Ice crystal dry granules, method for preparing the same, and ceramic tile

Abstract

This invention discloses a dry ice crystal particle, its preparation method, and a ceramic tile, relating to the field of ceramic tile technology. The dry ice crystal particle is prepared from a first flashing frit, a second flashing frit, and a matte frit. Since the dry ice crystal particle is composed of three frits with different refractive indices and firing temperatures, different phases can be formed due to the different firing temperatures of each frit. The differences in light transmittance and refractive index between these phases are then utilized to create a better flashing effect. Simultaneously, the matte glaze serves as a backdrop, further enhancing the display of the flashing effect.

Description

Technical Field

[0001] This invention relates to the field of ceramic technology, and in particular to a dry ice crystal granule, its preparation method, and ceramic tiles. Background Technology

[0002] Tiles, as a decorative material, are widely used for decorating both floors and walls. Among existing technologies, shimmering dry-granule tiles are particularly popular with consumers because they produce a shimmering effect under light and are widely used in hotels, bars, and other entertainment venues. However, existing shimmering dry-granule tiles typically achieve their effect through the refraction of pyroxene and sphene crystals, or by introducing diamond-like luster sand with high refractive index and high initial melting temperature. However, these shimmering components are highly sensitive to incident light; otherwise, the shimmering effect is not noticeable under normal or dim light conditions. Therefore, existing technology still needs improvement and enhancement. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the purpose of this invention is to provide ice crystal dry granules, a method for preparing the same, and ceramic tiles, in order to solve the problem that existing ice crystal dry granules do not have a good enough shimmering effect under low light conditions.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A type of dry ice crystal pellet, wherein the dry ice crystal pellet comprises a first flashing melt, a second flashing melt, and a matte melt.

[0006] The chemical composition of the first flashing molten block, by mass percentage, in the aforementioned ice crystal dry particles is: SiO2: 60-70%, Al2O3: 15.3-18.6%, CaO: 5.1-8.5%, Na2O: 3.0-7.4%, K2O: 0.5-2.1%, ZnO: 1.1-2%, TiO2: 0.8-1.3%, with the balance being loss on ignition.

[0007] According to claim 1, the chemical composition of the second flashing molten metal, by mass percentage, is: SiO2: 56.2-60%, Al2O3: 11.3-14.5%, CaO: 8.2-9.8%, ZnO: 5.7-6.9%, MgO: 2.1-3.1%, K2O: 4.4-6.2%, Na2O: 1.5-3.1%, with the balance being loss on ignition.

[0008] The chemical composition of the matte frit, by mass percentage, in the ice crystal dry particles is as follows: SiO2: 54-61%, Al2O3: 17-21%, CaO: 4.9-5.6%, K2O: 4.9-5.5%, Na2O: 6.0-7.0%, BaO: 1.2-2.1%, Li2O: 0.2-0.3%, F: 0.05-0.1%, SrO: 0.08-0.2%, with the balance being loss on ignition.

[0009] In the aforementioned dry ice crystal particles, the weight ratio of the first flashing melt, the second flashing melt, and the matte melt is 2:3:2.

[0010] A method for preparing ice crystal dry granules as described above, wherein a first flashing melt, a second flashing melt, and a matte melt are ball-milled and sieved to obtain a mixed powder; the mixed powder, additives, and water are taken and stirred to obtain a mixed slurry; the mixed slurry is granulated by passing it through a centrifugal spray drying tower to obtain ice crystal dry granules.

[0011] In the method for preparing ice crystal dry granules, the additives include polyvinyl alcohol, bentonite, and sodium lignin carbonate.

[0012] In the method for preparing the ice crystal dry particles, the particle size of the ice crystal dry particles is 100-150 μm.

[0013] In the method for preparing ice crystal dry granules, the temperature inside the centrifugal spray drying tower is 250–350°C.

