CN118388138A - Needle-like crystal particles and application thereof - Google Patents
Needle-like crystal particles and application thereof Download PDFInfo
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- CN118388138A CN118388138A CN202410832020.9A CN202410832020A CN118388138A CN 118388138 A CN118388138 A CN 118388138A CN 202410832020 A CN202410832020 A CN 202410832020A CN 118388138 A CN118388138 A CN 118388138A
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- 239000013078 crystal Substances 0.000 title claims abstract description 128
- 239000002245 particle Substances 0.000 title claims abstract description 56
- 239000000919 ceramic Substances 0.000 claims abstract description 31
- 230000000694 effects Effects 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000000049 pigment Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000002844 melting Methods 0.000 claims abstract description 11
- 230000008018 melting Effects 0.000 claims abstract description 11
- 238000010304 firing Methods 0.000 claims abstract description 10
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 235000019738 Limestone Nutrition 0.000 claims abstract description 5
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 5
- 239000010459 dolomite Substances 0.000 claims abstract description 5
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 5
- 239000010433 feldspar Substances 0.000 claims abstract description 5
- 239000006028 limestone Substances 0.000 claims abstract description 5
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010456 wollastonite Substances 0.000 claims abstract description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 5
- 238000007670 refining Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000011534 incubation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003086 colorant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004579 marble Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000001609 comparable effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention belongs to the field of ceramics, and discloses needle-shaped crystal particles and application thereof. The needle-like crystal particles are prepared from potassium-sodium feldspar, wollastonite, dolomite, limestone, boron oxide and pigment by refining, mixing, melting at above 1700 deg.C, maintaining temperature, crystallizing, cooling, disintegrating, and cutting. The invention initiates needle crystal particles in the ceramic industry, and can be conveniently fired to obtain the needle effect ceramic. The raw materials are melted at 1700-2000 ℃ while being stirred at a constant temperature, so that the raw materials are fully fused to be completely melted to form a liquid state, then the liquid state is cooled and crystallized, and after rapid cooling, the liquid state is disintegrated into incomplete small-block crystals, and needle-like effect textures in various forms can be naturally formed in the crystals to obtain needle-like crystal particles. The needle-shaped crystal particles have good thermal stability and good stability at the firing temperature of ceramics, and the needle-shaped effect of the needle-shaped crystal particles is still maintained after firing, so that the firing of the needle-shaped effect ceramics is possible.
Description
Technical Field
The invention belongs to the field of ceramics, and particularly relates to needle-shaped crystal particles and application thereof.
Background
With the upgrading of the demand of decoration consumption and the mature development of industry technology, rock crystals also start to appear in the field of building ceramics as high-quality ornamental elements, and a strand of ceramic tiles are lifted to be 'crystal tide'. However, rock crystals are rare products of nature, and the formation conditions are severe, so that the rock crystals are difficult to imitate, and the aim of realizing special crystallization effects like rock crystals on ceramic tiles in a stable and controllable manner by manual means is not easy.
The existing crystal ceramic tile products basically have granular crystal forms. The main presentation forms of the needle-like effect are radial fiber, flocculent, needle-like, dry granular, platy and strip-like, and the visual sense is novel and unique, so that not only can the crystal types of the tile decoration be further enriched, but also a tile product designer can obtain new choices in element collocation and citation, and the inspiration creation space is widened. In addition, when the needle-shaped dry particles are applied to the re-engraving of natural marble containing various bar-shaped crystals, higher reduction degree and fidelity can be obtained, and the natural aesthetic feeling of the product is improved.
The needle-shaped material is easy to deform and even co-melt with other glaze raw materials in the firing process, and the preset shape of the needle-shaped material cannot be maintained, so that ceramic tiles with needle-shaped effects are not seen in the market. It is a difficult task to develop crystalline particles that can fire acicular effect ceramics.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art and provides needle-shaped crystal particles and application thereof.
