CN113713944B - Raw material treatment method for digital ceramic glaze ink - Google Patents
Raw material treatment method for digital ceramic glaze ink Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C21/00—Disintegrating plant with or without drying of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/20—Disintegrating members
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/08—Separating or sorting of material, associated with crushing or disintegrating
- B02C23/14—Separating or sorting of material, associated with crushing or disintegrating with more than one separator
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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Abstract
The invention discloses a raw material treatment method for digital ceramic glaze ink, which comprises the following steps: selecting a natural mineral raw material or a rough mineral raw material required for preparing the digital ceramic glaze ink; calcining each selected raw material respectively; proportioning the calcined raw materials according to a formula to obtain a mixture; grinding the mixture in sequence, removing iron, drying, crushing and grading; and (3) calcining, crushing and grading the mixture subjected to the grading treatment in sequence to obtain raw material powder. The method can be used for preparing raw material powder of the digital ceramic glaze ink directly; the powder has the characteristics of high purity and high grade; the calcined raw materials are easy to crush, so that the grinding efficiency is improved, and the ink preparation time is shortened; the digital ceramic glaze ink prepared by the powder has the characteristics of good dispersibility and high stability in a dispersion system of an ink solvent.
Description
Technical Field
The invention relates to the technical field of ink, in particular to a raw material treatment method for digital ceramic glaze ink.
Background
The architectural ceramic industry has evolved to the present day, and the pattern decoration of ceramic tiles produced therefrom has become popular basically with decoration techniques using digital ink-jet printing. The advantages of digital ink-jet printing are very obvious compared with the traditional silk screen printing and rubber roller printing decoration, and especially the advantages which are incomparable in the aspects of color decoration, replacement design and the like are obvious. Along with the popularization of the ink-jet technology and the continuous improvement of the requirements of ceramic enterprises on the product decoration effect, the decoration of the digital glaze also gradually enters the ceramic production enterprises, such as digital white ink, which has higher whiteness, so that the digital white ink can replace a part of traditional glaze to cover the green body color with low whiteness, and is beneficial to the color development of decorative patterns; and after replacing part of the traditional glaze, the processing and performance adjustment glaze line equipment and personnel matching investment and management of the traditional glaze can be reduced. Therefore, the application and popularization of the digital ceramic glaze ink with special effect or function will become the important conditions for the ceramic production enterprises to modern, technological and digital, and the ink companies are developing various digital ceramic glaze inks in the direction of the demand.
The digital ceramic glaze ink is prepared by selecting high-quality mineral raw materials as raw materials used by the traditional ceramic glaze, or introducing special materials such as various frits to adjust the sintering performance of the digital ceramic glaze ink. However, the existing processing mode generally has a problem that the processing difficulty is high, part of natural minerals are high in hardness and difficult to crush, and especially part of frit is introduced, so that a plurality of frit particles are formed after processing, and the processing time is very long, and is even 120 hours. At present, most of digital white glaze ink is prepared by adopting zirconium silicate or cerium oxide ceramic raw materials as main raw materials, wherein the raw materials are not obtained by processing natural mineral raw materials by ink companies, but are powder obtained by processing by upstream professional clients, and then are used as raw materials of the digital white glaze ink.
The raw materials for preparing the digital ceramic glaze ink are different from the traditional ceramic glaze particles, the fineness is generally controlled to be below 1-5 mu m, so that the more natural minerals with higher hardness are introduced into the digital ceramic glaze ink formula, the greater the processing difficulty is, and the longer the ink preparation time is. The prepared ceramic ink particles have wide range distribution, insufficient concentrated granularity, poor dispersibility and low stability of the material in an ink solvent system, are easy to cause layering of the ink material, are inconvenient to store, influence the spraying performance, easily block a spray head and finally influence production.
Accordingly, there is a need for improvement and development in the art.
Disclosure of Invention
In view of the defects of the technology, the invention provides a raw material treatment method for digital ceramic glaze ink, which aims to solve the problems that when the existing raw materials are used for preparing the digital ceramic glaze ink, part of mineral raw materials are high in hardness and difficult to crush, and the time for preparing the ink is long.
Specifically, the technical scheme of the invention is as follows:
the method for treating the raw material for the digital ceramic glaze ink comprises the following steps:
step A, selecting a natural mineral raw material or a rough mineral raw material required for preparing the digital ceramic glaze ink;
step B, calcining each selected raw material respectively;
step C, proportioning the calcined raw materials according to a formula to obtain a mixture;
step D, grinding the mixture in sequence, removing iron, drying, crushing and grading;
and E, calcining, crushing and grading the mixture treated in the step D in sequence to obtain raw material powder.