[0014] A ceramic tile includes a body, a base glaze layer disposed on the body, a pattern layer disposed on the base glaze layer, a top glaze layer disposed on the pattern layer, a dry granule layer disposed on the top glaze layer, and a protective glaze layer disposed on the dry granule layer; the dry granule layer is prepared from ice crystal dry granules as described above.

[0015] Beneficial effects:

[0016] This invention provides ice crystal dry granules, their preparation method, and ceramic tiles. The ice crystal dry granules are composed of three frits with different refractive indices and firing temperatures. Different phases are formed by utilizing the different firing temperatures, and the differences in light transmittance and refractive index between the phases are used to create a better glitter effect. At the same time, the matte glaze can be used as a backdrop, and the glitter effect is good under both normal light and dark light conditions.

[0017] The ice crystal dry granules are formed into granules from three different frits using a centrifugal spray drying device, resulting in ice crystal dry granules of suitable size with a good flashing effect.

[0018] Tiles using these ice crystal dry granules as the dry granule layer can achieve a higher refractive index. At the same time, the matte frit can reduce the gloss of the glaze, thus allowing the ice crystal dry granules to still have a shimmering effect even in poor lighting conditions. Attached Figure Description

[0019] Figure 1 The image shows a physical example of a ceramic tile with a shimmering effect, provided by this invention.

[0020] Figure 2 This is a photograph of the actual tile described in Comparative Example 1. Detailed Implementation

[0021] This invention provides dry ice crystal granules, a method for preparing the same, and ceramic tiles. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the following embodiments are provided for further detailed explanation. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0022] This invention provides ice crystal dry granules, which are composed of multiple frits, including a first flashing frit, a second flashing frit, and a matte frit. The first and second flashing frits have high refractive indices, thus exhibiting a flashing effect. The matte frit, possessing matte properties, serves as a backdrop for the first and second flashing frits. During firing, the ice crystal dry granules composed of the first flashing frit, the second flashing frit, and the matte frit result in the formation of different phases within the same granule due to varying firing temperatures. This creates an ice crystal effect between the phases, resulting in a higher refractive index and, with the matte frit as a backdrop, an even better flashing effect.

[0023] In this embodiment, ice crystal dry particles are formed by combining three frits with different refractive indices and firing temperatures. The different firing temperatures create different phases, and the differences in light transmittance and refractive index between these phases result in a better flashing effect. To ensure that the first flashing frit, the second flashing frit, and the matte frit have different refractive indices, in a preferred embodiment, the chemical compositions of the first flashing frit, the second flashing frit, and the matte frit are as follows:

[0024] The chemical composition of the first flashing frit, by mass percentage, is: SiO2: 60–70%, Al2O3: 15.3–18.6%, CaO: 5.1–8.5%, Na2O: 3.0–7.4%, K2O: 0.5–2.1%, ZnO: 1.1–2%, TiO2: 0.8–1.3%, with the balance being loss on ignition. The high proportions of SiO2 and Al2O3 in this first flashing frit result in a higher firing temperature; both ZnO and TiO2 can increase the refractive index of the frit, and ZnO, in particular, can form a crystalline glaze, resulting in a better flashing effect.

[0025] The chemical composition of the second flash frit, by mass percentage, is as follows: SiO2: 56.2–60%, Al2O3: 11.3–14.5%, CaO: 8.2–9.8%, ZnO: 5.7–6.9%, MgO: 2.1–3.1%, K2O: 4.4–6.2%, Na2O: 1.5–3.1%, with the balance being loss on ignition. The proportions of SiO2 and Al2O3 in this second flash frit are lower than those in the first flash frit. Furthermore, the addition of a higher content of ZnO lowers its firing temperature. Simultaneously, the ZnO can form crystal patterns, resulting in a better flashing effect.