The technical scheme adopted by the invention is as follows:
In a first aspect of the invention, there is provided:
The needle-shaped crystal particles comprise the following raw materials in parts by mass: 10-35 parts of potassium-sodium feldspar, 40-60 parts of wollastonite, 20-45 parts of dolomite, 7-15 parts of limestone, 0-15 parts of boron oxide and a proper amount of pigment, and the preparation method comprises the following steps:
S1) weighing raw materials according to the composition of needle crystal particles, refining and uniformly mixing;
S2) melting the uniformly mixed raw materials at 1700-2000 ℃, and keeping the temperature and stirring to be not lower than 4h to obtain a molten liquid;
S3) feeding the molten liquid into a 1350-1500 ℃ crystallizing furnace, and continuously preserving heat to enable the molten liquid to be completely crystallized to obtain crystals;
s4) cooling the completely crystallized crystals while the crystals are hot, so that the crystals are cracked and disintegrated into incomplete small-block crystals due to the temperature difference between the inside and the outside, and shearing the small-block crystals to a specified mesh number to obtain needle-shaped crystal particles.
In some examples of needle-like crystal particles, in step S2), the incubation time is 4 to 7 hours.
In some examples of needle-like crystal particles, in step S3), the incubation time is 3 to 7 hours.
In some examples of needle-like crystal particles, in step S4), the cooling rate is not less than 50 ℃/min.
In some examples of needle-like crystal particles, in step S4), the cooling is room temperature air cooling.
In some examples of needle-like crystal particles, the chemical mass composition is: siO 2 45～70%、Al2O3 5～15%、CaO 10～30%、MgO 0～3%、B2O3 is 0-8%, pigment is proper, and the rest is impurity.
In some examples of needle-like crystal particles, the pigment is used in an amount of 0 to 3% of the total mass of the needle-like crystal particles.
In some examples of needle-like crystal particles, the pigment is selected from at least one of a glaze color, a green color, and a dry mix color.
In some examples of acicular crystal particles, the shape is radial fiber, floc, acicular, plate, or strip.
The above technical features can be arbitrarily combined without conflict.
In a second aspect of the invention, there is provided:
an acicular effect glaze is obtained by adding the acicular crystal particles according to the first aspect of the present invention to glaze slip or dry granular glaze.
In some examples of acicular effect glazes, the glaze slip is selected from colored glaze slips or transparent glaze slips; the dry grain glaze is selected from colored dry grain glaze, transparent dry grain glaze, matte dry grain glaze or bright dry grain glaze.
In a third aspect of the invention, there is provided:
a ceramic having an acicular effect, the glaze of which is added with acicular crystal particles according to the first aspect of the present invention.
In some examples of ceramics, the firing temperature is 1170-1230 ℃.
The beneficial effects of the invention are as follows:
The invention initiates needle crystal particles in the ceramic industry, and can be conveniently fired to obtain the needle effect ceramic.
The inventor fuses raw materials at 1700-2000 ℃ while preserving heat and stirring, so that the raw materials are fully fused to be completely fused to form a liquid state, then cooling and crystallizing, rapidly cooling and then disintegrating into incomplete small-block crystals, and naturally forming needle-like effect textures in various forms in the crystals to obtain needle-like crystal particles. The needle-shaped crystal particles have good thermal stability and good stability at common ceramic firing temperature, and the needle-shaped effect of the needle-shaped crystal particles is still maintained after firing, so that the firing of the needle-shaped effect ceramic is possible.
Drawings
Fig. 1 is a photograph of the sample tile of examples 1 to 5.
FIG. 2 is a photograph of the sample tiles of comparative examples 1 to 6.
