Iron-titanium bicrystal flower crystal glaze and preparation method thereof

Abstract

The invention provides an iron-titanium bicrystal flower crystal glaze and a preparation method thereof. The iron-titanium bicrystal flower crystal glaze is prepared from the following raw materials in parts by weight: 20 to 30 parts of glass powder, 20 to 30 parts of quartz, 15 to 25 parts of calcite, 4 to 10 parts of talc, 1 to 4 parts of bovine bone ash, 3 to 7 parts of zinc oxide, 3 to 8 parts of ferric oxide and 9 to 14 parts of titanium oxide, and the crystal glaze is prepared from the following chemical components in percentage by mass: 47 to 53 percent of SiO2, 1 to 3 percent of Al2O3, 11 to 21 percent of CaO, 2 to 6 percent of MgO, 0 to 1 percent of K2O, 2 to 5 percent of Na2O, 0.4 to 1.8 percent of P2O5, 3 to 8 percent of ZnO, 3 to 9 percent of Fe2O3 and 9 to 16 percent of TiO2. The crystal glaze disclosed by the invention is simple in operation process, easy to control, suitable for decorating domestic ceramics and display ceramics and capable of being produced on a large scale.

Description

Technical Field

[0001] The present invention relates to an iron-titanium double-crystal flower crystallization glaze and a preparation method thereof, belonging to the technical field of ceramic glaze preparation. Background Art

[0002] Crystallization glaze is an artificial crystal flower glaze. By introducing a crystallization agent into the base glaze and controlling the firing process, various-shaped flower crystals are formed in the glaze layer. The crystal flowers are approximately natural and changeable, giving people a beautiful feeling. Its unique artistic decoration effect has high ornamental value and is quite popular among consumers.

[0003] At present, most crystallization glaze products are decorative ceramic products. Products decorated with crystallization glaze have special artistic effects and are deeply favored by the market. However, traditional crystallization glaze is often single-crystallization glaze, that is, only one type of crystal flower is formed on the glaze surface, and there are few double-crystal flower crystallization glazes that form two different types of crystal flowers on the glaze surface, resulting in a single glaze surface decoration effect. Chinese patent document CN115959828A provides a double-crystal flower colored crystallization glaze, a double-crystal flower colored crystallization glaze ceramic tile and a preparation method thereof. The raw material composition of the double-crystal flower colored crystallization glaze includes: 90-95% of zinc zirconium crystallization glaze and 5-10% of colored crystallization dry particles by mass percentage. The preparation method is as follows: First, apply a surface glaze on the brick blank surface, second, inkjet print a design pattern on the brick blank surface after applying the surface glaze, then apply the above double-crystal flower colored crystallization glaze on the brick blank surface after inkjet printing the design pattern, and finally fire and polish the green body after applying the double-crystal flower colored crystallization glaze to obtain the double-crystal flower colored crystallization glaze ceramic tile. This double-crystal flower colored crystallization glaze precipitates white zinc zirconium-based crystal flowers and colored crystal flowers during the firing process, and the glaze surface presents two patterns and crystal flowers of different colors. Using this process to produce double-crystal flower colored crystallization glaze is only suitable for ceramic brick blanks, and the process is relatively complex and not suitable for decorating daily-use ceramics and decorative ceramics.

[0004] With the improvement of people's living quality and the change of consumption concepts, it is required that ceramic products have both practicality, artistry and ornamental value. Therefore, it is of great significance for daily-use ceramics, decorative ceramics, etc. to develop a double-crystal flower crystallization glaze with a simple preparation process, easy to control, suitable for decorating daily-use ceramics and decorative ceramics and capable of large-scale production. Summary of the Invention

[0005] Aiming at the deficiencies of the prior art, especially the deficiency that only single-type crystal flowers appear on the glaze surface of the crystallization glaze for existing daily-use ceramics and decorative ceramics, the present invention provides an iron-titanium double-crystal flower crystallization glaze and a preparation method thereof. By introducing a specific amount of iron oxide and titanium oxide into the ordinary glaze base material of ceramics and following the firing process of conventional crystallization glaze, a double-crystal flower crystallization glaze can be fired on daily-use ceramics and decorative ceramics. The crystallization glaze of the present invention has a simple operation process, is easy to control, is suitable for decorating daily-use ceramics and decorative ceramics and can be produced on a large scale.