Optionally, the natural mineral raw material is selected from one or more of feldspar raw material, quartz raw material and clay raw material;
alternatively, the raw mineral raw material is selected from one or more of feldspar-based raw materials, quartz sand-based raw materials, and clay-based raw materials.
Optionally, in the step D, the grinding process conditions are as follows: and under the action of grinding balls, the mixture is subjected to wet grinding by taking water as a medium, and the particle size of the grinding balls is 3-5 mm.
Optionally, in the step D, the particle size of the raw material after the grinding treatment is controlled under a 325 mesh screen.
Optionally, in the step D, the particle size of the raw material after classification is controlled under a 200 mesh screen.
Optionally, in the step E, the calcining temperature is 900-1200 ℃.
Optionally, in the step E, the particle diameter of the raw material powder is controlled to be 10 μm or less.
The method for treating the raw material for the digital ceramic glaze ink comprises the following steps:
step A', selecting a natural mineral raw material or a rough mineral raw material required for preparing the digital ceramic glaze ink;
step B', the screened raw materials are respectively proportioned according to the formula to obtain a mixture;
and C', sequentially grinding the mixture, removing iron, drying, crushing, grading, calcining, crushing and grading to obtain raw material powder.
Optionally, in the step C', the process conditions of the grinding are as follows: and under the action of grinding balls, the mixture is subjected to wet grinding by taking water as a medium, and the particle size of the grinding balls is 3-5 mm.
Optionally, in the step C', the temperature of the calcination is 1100 ℃ to 1200 ℃.
The beneficial effects are that: the invention provides a method for processing raw materials of digital ceramic glaze ink, by which raw material powder which can be directly used for preparing the digital ceramic glaze ink is obtained; the raw material powder obtained by the method has the characteristics of high purity and high grade; the calcined raw materials are easy to crush, so that the grinding efficiency is improved, and the ink preparation time is shortened; the digital ceramic glaze ink prepared from the raw material powder obtained by the method has the characteristics of good dispersibility, good uniformity and high stability in a dispersion system of an ink solvent, and is convenient for later storage and jet printing of an ink jet printer.
Drawings
FIG. 1 is a graph showing the particle size distribution of ink particles after calcination and milling in accordance with an embodiment of the present invention.
Detailed Description
The invention provides a raw material treatment method for digital ceramic glaze ink, which is used for making the purposes, technical schemes and effects of the invention clearer and more definite, and is further described in detail below. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a raw material treatment method for digital ceramic glaze ink, which comprises the following steps:
s1, selecting a natural mineral raw material or a rough mineral raw material required for preparing the digital ceramic glaze ink;
s2, calcining each selected raw material respectively;
s3, proportioning the calcined raw materials according to a formula to obtain a mixture;
s4, sequentially grinding the mixture, removing iron, drying, crushing and grading;
and S5, calcining, crushing and grading the graded mixture in sequence to obtain raw material powder.
The embodiment provides a method for processing raw materials of digital ceramic glaze ink, by which raw material powder which can be directly used for preparing the digital ceramic glaze ink is obtained; the raw material powder obtained by the method has the characteristics of high purity and high grade; the calcined raw materials are easy to crush, so that the crushing efficiency is improved, and the ink preparation time is shortened; the digital ceramic glaze ink prepared from the raw material powder obtained by the method has the characteristics of good uniformity and high stability in a dispersion system of an ink solvent.
The selection in step S1 is because many natural mineral raw materials or crude mineral raw materials can be used for preparing the digital ceramic glaze ink, but the raw materials cannot be directly used, and the requirements of the digital ceramic glaze ink are higher than those of the traditional glaze materials, and the natural mineral raw materials or the crude mineral raw materials with high grade and few impurities need to be screened and screened.
The natural mineral raw materials are raw materials which are directly purchased and transported from mines and are not subjected to any artificial treatment, and generally comprise feldspar type, quartz type and various clay type raw materials (mainly comprising kaolin type minerals, montmorillonite type minerals, illite type minerals and the like);
the raw mineral materials are simply crushed or elutriated, and generally comprise feldspar, quartz sand and clay.
In step S2, it should be noted that the selected raw materials are calcined separately, instead of being calcined after being mixed together.