[0026] The chemical composition of the matte frit, by mass percentage, is as follows: SiO2: 54–61%, Al2O3: 17–21%, CaO: 4.9–5.6%, K2O: 4.9–5.5%, Na2O: 6.0–7.0%, BaO: 1.2–2.1%, Li2O: 0.2–0.3%, F: 0.05–0.1%, SrO: 0.08–0.2%, with the balance being loss on ignition. The ratio of SiO2 to Al2O3 in this matte frit is between 3 and 4, giving it a matte finish. To achieve a lower melting temperature, a higher content of fluxes K2O and Na2O is added.

[0027] Therefore, in this embodiment, by using a first flashing frit, a second flashing frit, and a matte frit with different chemical compositions, different phases can be formed during firing due to their different melting temperatures. At the same time, ZnO or TiO2, which can improve the refractive index, is added to the first flashing frit and the second flashing frit, thereby enabling both to have a better flashing effect. Meanwhile, using the matte frit as a separator between the two allows the first flashing frit and the second flashing frit to still have a good flashing effect even under insufficient light conditions.

[0028] In the aforementioned dried ice crystal particles, the ratio of the first flashing melt, the second flashing melt, and the matte melt affects the flashing effect. The matte melt, serving as a complement to the first and second flashing melts, should not be present in too low a concentration; otherwise, the flashing effect of both melts will decrease. Experiments have shown that a better flashing effect is achieved when the weight ratio of the first flashing melt to the second flashing melt is (1-3):(1-3):(1-3). More preferably, an even better flashing effect is achieved when the weight ratio of the first flashing melt to the second flashing melt is 2:3:2.

[0029] A second aspect of this invention also provides a method for preparing ice crystal dry granules. This method involves forming spherical particles from a first flashing frit, a second flashing frit, and a matte frit in a centrifugal spray drying tower through the binding action of an additive. This facilitates the formation of ice crystal particles after firing, thereby creating a flashing effect. Specifically, the method for preparing ice crystal dry granules includes the following steps: taking the first flashing frit, the second flashing frit, and the matte frit according to a specified ratio, ball milling them at high speed using a ball mill, and then sieving them through a sieve to obtain a mixed powder; taking the mixed powder, additive, and water, stirring and mixing them to form a mixed slurry; and granulating the mixed slurry through a centrifugal spray drying tower to obtain ice crystal dry granules.

[0030] In this preparation method, the sprayed mixed slurry can be dried rapidly by the action of a centrifugal spray drying tower. During the drying process, the first flash frit, the second flash frit, and the matte frit are agglomerated into spherical particles by the action of additives, which makes it easier to use as dry granules.

[0031] In the above preparation method, the additives include polyvinyl alcohol, bentonite, and sodium lignin carbonate. Polyvinyl alcohol has good binding properties, enabling the first flash melt, second flash melt, and matte melt to agglomerate into particles. Bentonite has a suspending effect, preventing the deposition of the first flash melt, second flash melt, and matte melt. Sodium lignin carbonate is a dispersant, allowing the first flash melt, second flash melt, and matte melt to be well dispersed in water, forming a uniform mixed slurry. Through the action of these additives, a uniform mixed slurry can be obtained, preventing clogging of the spray pipe during centrifugal spray drying, and also ensuring a more uniform particle size.

[0032] In a preferred embodiment, the ice crystal dry particles have a particle size of 100–150 μm. Ice crystal dry particles within this particle size range produce a better flashing effect. To obtain ice crystal dry particles within this particle size range, it is necessary to control the particle size of the mixed powder, the solid content of the mixed slurry, the rotation speed of the spray head, and the temperature inside the centrifugal spray drying tower. In a preferred embodiment, the particle size of the mixed powder is ≤5μm by ball milling and sieving, so that the mixed powder can be better dispersed in water. At the same time, the solid content in the mixed slurry is kept between 50% by adjusting the ratio of mixed powder, additives and water. Furthermore, the rotation speed of the spray head is controlled at 8000-12000 r / min to ensure that the speed at which the mixed slurry is sprayed into the drying tower is moderate and the residence time in the drying tower is appropriate. Moreover, the temperature inside the centrifugal spray drying tower is controlled at 250-350℃ to ensure that the sprayed mixed slurry particles are dried rapidly, forming ice crystal dry particles with a particle size of 100-150μm, which have a better flashing effect.