[0006] The technical solution of the present invention is as follows:

[0007] An iron-titanium twin crystal flower crystallization glaze, comprising raw materials in the following parts by weight:

[0008] 20-30 parts of glass powder, 20-30 parts of quartz, 15-25 parts of calcite, 4-10 parts of talc, 1-4 parts of bovine bone ash, 3-7 parts of zinc oxide, 3-8 parts of iron oxide, 9-14 parts of titanium dioxide.

[0009] Preferably according to the present invention, the iron-titanium twin crystal flower crystallization glaze comprises the following chemical components in mass percentages:

[0010] SiO2: 47-53%, Al2O3: 1-3%, CaO: 11-21%, MgO: 2-6%, K2O: 0-1%, Na2O: 2-5%, P2O5: 0.4-1.8%, ZnO: 3-8%, Fe2O3: 3-9%, TiO2: 9-16%.

[0011] According to the present invention, the preparation method of the above iron-titanium twin crystal flower crystallization glaze comprises the following steps:

[0012] (1) According to the ratio, put glass powder, iron oxide, quartz, talc, and bovine bone ash into a ball mill tank for ball milling, then add calcite and zinc oxide for ball milling, then add titanium dioxide for ball milling, and then sieve to obtain glaze slurry;

[0013] (2) Apply the glaze slurry obtained in step (1) to the ceramic green body by the spraying method to obtain a ceramic semi-finished product;

[0014] (3) Dry the ceramic semi-finished product obtained in step (2) and then fire it, and after cooling, an iron-titanium twin crystal flower crystallization glaze is obtained on the surface of the ceramic green body, and at the same time, an iron-titanium twin crystal flower crystallization glaze ceramic product is obtained.

[0015] Preferably according to the present invention, in step (1), water is added for ball milling during the ball milling process, and the mass ratio of water to the raw materials is 0.7-0.9:1.

[0016] Preferably according to the present invention, the ball-to-material ratio in the ball milling process in step (1) is 1.5-2:1, and the mass of the material is calculated based on the total mass of water and the raw materials.

[0017] According to the present invention, the mass of the raw materials is calculated based on the total mass of glass powder, quartz, calcite, talc, bovine bone ash, zinc oxide, iron oxide, and titanium dioxide.

[0018] Preferably according to the present invention, in step (1), the ball milling time after adding glass powder, iron oxide, quartz, talc, and bovine bone ash is 5 - 10 minutes; the ball milling time after adding calcite and zinc oxide is 1 - 5 minutes, and the ball milling time after adding titanium dioxide is 1 - 2 minutes; the rotation speed of the ball milling is 200 - 400 r / min.

[0019] Preferably according to the present invention, in step (1), the sieving is through a 100 - mesh sieve.

[0020] Preferably according to the present invention, in step (2), the thickness of the glaze layer on the surface of the ceramic semi - finished product is 0.5 - 0.8 mm.

[0021] Preferably according to the present invention, in step (3), the drying is carried out at 80°C for 0.5 h.

[0022] Preferably according to the present invention, the firing steps in step (3) are as follows: First, heat up to 300°C at a heating rate of 150°C / h, then heat up to 900°C at a heating rate of 180°C / h, and then heat up to 1250°C at a heating rate of 125°C / h, and hold at 1250°C for 120 min; the cooling is carried out by furnace cooling to room temperature.

[0023] The technical features and beneficial effects of the present invention are as follows:

[0024] 1. The production process and firing process of the crystalline glaze of the present invention are basically the same as those of ordinary colored glazes, without the need for special treatment, and are easy to implement.

[0025] 2. The crystalline glaze of the present invention changes the current situation that crystalline glaze for decorating daily - use ceramics often has only one type of crystal flower, and instead forms two different types of crystal flowers on the glaze surface, and has high artistic value. The present invention selects common raw materials for making glaze such as glass powder, quartz, calcite, talc, zinc oxide, and bovine bone ash, introduces specific proportions of iron oxide and titanium dioxide, adopts the common glaze - preparation process, and is fired in an electric furnace under an oxidizing atmosphere and specific firing parameters. On the smooth glaze surface, a large number of round crystal flowers of two different types, red and yellow, will appear. The red crystal flowers are the precipitation regions mainly composed of α - Fe2O3 crystals, and the diameter of the crystal flowers is mostly between 2 - 5 mm; the yellow crystal flowers are the precipitation regions of Fe 3+ , Ti 4+ mixed crystals, and the diameter of the crystal flowers is mostly between 5 - 10 mm. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 It is the glaze - surface effect diagram of the iron - titanium double - crystal - flower crystalline glaze prepared in Example 1.