The calcination in step S2 refers to the high-temperature calcination of each of the selected raw materials. The high-temperature calcination is a method for carrying out heat treatment on various screened raw materials by a physical method. For example, when the kaolin mineral is calcined at 900-1100 deg.c, some or all of the hydroxyl groups on the surface of the kaolin mineral may be removed, while new stable phases, such as mullite, cristobalite, etc. may not be formed yet, and the leaching amount of silicon and aluminum is the largest at this time, so that the clay has great activity and thus obtains special physical and chemical properties. In addition, all the selected raw materials contain certain water, and part of the raw materials contain structural water, interlayer water and crystallization water besides free water. Free water, structural water, interlayer water and crystal water in the raw materials can be removed after high-temperature calcination. In the high-temperature heating process of raw materials, free water, structural water, interlayer water and crystallization water are discharged, the lattice structure of hydrous minerals such as kaolin, clay and the like is destroyed, and the raw materials lose plasticity to become barren-like raw materials. In addition to the water in the minerals being removed during calcination, the carbon, sulfide and organics in the minerals are oxidized and the sulfate, carbonate and iron oxide are decomposed. The calcined raw materials lose weight and have high purity, which is beneficial to more accurate subsequent batching.
For kaolin minerals, the metakaolin with disordered structure is changed from the original ordered lamellar crystal structure after high-temperature calcination, so that partial groups of the inner layer of the original crystal are exposed. And the types and the number of the surface active points are increased due to the removal of the crystal water, so that the reactivity of the crystal water is increased. In addition, the particle size of the calcined kaolin minerals is increased, the specific surface area is reduced, the adsorptivity is reduced, but the surface energy is reduced, so that the dispersibility of the kaolin is improved, and the structure is loose due to the amorphous structure, thereby being beneficial to crushing and improving the dispersibility.
For clay minerals, the clay minerals lose crystal water when calcined at 800-850 ℃, the crystal structure is destroyed, the activity and whiteness are improved, and the granularity is regular, and the dispersibility is good.
By way of example, the process conditions for the high temperature calcination are as follows in table 1:
TABLE 1
The above parameters are only one example of the present invention, and are not exhaustive, as long as the purpose of calcining the raw material can be achieved, and the calcining temperature, calcining time, kiln length and kiln type, and the manner of calcining the raw material can be changed, such as changing the roller kiln into a shuttle kiln, etc.
In step S3, the calcined raw materials are mixed according to a formula, specifically, a single raw material is selected from the calcined raw materials to be mixed, or a plurality of raw materials are selected from the calcined raw materials to be mixed according to a formula, so as to obtain a required formula mixture; besides various calcined raw materials, other mineral chemical raw materials can be introduced into the formula for formula adjustment, such as calcite, wollastonite, zirconium silicate, burned zinc oxide and other raw materials. The digital ceramic glaze ink prepared from one or more raw materials is quite many, but the raw materials cannot be directly mixed for preparing the ink, because different raw materials have different raw material properties, especially the specific surface energy of the digital ceramic glaze ink is increased after the digital ceramic glaze ink is processed to the fineness required by the digital ceramic glaze ink, and the performances shown in a solvent dispersion system are different, so that the uniformity and the stability of the ink dispersion system can be influenced. After the treatment in step S2 of this embodiment, the ingredients can be formulated.
Preferably, when a plurality of raw materials are selected from various calcined raw materials and are mixed according to a formula, the selected raw materials are uniformly mixed all at once. As if mixed in batches, the uniformity of the raw material formulation is affected.
In step S4, the mixture may be milled using a ball mill. The grinding may be performed by dry or wet methods. Preferably, the mixture is milled using a ball mill to a 325 mesh screen. Preferably, the mixture is wet milled with an aqueous medium under the action of milling balls. More preferably, the particle size of the grinding balls is 3 mm-5 mm, and the grinding balls are high-alumina ball stones or zirconia balls.
The step S4 of removing iron refers to removing iron from the glaze slip with the fineness of grinding so as to improve the grade and whiteness of raw materials. Preferably, iron removal is performed using a iron removal bar.
The drying in step S4 refers to drying the slip after iron removal by drying, draining or squeezing, etc. to remove the excessive water in the slip.
And S4, carrying out iron removal and drying, then crushing, and grading the crushed raw materials according to the particle size. In this example, the size of the raw material particles after pulverization and classification was controlled under a 200 mesh sieve, and the recovery of the raw material particles on the 200 mesh sieve was continued. Of course, the particle size of the crushed raw materials is not necessarily controlled under a 200-mesh sieve, and the particle size can be adjusted according to the performance requirements of different raw materials.
In the step S5, the mixture processed in the step S4 is put into a sagger again for calcination, and the raw materials after secondary calcination are subjected to secondary crushing and classification. The high temperature calcination mainly fuses fine particles of various mixed raw materials into a raw material with one property except for removing excessive moisture in the raw material, so that the purity of the raw material and the dispersity of the raw material in an ink solvent system are improved, and the stability of the digital ceramic glaze ink is improved. Otherwise, the raw materials which are not subjected to secondary calcination and classification are directly used for preparing the ink, and in a dispersion system of an ink solvent, particles of each raw material still show the original properties of the original raw materials, so that the usability and the stability of the digital ceramic glaze ink are affected.