[0033] A third aspect of the present invention also provides a ceramic tile, which includes a body, a base glaze layer disposed on the body, a pattern layer disposed on the base glaze layer, a top glaze layer disposed on the pattern layer, a dry granule layer disposed on the top glaze layer, and a protective glaze layer disposed on the dry granule layer. The dry granule layer is prepared from ice crystal dry granules as described above. Therefore, after firing, a shimmering effect can be formed on the surface of the tile. This shimmering effect is obtained by the formation of different crystalline phases of the first and second shimmering frits in the ice crystal dry granules. At the same time, through the isolation and highlighting effect of the matte frits, a certain shimmering effect can be presented even under low light conditions.

[0034] It should be noted that the body, base glaze layer, pattern layer, top glaze layer and protective glaze layer are all existing technologies and will not be described in detail here.

[0035] To further illustrate the ice crystal dry granules, their preparation method, and ceramic tiles provided by this invention, the following embodiments are provided.

[0036] Example 1

[0037] A type of ice crystal dry granules, the granules comprising a first flashing frit, a second flashing frit, and a matte frit in a 1:1:1 weight ratio.

[0038] The chemical composition of the first flashing molten block, by mass percentage, is: SiO2: 60%, Al2O3: 18.6%, CaO: 8.5%, Na2O: 7.4%, K2O: 2.1%, ZnO: 2%, TiO2: 1.3%, with the balance being loss on ignition.

[0039] The chemical composition of the second flashing molten metal, by mass percentage, is: SiO2: 56.2%, Al2O3: 14.5%, CaO: 9.8%, ZnO: 6.9%, MgO: 3.1%, K2O: 6.2%, Na2O: 1.5-3.1%, with the balance being loss on ignition.

[0040] The chemical composition of the matte frit, by mass percentage, is: SiO2: 54%, Al2O3: 21%, CaO: 5.6%, K2O: 5.5%, Na2O: 7.0%, BaO: 2.1%, Li2O: 0.3%, F: 0.1%, SrO: 0.2%, with the balance being loss on ignition.

[0041] The method for preparing the ice crystal dry particles is as follows: take the first flashing frit, the second flashing frit, and the matte frit according to the ratio, ball mill them at high speed, and then sieve them to obtain a mixed powder with a particle size ≤5μm; take the mixed powder, additives, and water, stir and mix them to form a mixed slurry with a solid content of 50%; spray the mixed slurry into a centrifugal spray drying tower, with the spray head rotating at 12000r / min and the temperature inside the drying tower at 250-350℃, and obtain ice crystal dry particles with a particle size of 100-150μm by centrifugal drying.

[0042] The ice crystal dry granules described in Example 1 are used in the production of ceramic tiles, which include a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer.

[0043] Example 2

[0044] A type of ice crystal dry granules, the granules comprising a first flashing frit, a second flashing frit, and a matte frit in a weight ratio of 3:1:2.

[0045] The chemical composition of the first flashing molten block, by mass percentage, is: SiO2: 70%, Al2O3: 15.3%, CaO: 5.1%, Na2O: 3.0%, K2O: 0.5%, ZnO: 1.1%, TiO2: 0.8%, with the balance being loss on ignition.

[0046] The chemical composition of the second flashing molten block, by mass percentage, is: SiO2: 60%, Al2O3: 11.3%, CaO: 8.2%, ZnO: 5.7%, MgO: 2.1%, K2O: 4.4%, Na2O: 1.5%, with the balance being loss on ignition.

[0047] The chemical composition of the matte frit, by mass percentage, is: SiO2: 61%, Al2O3: 17%, CaO: 4.9%, K2O: 4.9%, Na2O: 6.0%, BaO: 1.2%, Li2O: 0.2%, F: 0.05%, SrO: 0.08%, with the balance being loss on ignition.