[0027] Figure 2 It is the glaze - surface effect diagram of the iron - titanium double - crystal - flower crystalline glaze prepared in Example 2.

[0028] Figure 3 The glaze surface effect picture of the iron-titanium twin crystal flower crystallization glaze prepared in Example 3.

[0029] Figure 4 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 1, where (a) is 2 parts and (b) is 12 parts.

[0030] Figure 5 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 2, where (a) is 7 parts and (b) is 18 parts.

[0031] Figure 6 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 3.

[0032] Figure 7 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 4.

[0033] Figure 8 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 5.

[0034] Figure 9 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 6.

[0035] Figure 10 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 7.

[0036] Figure 11 The glaze surface effect picture of the iron-titanium crystallization glaze prepared in Comparative Example 8. Specific Embodiments

[0037] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited thereto.

[0038] The chemical compositions of the minerals and chemical raw materials used in the examples are shown in Table 1 below:

[0039] Table 1 Chemical composition of raw materials wt%

[0040]

[0041] Example 1

[0042] An iron-titanium twin crystal flower crystallization glaze, comprising the following raw materials in parts by weight:

[0043] 20 parts of glass powder, 30 parts of quartz, 15 parts of calcite, 10 parts of talc, 1 part of bovine bone ash, 7 parts of zinc oxide, 8 parts of iron oxide, 9 parts of titanium dioxide.

[0044] The fired crystallization glaze comprises the following chemical composition in mass percentage:

[0045] SiO2: 52.80%, Al2O3: 1.62%, CaO: 11.73%, MgO: 4.40%, K2O: 0.34%, Na2O: 2.88%, P2O5: 0.43%, ZnO: 7.56%, Fe2O3: 8.58%, TiO2: 9.65%.

[0046] When calculating the mass percentages of the above chemical compositions, the mass of the crystalline glaze is based on the total mass of SiO2, Al2O3, CaO, MgO, K2O, Na2O, P2O5, ZnO, Fe2O3 and TiO2.

[0047] The preparation method of the above iron-titanium twin-crystal flower crystalline glaze includes the following steps:

[0048] (1) First, accurately weigh glass powder, iron oxide, quartz, talc, and bovine bone ash according to the formula and put them into a ball mill tank filled with water. After ball milling for 7 minutes, then add calcite and zinc oxide and ball mill for 2 minutes. Finally, add titanium dioxide and ball mill for 1 minute. Discharge and pass through a 100-mesh sieve to obtain the glaze; the rotation speed of the ball milling is 300 r / min, the ball-to-material ratio during the ball milling process is 2:1, and the mass ratio of water to raw materials during the ball milling process is 0.8:1 (the mass of the raw materials is based on the total mass of glass powder, quartz, calcite, talc, bovine bone ash, zinc oxide, iron oxide, and titanium dioxide).

[0049] (2) Apply the glaze obtained in step (1) to the green body (the body is a vase formed by slip casting and subjected to bisque firing at 800 °C) by spraying. Control the thickness of the glaze layer at 0.6 mm. After drying (drying at 80 °C for 0.5 h), put it into an electric furnace for firing. The firing steps are as follows: First, heat up at a heating rate of 150 °C / h to 300 °C, then heat up at a heating rate of 180 °C / h to 900 °C, and then heat up at a heating rate of 125 °C / h to 1250 °C. Keep it at 1250 °C for 120 min, and finally cool naturally with the kiln.

[0050] The ceramic product of the present invention has a fired background color of brown, and its glaze surface effect diagram is as Figure 1 shown. It can be seen from Figure 1 that the crystal flowers are red and yellow products respectively. The crystals in this glaze are evenly distributed, with regular shapes and good effects.