Further, the temperature of the secondary calcination is 900-1200 ℃.
Further, the secondary calcination time is 45-120 minutes.
Further, the particle diameter of the particles after the secondary pulverization and classification (i.e., the particle diameter of the obtained raw material powder) is controlled to 10 μm or less.
By way of example, the raw material powder parameters obtained after secondary calcination, secondary pulverization and classification in this example, which can be directly used for preparing digital ceramic glaze ink, are shown in table 2 below:
TABLE 2
The embodiment of the invention provides a raw material treatment method for digital ceramic glaze ink, which comprises the following steps:
s1', selecting a natural mineral raw material or a rough mineral raw material required for preparing the digital ceramic glaze ink;
s2', preparing the screened raw materials according to a formula to obtain a mixture;
and S3', sequentially grinding the mixture, removing iron, drying, crushing, grading, calcining, crushing and grading to obtain raw material powder.
The first treatment method comprises two times of calcination, wherein the first time is to calcine each selected raw material separately, and the second time is to calcine the prepared mixture. In this embodiment, each selected raw material is directly blended, and the blended mixture is calcined. Compared with the first treatment method, the embodiment only needs to calcine the formula mixture once, and can also obtain the uniform raw material powder for preparing the digital ceramic glaze ink, but the raw material powder needs to be crushed and graded for multiple times, and the performance of the actual formula raw material has a certain error with the theoretical value and needs to be corrected for multiple times in the later period.
In step S3', further, the mixture particles are ground to a D50 of 5 μm to 10. Mu.m.
Further, under the action of the grinding balls, wet grinding is performed by adopting an aqueous medium. Further, the particle size of the grinding balls is 3-5 mm, and the grinding balls are high-alumina ball stones or zirconia balls.
Further, the drying temperature is 120-220 ℃.
Further, the drying time is as follows: 2-6 h.
Further, preliminary classification (i.e., classification before calcination) is performed to obtain a mixture having a fineness of 80 to 120 mesh.
Further, the calcination temperature is 1100-1200 ℃.
Further, the particle diameter of the particles after the secondary pulverization and classification (i.e., the particle diameter of the obtained raw material powder) is controlled to 10 μm or less.
The two methods for processing the raw materials provided by the embodiment of the invention have the following technical advantages:
1) The raw material powder obtained by the treatment method of the embodiment of the invention has higher purity and better grade. The clay single raw material calcined by the embodiment of the invention can be directly added into balls to be processed into ceramic ink, so that the problems of incapability of sieving, thixotropic processing slurry and the like do not occur;
2) The raw material powder obtained by the treatment method of the embodiment of the invention is used for preparing the digital ceramic glaze ink, so that the loss on ignition is not required to be considered during the batching, and the batching is more accurate and is closer to the theoretical formula value;
3) The raw material powder obtained by the treatment method of the embodiment of the invention is used for preparing the digital ceramic glaze ink, so that the grinding efficiency can be improved, the preparation time of the ink can be shortened, the raw material before calcination is ground to the required fineness for 12-15 hours, and the grinding time is shortened after calcination for only 3 hours;
4) The digital ceramic glaze ink prepared from the raw material powder obtained by the treatment method provided by the embodiment of the invention has better dispersibility, more uniform and stable particle distribution, and is favorable for storing the ink and spraying performance of an ink jet. The raw materials which are not calcined are seriously agglomerated when being ground, cannot be screened, and are difficult to continue to process.
The invention is further illustrated by the following specific examples.
Example 1
According to the mass percentage, 80% of calcined clay, 5% of zirconium silicate, 2% of zinc oxide and 13% of calcined potassium sand are selected for carrying out material mixing and uniform mixing to obtain a mixture, and the mixture is ball-milled into glaze slurry and deironing and drying are carried out. Crushing and classifying the dried mixture, loading the mixture into a sagger by adopting a 200-mesh sieve, calcining the mixture for 90 minutes at a high temperature of 1200 ℃ by adopting a shuttle kiln, taking out the calcined material, crushing and classifying the calcined material again, and obtaining the raw material powder for preparing the ceramic ink. The specific parameters are as follows:
batching parameters: 240g of calcined clay, 15g of zirconium silicate, 6g of zinc oxide and 39g of calcined potassium sand;
grinding time: 15 minutes;
drying temperature: 125 ℃;
drying time: 6h;
first particle classification: sieving with 200 mesh sieve;
second particle classification: and < 10 μm.
