agent and 0.1-3.0% of liquid dispersing agent by volume percentage;
when the pretreatment material is pug, the auxiliary reagent comprises: 0.1-3.0% by mass of a solid dispersing agent, 0.001-5.0% by mass of a solid forming agent, 0-2.0% by mass of a foaming agent, and 5-20% by volume of a thickening binder solution, wherein the thickening binder solution is 10-50% by mass of a ceramic pigment and/or a ceramic glaze, the solid dispersing agent, the solid forming agent and the foaming agent;
(2) forming the pretreatment material into a formed object with a certain shape;
the strength of the chalk is 12N/cm2-15 N/cm2The chalk can be used for drawing or marking on a substrate, and can be sintered at 700-850 ℃ after drawing or marking.
2. The low temperature ceramic painting/marking chalk of claim 1,
the ceramic pigment is at least one of glaze pigment, blank pigment and ceramic pigment;
the glaze for the ceramic is selected from at least one of transparent glaze, semi-transparent glaze and opaque glaze.
3. The low temperature ceramic color drawing/marking chalk of claim 2, wherein the ceramic pigment is selected from at least one of western red, agate red, zirco-iron red, white flux, zirco-yellow, green grass, zirco-ash, red ochre, and brilliant black.
4. The low temperature ceramic chalk for painting/marking according to claim 1, wherein the chalk is white or colored in color.
5. The low temperature ceramic chalk for painting/marking according to claim 4, wherein the color of the chalk is at least one selected from the group consisting of white, red, green, blue, yellow and black.
6. The low temperature ceramic chalk for painting/marking according to claim 1, wherein the dry powder is prepared by a method comprising: respectively weighing 80.0-99.0% of colored glaze, 0.1-3.0% of solid dispersing agent, 0-5.0% of fixing agent and 0-2.0% of foaming agent by mass percent, filling the materials into a ball milling tank, mixing for 1.5-5 hours, taking out the mixed materials, and repeatedly sieving the materials for a plurality of times by using a 40-mesh sieve.
7. The low temperature ceramic chalk for painting/marking according to claim 1, wherein the wet powder is prepared by a method comprising: respectively weighing 75.0-97.9% by mass of colored glaze, 0.1-3.0% by mass of solid dispersing agent, 0-5.0% by mass of fixing agent and 0-2.0% by mass of foaming agent, filling the materials into a ball milling tank, mixing for 1.5-5 hours, taking out the mixed materials, then weighing 2.0-10.0% by mass of water, and atomizing and spraying the water on the mixture; the atomized water treated mixture was sieved several times through a 40 mesh sieve.
8. The low temperature ceramic chalk for painting/marking according to claim 1, wherein the slurry is prepared by a method comprising: weighing 70.0-98.9% of color glaze, 0-20% of thickening binder, 1.0-5.0% of fixing agent and 0-2.0% of foaming agent by mass percent respectively, filling the materials into a ball milling tank 314, weighing ball milling stones with a certain particle diameter ratio, putting the ball milling stones into the ball milling tank, adding a proper amount of distilled water as a ball milling medium, weighing 0.1-3.0% of liquid dispersing agent by volume percent, mixing for 5-45 minutes, pouring out the mixed slurry, and sieving with a 200-mesh sieve.
9. The low-temperature ceramic chalk for painting/marking according to claim 1, wherein the preparation method of the pug comprises the following steps: preparing a thickening binder solution with the volume percentage of 5-20%; respectively weighing 75.0-99.999% by mass of colored glaze, 0.1-3.0% by mass of solid dispersing agent, 0.001-5.0% by mass of fixing agent and 0-2.0% by mass of foaming agent, filling the materials into a ball milling tank, mixing for 1.5-5 hours, taking out the mixed materials, repeatedly sieving the materials for a plurality of times by using a 40-mesh sieve, placing the materials into a container, and then adding 5-20% by volume of thickening binder solution according to a certain proportion to form mud.
10. The low-temperature ceramic chalk for painting/marking according to claim 1, further comprising aging the pretreatment material for 1-7 days between the step (1) and the step (2).
11. The low-temperature ceramic chalk for painting/marking according to claim 1, wherein in the step (2), the forming method is dry forming or wet forming.
12. The low temperature ceramic colored drawing/marking chalk according to claim 11, wherein the dry molding is selected from any one of powder dry pressing, isostatic pressing and molding, and the wet molding is selected from any one of extrusion, molding, slurry casting and molding.
13. The low temperature ceramic painting/marking chalk of claim 11, wherein in step (2),
pressing the dry powder or the wet powder into a required shape by using powder forming equipment;
injecting the slurry into a mold for forming;
the pug is moulded into various required shapes by manual kneading, extrusion forming or stamping.
14. The low temperature ceramic chalk for painting/marking according to claim 1, further comprising post-treating the molded article after step (2).
15. The low-temperature ceramic chalk for painting/marking according to claim 14, wherein the post-treatment is one or more selected from the group consisting of drying treatment at 35-200 ℃, micro-sintering treatment at 200-350 ℃, thermal infrared drying treatment, ultraviolet aging treatment, and laser micro-sintering.
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| CN201710612508.0A CN107384027B (en) | 2017-07-25 | 2017-07-25 | Chalk for low-temperature ceramic colored drawing/marking and preparation method thereof |
| PCT/CN2018/084364 WO2019019722A1 (en) | 2017-07-25 | 2018-04-25 | Chalk for ceramic painting/marking and preparation method therefor |
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| CN201710612508.0A CN107384027B (en) | 2017-07-25 | 2017-07-25 | Chalk for low-temperature ceramic colored drawing/marking and preparation method thereof |
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| CN109306211A (en) * | 2018-09-25 | 2019-02-05 | 南昌蓝珀笔业画材有限公司 | A kind of environmental protection encaustic color stick and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9705686A (en) * | 1997-08-25 | 1999-06-29 | De Souza Elliana Figueiredo | Chalk manufacturing process for decoration of ceramic pieces |
| WO2005105688A2 (en) * | 2004-04-30 | 2005-11-10 | Lucien Tink | Compound for the decoration of ceramics |
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| CN1065260C (en) * | 1994-02-22 | 2001-05-02 | 蒋采苹 | Pigment paste and block for painting and method for processing same |
| CN1151989C (en) * | 1999-08-11 | 2004-06-02 | 淄博赛德克陶瓷颜料有限公司 | Overglaze cobalt blue pigment for ceramic and its preparation |
| CN103963547B (en) * | 2014-05-09 | 2016-08-31 | 操驰 | A kind of pottery boneless painting and manufacture technique thereof |
| CN106675209A (en) * | 2017-01-03 | 2017-05-17 | 上海满意文化传播有限公司 | Pigment pencil for underglaze painting of ceramics and application method of pigment pencil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9705686A (en) * | 1997-08-25 | 1999-06-29 | De Souza Elliana Figueiredo | Chalk manufacturing process for decoration of ceramic pieces |
| WO2005105688A2 (en) * | 2004-04-30 | 2005-11-10 | Lucien Tink | Compound for the decoration of ceramics |
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