[0048] The ice crystal dry granules described in Example 2 are used in the production of ceramic tiles, which include a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer.

[0049] Example 3

[0050] A type of dry ice crystal pellet, wherein the pellet comprises a first flashing frit, a second flashing frit, and a matte frit in a weight ratio of 2:3:2.

[0051] The chemical composition of the first flashing molten block, by mass percentage, is: SiO2: 68%, Al2O3: 16.6%, CaO: 6.2%, Na2O: 4.5%, K2O: 1.5%, ZnO: 1.5%, TiO2: 1.1%, with the balance being loss on ignition.

[0052] The chemical composition of the second flashing molten block, by mass percentage, is: SiO2: 58%, Al2O3: 12%, CaO: 8.8%, ZnO: 5.5%, MgO: 2.8%, K2O: 5%, Na2O: 2%, with the balance being loss on ignition.

[0053] The chemical composition of the matte frit, by mass percentage, is: SiO2: 55%, Al2O3: 18%, CaO: 5%, K2O: 5.2%, Na2O: 6.5%, BaO: 1.8%, Li2O: 0.2%, F: 0.08%, SrO: 0.1%, with the balance being loss on ignition.

[0054] The ice crystal dry granules described in Example 3 are used in the production of ceramic tiles, which include a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer.

[0055] Example 4

[0056] A type of dry ice crystal pellet, wherein the pellet comprises a first flashing frit, a second flashing frit, and a matte frit in a weight ratio of 1:2:3.

[0057] The chemical composition of the first flashing molten block, by mass percentage, is: SiO2: 66%, Al2O3: 17.0%, CaO: 8%, Na2O: 4.0%, K2O: 1%, ZnO: 1.2%, TiO2: 0.9%, with the balance being loss on ignition.

[0058] The chemical composition of the second flashing molten block, by mass percentage, is: SiO2: 57%, Al2O3: 13%, CaO: 9%, ZnO: 6%, MgO: 2.3%, K2O: 5.5%, Na2O: 2.5%, with the balance being loss on ignition.

[0059] The chemical composition of the matte frit, by mass percentage, is: SiO2: 58%, Al2O3: 19%, CaO: 5%, K2O: 5%, Na2O: 6.2%, BaO: 1.3%, Li2O: 0.3%, F: 0.1%, SrO: 0.2%, with the balance being loss on ignition.

[0060] The ice crystal dry granules described in Example 4 are used in the production of ceramic tiles. These tiles include a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer, and can be prepared as follows: Figure 1The tile shown has an ice crystal dry particle effect.

[0061] Comparative Example 1

[0062] A ceramic tile includes a body, a base glaze layer disposed on the body, a pattern layer disposed on the base glaze layer, a top glaze layer disposed on the pattern layer, and a protective glaze layer disposed on a dry granule layer of the top glaze layer. The ceramic tile... Figure 2 As shown, it does not have a flashing effect.

[0063] Comparative Example 2

[0064] A ceramic tile comprising a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer, wherein the dry granule layer is prepared from the first flash frit in Example 1.

[0065] Comparative Example 3

[0066] A ceramic tile comprising a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer, wherein the dry granule layer is prepared from the second flash frit in Example 1.

[0067] Comparative Example 4

[0068] A ceramic tile comprising a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer, wherein the dry granule layer is prepared from a first flash frit and a second flash frit as described in Example 1, wherein the ratio of the first flash frit to the second flash frit is 1:1.

[0069] Comparative Example 5

[0070] A ceramic tile comprising a body, a base glaze layer, a pattern layer, a top glaze layer, a dry granule layer, and a protective glaze layer, wherein the dry granule layer is prepared from ice crystal dry granules with the same composition as in Example 1, except that the particle size of the ice crystal dry granules is 250 μm.