[0051] Example 2

[0052] An iron-titanium twin-crystal flower crystalline glaze, comprising the following raw materials in parts by weight:

[0053] 30 parts of glass powder, 20 parts of quartz, 25 parts of calcite, 4 parts of talc, 4 parts of bovine bone ash, 3 parts of zinc oxide, 3 parts of iron oxide, and 14 parts of titanium dioxide.

[0054] The fired crystalline glaze includes the following chemical composition in mass percentages:

[0055] SiO2: 47.01%, Al2O3: 1.28%, CaO: 20.61%, MgO: 2.84%, K2O: 0.46%, Na2O: 4.37%, P2O5: 1.75%, ZnO: 3.27%, Fe2O3: 3.25%, TiO2: 15.16%.

[0056] When calculating the mass percentages of the above chemical components, the mass of the crystalline glaze is calculated based on the total mass of SiO2, Al2O3, CaO, MgO, K2O, Na2O, P2O5, ZnO, Fe2O3 and TiO2.

[0057] The preparation method of the above iron-titanium twin-crystal flower crystalline glaze is as described in Example 1.

[0058] The ceramic product of the present invention has a fired background color of brown, and its glaze surface effect diagram is as Figure 2 shown, and it can be seen from Figure 2 that the crystal flowers are red and yellow products respectively, and the crystals in this glaze are evenly distributed, regular in shape, and have a very good effect.

[0059] Example 3

[0060] An iron-titanium twin-crystal flower crystalline glaze, comprising the following raw materials in parts by weight:

[0061] 25 parts of glass powder, 25 parts of quartz, 20 parts of calcite, 8 parts of talc, 3 parts of bovine bone ash, 5 parts of zinc oxide, 5 parts of iron oxide, 12 parts of titanium dioxide.

[0062] The fired crystalline glaze comprises the following chemical components in mass percentages:

[0063] SiO2: 49.74%, Al2O3: 1.50%, CaO: 16.22%, MgO: 3.92%, K2O: 0.39%, Na2O: 3.56%, P2O5: 1.28%, ZnO: 5.35%, Fe2O3: 5.31%, TiO2: 12.73%.

[0064] When calculating the mass percentages of the above chemical components, the mass of the crystalline glaze is calculated based on the total mass of SiO2, Al2O3, CaO, MgO, K2O, Na2O, P2O5, ZnO, Fe2O3 and TiO2.

[0065] The preparation method of the above iron-titanium twin-crystal flower crystalline glaze is as described in Example 1.

[0066] The ceramic product of the present invention has a fired background color of brown, and its glaze surface effect diagram is as Figure 3 shown, and it can be seen from Figure 3It can be seen that the crystal flowers are red and yellow products respectively. The crystals in this glaze are evenly distributed with regular shapes and good effects.

[0067] Comparative Example 1

[0068] An iron-titanium crystalline glaze is as described in Example 3, except that: the iron oxide is 2 parts or 12 parts; the glaze surface effect diagram is as Figure 4 shown, by Figure 4 It can be seen that there are no twin crystal flowers on the glaze surface, and it is just a single-color glaze.

[0069] Comparative Example 2

[0070] An iron-titanium twin crystal flower crystalline glaze is as described in Example 3, except that: the titanium dioxide is 7 parts or 18 parts; the glaze surface effect diagram is as Figure 5 shown, by Figure 5 It can be seen that there are no crystal flowers on the glaze surface, and it is just a single-color glaze.

[0071] Comparative Example 3

[0072] An iron-titanium twin crystal flower crystalline glaze is as described in Example 3, except that: the glass powder is 10 parts; the glaze surface effect diagram is as Figure 6 shown, by Figure 6 It can be seen that the glaze surface is rough, the glossiness is not good, and there are no crystal flowers.

[0073] Comparative Example 4

[0074] An iron-titanium twin crystal flower crystalline glaze is as described in Example 3, except that: the glass powder is 50 parts; the glaze surface effect diagram is as Figure 7 shown, by Figure 7 It can be seen that there is a glaze flow phenomenon on the glaze surface, and twin crystal flowers appear.

[0075] Comparative Example 5

[0076] An iron-titanium twin crystal flower crystalline glaze is as described in Example 3, except that: the quartz is 10 parts; the glaze surface effect diagram is as Figure 8 shown, by Figure 8 It can be seen that relatively large crystal flowers appear and are connected together, affecting the appearance.