Detailed Description
In a first aspect of the invention, there is provided:
The needle-shaped crystal particles comprise the following raw materials in parts by mass: 10-35 parts of potassium-sodium feldspar, 40-60 parts of wollastonite, 20-45 parts of dolomite, 7-15 parts of limestone, 0-15 parts of boron oxide and a proper amount of pigment, and the preparation method comprises the following steps:
S1) weighing raw materials according to the composition of needle crystal particles, refining and uniformly mixing;
S2) melting the uniformly mixed raw materials at 1700-2000 ℃, and keeping the temperature and stirring to be not lower than 4h to obtain a molten liquid;
S3) feeding the molten liquid into a 1350-1500 ℃ crystallizing furnace, and continuously preserving heat to enable the molten liquid to be completely crystallized to obtain crystals;
s4) cooling the completely crystallized crystals while the crystals are hot, so that the crystals are cracked and disintegrated into incomplete small-block crystals due to the temperature difference between the inside and the outside, and shearing the small-block crystals to a specified mesh number to obtain needle-shaped crystal particles.
The raw materials are melted at 1700-2000 ℃, on one hand, the raw materials are melted to facilitate the subsequent uniform mixing, and on the other hand, the melted raw materials are further reacted to form a new crystal structure by the high temperature effect, so that the needle-shaped crystal particles are facilitated to be obtained. The lower the melting temperature, the more difficult it is to form new crystal structure, and the more difficult it is to prepare needle crystal particles.
The longer the stirring time is, the more homogeneous molten liquid is obtained, and the uniformity of the product is ensured. However, the heat preservation time is too long, more energy sources are required to be consumed, and the production cost is increased. In some examples of needle-like crystal particles, in step S2), the incubation time is 4 to 7 hours. This ensures the quality of the melt and is also relatively economical.
The growth of the crystal is facilitated by prolonging the time of heat preservation and crystallization. However, the heat preservation time is too long, more energy sources are required to be consumed, and the production cost is increased. In some examples of needle-like crystal particles, in step S3), the incubation time is 3 to 7 hours. This ensures that sufficiently large crystals are obtained, which is also relatively economical.
In some examples of needle-like crystal particles, in step S4), the cooling rate is not less than 50 ℃/min. At this cooling rate, various needle-like streaks are advantageously formed inside the crystal.
In some examples of needle-like crystal particles, in step S4), the cooling is room temperature air cooling. This makes it possible to obtain a satisfactory cooling rate. Of course, other methods of cooling may be used.
In some examples of needle-like crystal particles, the raw materials have the following mass composition: 10-20 parts of potassium-sodium feldspar, 40-50 parts of wollastonite, 20-25 parts of dolomite, 7-10 parts of limestone, 3-10 parts of boron oxide and 1-3 parts of pigment. In particular, the pigment is rutile.
In some examples of needle-like crystal particles, the chemical mass composition is: siO 2 45～70%、Al2O3 5～15%、CaO 10～30%、MgO 0～3%、B2O3 is 0-8%, pigment is proper, and the rest is impurity.
The amount of pigment can be adjusted accordingly according to the color requirements. In some examples of needle-like crystal particles, the pigment is used in an amount of 0 to 3% of the total mass of the needle-like crystal particles.
The kind of pigment is not particularly limited, and in some examples of the needle-like crystal particles, the pigment is selected from at least one of a colorant for glaze, a colorant for green, and a dry-mixed colorant.
In some examples of needle-like crystal particles, the pigment includes rutile, titanium dioxide, and the like. TiO 2 can improve whiteness and is favorable for color development.
In some examples of acicular crystal particles, the shape is radial fiber, floc, acicular, plate, or strip.
In a second aspect of the invention, there is provided:
an acicular effect glaze is obtained by adding the acicular crystal particles according to the first aspect of the present invention to glaze slip or dry granular glaze.
In some examples of acicular effect glazes, the glaze slip is selected from colored glaze slips or transparent glaze slips; the dry grain glaze is selected from colored dry grain glaze, transparent dry grain glaze, matte dry grain glaze or bright dry grain glaze. The glaze slip is not particularly limited, and may be selected as required, and needle-like crystal particles may be added after the glaze slip is prepared.