[0071] The ceramic tiles prepared by the ice crystal dry granules described in Examples 1-4 and the ceramic tiles described in Comparative Examples 1-5 were subjected to gloss and refractive index tests. At the same time, their visual effects under dark light conditions were observed. The specific test results are shown in Table 1.

[0072] Table 1. Test Results

[0073]

[0074] As shown in Table 1, the ceramic tiles prepared from the ice crystal dry granules described in Examples 1-4 exhibit a lower gloss, a higher refractive index, and a better shimmering effect. However, the ceramic tile in Comparative Example 1, lacking a shimmering frit, does not possess a shimmering effect. Comparative Examples 2, 3, and 4, using a first shimmering frit, a second shimmering frit, or a mixture of both as the dry granule layer material, respectively, result in a high gloss level. Although the refractive index is also high, the lack of a matte frit makes the shimmering effect less noticeable in low light. Comparative Example 5, while exhibiting a shimmering effect, suffers from an uneven surface due to the large particle size of the shimmering dry granules, affecting the overall visual effect. Therefore, the combined action of the first shimmering frit, the second shimmering frit, and the matte frit achieves a higher refractive index while reducing gloss, thus better creating a shimmering visual effect.

[0075] It is understood that those skilled in the art can make equivalent substitutions or modifications to the technical solution and inventive concept of the present invention, and all such substitutions or modifications should fall within the protection scope of the appended claims.

Claims

1. A type of dry ice crystal granules, characterized in that, The ice crystal dry particles include a first flash melt, a second flash melt, and a matte melt; The chemical composition of the first flashing molten metal, by mass percentage, is: SiO2: 60-70%, Al2O3: 15.3-18.6%, CaO: 5.1-8.5%, Na2O: 3.0-7.4%, K2O: 0.5-2.1%, ZnO: 1.1-2%, TiO2: 0.8-1.3%, with the balance being loss on ignition; The chemical composition of the second flashing molten metal, by mass percentage, is as follows: SiO2: 56.2–60%, Al2O3: 11.3–14.5%, CaO: 8.2–9.8%, ZnO: 5.7–6.9%, MgO: 2.1–3.1%, K2O: 4.4–6.2%, Na2O: 1.5–3.1%, with the balance being loss on ignition. The chemical composition of the matte frit, by mass percentage, is as follows: SiO2: 54–61%, Al2O3: 17–21%, CaO: 4.9–5.6%, K2O: 4.9–5.5%, Na2O: 6.0–7.0%, BaO: 1.2–2.1%, Li2O: 0.2–0.3%, F: 0.05–0.1%, SrO: 0.08–0.2%, with the balance being loss on ignition.

2. The dry ice crystal particles according to claim 1, characterized in that, The weight ratio of the first flashing frit, the second flashing frit, and the matte frit is 2:3:

2.

3. A method for preparing dry ice crystal particles as described in claim 1 or 2, characterized in that, Take the first flashing frit, the second flashing frit, and the matte frit, ball mill and sieve them to obtain a mixed powder; take the mixed powder, additives and water, stir and mix them to obtain a mixed slurry; granulate the mixed slurry through a centrifugal spray drying tower to obtain ice crystal dry granules.

4. The method for preparing dry ice crystal granules according to claim 3, characterized in that, The additives include polyvinyl alcohol, bentonite, and sodium lignin carbonate.

5. The method for preparing dry ice crystal granules according to claim 3, characterized in that, The particle size of the ice crystal dry particles is 100-150 μm.

6. The method for preparing dry ice crystal granules according to claim 3, characterized in that, The temperature inside the centrifugal spray drying tower is 250–350°C.

7. A type of ceramic tile, characterized in that, It includes a blank body, a base glaze layer disposed on the blank body, a pattern layer disposed on the base glaze layer, a top glaze layer disposed on the pattern layer, a dry granule layer disposed on the top glaze layer, and a protective glaze layer disposed on the dry granule layer; the dry granule layer is prepared from ice crystal dry granules as described in claim 1 or 2.

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