[0077] Comparative Example 6

[0078] An iron-titanium twin crystal flower crystalline glaze is as described in Example 3, except that: the quartz is 40 parts; the glaze surface effect diagram is as Figure 9 shown, by Figure 9 It can be seen that there are a small number of fine crystal flowers on the glaze surface.

[0079] Comparative Example 7

[0080] The preparation method of an iron-titanium twin-crystal flower crystallization glaze is as described in Example 1, except that the heat preservation time is 90 min; the effect picture of its glaze surface is as Figure 10 shown, and it can be seen from Figure 10 that the glaze surface is rough and dull, no crystal flowers appear, and there is a certain phenomenon of underfiring.

[0081] Comparative Example 8

[0082] The preparation method of an iron-titanium twin-crystal flower crystallization glaze is as described in Example 1, except that the heat preservation time is 150 min; the effect picture of its glaze surface is as Figure 11 shown, and it can be seen from Figure 11 that twin crystal flowers appear, but there is an obvious phenomenon of glaze running.

Claims

1. An iron-titanium twin flower crystal glaze, characterized in that: The invention comprises the following raw materials in parts by weight: 20-30 parts of glass powder, 20-30 parts of quartz, 15-25 parts of calcite, 4-10 parts of talc, 1-4 parts of cow bone ash, 3-7 parts of zinc oxide, 3-8 parts of iron oxide, and 9-14 parts of titanium oxide.

2. The iron-titanium twin flower crystal glaze according to claim 1, characterized in that: The chemical composition includes the following mass percentages: SiO2: 47-53%, Al2O3: 1-3%, CaO: 11-21%, MgO: 2-6%, K2O: 0-1%, Na2O: 2-5%, P2O5: 0.4-1.8%, ZnO: 3-8%, Fe2O3: 3-9%, TiO2: 9-16%.

3. The method for preparing the iron-titanium twin flower crystal glaze according to claim 1 comprises the following steps: (1) according to the proportion, glass powder, iron oxide, quartz, talc, and cattle bone ash are put into a ball mill for ball milling, then calcite and zinc oxide are added for ball milling, and then titanium dioxide is added for ball milling, and then sieved to obtain glaze slurry; (2) applying glaze slurry obtained in step (1) to a ceramic blank by spraying to obtain a ceramic semi-finished product; (3) The ceramic semi-finished product obtained in step (2) is dried and then fired, and after cooling, an iron-titanium twin flower crystal glaze is obtained on the surface of the ceramic blank, and an iron-titanium twin flower crystal glaze ceramic product is obtained.

4. The method for preparing the iron-titanium twin flower crystalline glaze according to claim 3, characterized in that: In step (1), water is added during the ball milling process, and the mass ratio of water to raw material is 0.7-0.9:

1.

5. The method for preparing the iron-titanium twin flower crystalline glaze according to claim 3, characterized in that: The ball-to-material ratio in the ball milling process in step (1) is 1.5-2:1, and the mass of the material is calculated based on the total mass of water and raw materials.

6. The method for preparing the iron-titanium twin flower crystalline glaze according to claim 3, characterized in that: In step (1), the ball milling time after adding glass powder, iron oxide, quartz, talc and cattle bone ash is 5-10 minutes; the ball milling time after adding calcite and zinc oxide is 1-5 minutes, and the ball milling time after adding titanium dioxide is 1-2 minutes; the rotation speed of the ball mill is 200-400r / min.

7. The method for preparing the iron-titanium twin flower crystalline glaze according to claim 3, characterized in that: The sieving in step (1) is through a 100-mesh sieve.

8. The method for preparing the iron-titanium twin flower crystalline glaze according to claim 3, characterized in that: In step (2), the thickness of the glaze layer on the surface of the ceramic semi-finished product is 0.5-0.8 mm.

9. The method for preparing the iron-titanium twin flower crystal glaze according to claim 3, characterized in that: The drying in step (3) is performed at 80° C. for 0.5 h.

10. The method for preparing the iron-titanium twin flower crystalline glaze according to claim 3, characterized in that: The firing step in step (3) is: firstly heating to 300°C at a heating rate of 150°C / h, then heating to 900°C at a heating rate of 180°C / h, then heating to 1250°C at a heating rate of 125°C / h, and keeping at 1250°C for 120 minutes; and the cooling is cooling to room temperature along with the furnace.

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