The clay before calcination in this example contains more organic matters and other impurities, the purity of the clay is changed, the iron content is reduced, the taste is improved after high-temperature calcination, grinding and deironing, and the detection results are shown in table 3 below:
TABLE 3 Table 3
| Raw materials | IL | SiO 2 | Al 2 O 3 | K 2 O | Na 2 O | CaO | MgO | Fe 2 O 3 | TiO 2 | Total amount of |
| Before calcination | 10.82 | 53.08 | 31.47 | 2.28 | 0.15 | 0.21 | 1.36 | 0.52 | 0.03 | 99.92 |
| After calcination | 0 | 59.84 | 35.48 | 2.57 | 0.17 | 0.24 | 1.53 | 0.13 | 0.03 | 99.99 |
The raw material powder obtained after calcination and grinding in this example is used for preparing the digital ceramic glaze ink: the raw material powder obtained in this example was mixed with a solvent (solvent 1, solvent 2, dispersant and anti-settling agent) to prepare the ink. The ink was prepared in accordance with the following formulations shown in Table 4 (solvent formulation) and Table 5 (ink formulation).
TABLE 4 Table 4
TABLE 5
| Name of the name | Solvent formulation | Raw material powder |
| Material ratio (mass ratio meter) | 60 | 40 |
TABLE 6
| Ink Performance | Viscosity of the mixture | Surface tension | Solid content | D10 | D50 | D90 | Specific surface area |
| Ink parameters | 20mpas | 27mN/m | 40％ | 228nm | 374nm | 615nm | 1718m 2 /kg |
The results of the performance test of the ink prepared according to the above formula are shown in table 6, and the particle size distribution of the ink is: d (10) 228nm; d (50) 374nm; d (90) 615nm, and the particle size distribution diagram is shown in figure 1, so that the particle size distribution diagram is concentrated, the range is narrow, the size difference span of particles is small, the uniform dispersion and the stability in an ink solvent system are facilitated, and the precipitation and the agglomeration are not easy to occur.
Example 2
According to the mass percentage, 60% of natural clay, 15% of potassium feldspar and 25% of albite are selected for proportioning to obtain a mixture, the mixture is subjected to ball grinding, iron removal and drying, the mixture is subjected to preliminary grinding and classification, 120-mesh undersize materials are taken and put into a sagger, and the sagger is subjected to high-temperature calcination at 1200 ℃ for 120 minutes by adopting a shuttle kiln. And crushing and grading the calcined material to obtain the powder for preparing the ceramic ink. The specific parameters are as follows:
batching parameters: 180g of natural clay, 45g of potassium feldspar and 75g of albite;
grinding time: 15 minutes;
drying temperature: 125 ℃;
drying time: 6h;
first particle classification: sieving with 120 mesh sieve;
second particle classification: and < 10 μm.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (1)
1. The method for processing the raw material for the digital ceramic glaze ink is characterized by comprising the following steps of:
step A, selecting a natural mineral raw material or a rough mineral raw material required for preparing the digital ceramic glaze ink;
step B, calcining each selected raw material respectively;
step C, proportioning the calcined raw materials according to a formula to obtain a mixture;
step D, grinding the mixture in sequence, removing iron, drying, crushing and grading;
step E, the mixture processed in the step D is calcined, crushed and graded in sequence to obtain raw material powder;
the mineral raw material is selected from one or more of feldspar raw materials, quartz raw materials and clay raw materials;
the particle size of the raw material powder is controlled below 10 mu m;
the grinding process conditions are as follows: under the action of grinding balls, water is used as a medium, the mixture is subjected to wet grinding, and the particle size of the grinding balls is 3-5 mm;
in the step D, the particle size of the raw material after grinding treatment is controlled under a 325-mesh screen;
in the step D, the particle size of the raw material after classification is controlled under a 200-mesh screen;
in the step E, the calcining temperature is 900-1200 ℃.
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| CN108483908A (en) * | 2018-05-08 | 2018-09-04 | 日照众文陶瓷科技有限公司 | A kind of granite tailing extract prepares yellowish-brown and has the method for pearl effect powdered frit |
| CN110964524A (en) * | 2019-12-25 | 2020-04-07 | 温州大学新材料与产业技术研究院 | Red, green, yellow and blue fluorescent powder and preparation method thereof |
| CN112608028A (en) * | 2020-12-31 | 2021-04-06 | 江苏南瓷绝缘子股份有限公司 | High-strength suspension insulator head glaze and preparation method thereof |
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