In a third aspect of the invention, there is provided:
a ceramic having an acicular effect, the glaze of which is added with acicular crystal particles according to the first aspect of the present invention.
In some examples of ceramics, the firing temperature is 1170-1230 ℃.
The technical scheme of the invention is further described below by combining examples.
For convenience, in the following examples, if not specifically stated, the melting temperature is unified to 1850 ℃, the crystallization reaction temperature is unified to 1450 ℃, the cooling mode is unified to air cooling, the blank is a conventional blank, and the tile process is unified to a full polishing process.
TABLE 1 raw materials weight parts composition (parts) and melting time (h) State Table in different examples
Note that: s represents the example and D represents the comparative example.
Comparative example 5, which is identical to example 1, differs in that the melting temperature is 1500 ℃.
Comparative example 6, which is identical to example 1, differs in that the crystallization temperature is 1300 ℃.
Preparation of sample tiles
Crushing the crystals prepared by sintering the raw materials into 30-60 meshes, and mixing with common transparent glaze slurry according to the following ratio of 1:1, uniformly mixing, scraping the mixture on the surface of the green brick by using a 0.7mm thick glaze scraper, drying, sintering at 1180 ℃ and fully polishing.
The photographs of the sample tiles of examples 1 to 5 are shown in fig. 1, and the photographs of the sample tiles of comparative examples 1 to 6 are shown in fig. 2.
The ceramic tile of example 1 has a smooth glaze, a long and distinct crystal, a strong gloss, and a comparable effect to natural crystals at a certain angle.
The tile of example 2 has a smooth glaze, long but densely distributed crystals, strong gloss, and a cotton-like effect comparable to that naturally produced in natural marble at a certain angle.
The ceramic tile of example 3 has flat glaze, long crystals, wide crystal spacing, wide crystal refraction surface, strong decorative effect and obvious single crystal.
The ceramic tile of example 4 has smooth glaze, short crystals and wider crystal spacing, rich crystal accumulation effect, strong decorative effect and obvious single crystal.
The ceramic tile of example 5 has smooth glaze, long crystals, wide crystal spacing, wide crystal refraction surface and beautiful decorative effect.
The tile of comparative example 1 has a smooth glaze, incomplete crystal melting, yellowing crystal color, poor gloss and poor decorative effect.
The ceramic tile of comparative example 2 has a smooth glaze, incomplete crystal reaction, few crystals generated by the large-sized frit, high material cost and difficult crushing.
The ceramic tile of comparative example 3 has smooth glaze, disordered crystal distribution, short and thin crystal, small range of crystal refractive surface, weak decorative effect, few visible crystals and no obvious single crystal.
The ceramic tile of comparative example 4 has a smooth glaze, no crystal disappearing, no crystal refracting surface, and no decorative effect.
The ceramic tile of comparative example 5 has a smoother glaze, but the melting temperature is not enough, no crystal is precipitated, and the effect is not different from that of the common frit.
The ceramic tile of comparative example 6 has more pits on the glaze, insufficient crystallization temperature, difficult crystal precipitation and no application value.
From the observation data, the content in the formula and the specific temperature deviate from the normal range, and the growth and the crystal form of needle-shaped crystals can be caused; insufficient melting temperature can not sufficiently melt the material, and failure of needle crystals can be caused by failure of the temperature point of the crystal form transition; when the crystallization temperature is insufficient, the crystal formation is difficult, no crystal is directly precipitated, and the crystal effect is directly lost.
The above description of the present invention is further illustrated in detail and should not be taken as limiting the practice of the present invention. It is within the scope of the present invention for those skilled in the art to make simple deductions or substitutions without departing from the concept of the present invention.
Claims (10)
1. The needle-shaped crystal particles are characterized by comprising the following raw materials in mass: 10-35 parts of potassium-sodium feldspar, 40-60 parts of wollastonite, 20-45 parts of dolomite, 7-15 parts of limestone, 0-15 parts of boron oxide and a proper amount of pigment, and the preparation method comprises the following steps:
S1) weighing raw materials according to the composition of needle crystal particles, refining and uniformly mixing;
S2) melting the uniformly mixed raw materials at 1700-2000 ℃, and keeping the temperature and stirring to be not lower than 4h to obtain a molten liquid;
S3) feeding the molten liquid into a 1350-1500 ℃ crystallizing furnace, and continuously preserving heat to enable the molten liquid to be completely crystallized to obtain crystals;
s4) cooling the completely crystallized crystals while the crystals are hot, so that the crystals are cracked and disintegrated into incomplete small-block crystals due to the temperature difference between the inside and the outside, and shearing the small-block crystals to a specified mesh number to obtain needle-shaped crystal particles.
2. The needle-like crystal grain according to claim 1, wherein in step S2), the time for heat preservation is 4 to 7 hours.
3. The needle-like crystal grain according to claim 1, wherein in step S3), the holding time is 3 to 7 hours.
4. The needle-like crystal grain according to claim 1, wherein in step S4), the cooling rate is not lower than 50 ℃/min.
5. Needle-like crystal particles according to claim 1, characterized in that they have the chemical mass composition: siO 2 45～70%、Al2O3 5～15%、CaO 10～30%、MgO 0～3%、B2O3 is 0-8%, pigment is proper, and the rest is impurity.
6. The needle-like crystal particles according to claim 1, which are in the form of radial fibers, flocs, needles, plates or strips.
7. An acicular effect glaze characterized by being obtained by adding the acicular crystal particles according to any one of claims 1 to 6 to a glaze slip or a dry granular glaze.
8. The acicular effect glaze according to claim 7, wherein the glaze slip is selected from colored glaze slips or transparent glaze slips; the dry grain glaze is selected from colored dry grain glaze, transparent dry grain glaze, matte dry grain glaze or bright dry grain glaze.
9. A ceramic having an acicular effect, characterized in that the acicular crystal particles as defined in any one of claims 1 to 6 are added to the glaze.
10. The ceramic of claim 9, wherein the firing temperature is 1170-1230 ℃.
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| CN202410832020.9A CN118388138B (en) | 2024-06-26 | 2024-06-26 | Needle-like crystal particles and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202410832020.9A CN118388138B (en) | 2024-06-26 | 2024-06-26 | Needle-like crystal particles and application thereof |
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| CN118388138A true CN118388138A (en) | 2024-07-26 |
| CN118388138B CN118388138B (en) | 2024-08-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145456A (en) * | 1988-11-28 | 1990-06-04 | Central Glass Co Ltd | Crystalline glass and production thereof |
| JPH11314942A (en) * | 1998-04-30 | 1999-11-16 | Nitto Boseki Co Ltd | Colored glass powder |
| CN112851120A (en) * | 2021-01-21 | 2021-05-28 | 景德镇陶瓷大学 | Microcrystalline wear-resistant transparent glaze and preparation method and application of glaze slip thereof |
| CN115521071A (en) * | 2022-10-29 | 2022-12-27 | 广东道氏陶瓷材料有限公司 | Dry particles of composite high-temperature wear-resistant material and ceramic |
-
2024
- 2024-06-26 CN CN202410832020.9A patent/CN118388138B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02145456A (en) * | 1988-11-28 | 1990-06-04 | Central Glass Co Ltd | Crystalline glass and production thereof |
| JPH11314942A (en) * | 1998-04-30 | 1999-11-16 | Nitto Boseki Co Ltd | Colored glass powder |
| CN112851120A (en) * | 2021-01-21 | 2021-05-28 | 景德镇陶瓷大学 | Microcrystalline wear-resistant transparent glaze and preparation method and application of glaze slip thereof |
| CN115521071A (en) * | 2022-10-29 | 2022-12-27 | 广东道氏陶瓷材料有限公司 | Dry particles of composite high-temperature wear-resistant material and ceramic |
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