A ferrous metal devitrifying glaze with natural boundary lines and a method of making the same
By preparing a black metallic crystallized glaze containing raw materials such as anhydrous borax and iron oxide red, and utilizing the fluidity of the glaze and the precipitation of iron elements to form natural boundary lines, the problem of insufficient decorative and artistic value of traditional crystallized glaze porcelain is solved, realizing low-cost production and high artistic value of the glaze.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- LILING GUANQIAN PORCELAIN IND CO LTD
- Filing Date
- 2024-02-19
- Publication Date
- 2026-07-31
AI Technical Summary
The decorative and artistic value of traditional crystallized glaze porcelain needs to be improved, especially since the metallic edge effect at the edge of the glaze layer is not natural or prominent enough.
Using anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide as the main raw materials, a ferrous metal crystallization glaze is prepared by ball milling, drying, calcination and mixing with a water-blocking agent. The glaze's fluidity and the precipitation of iron elements form natural boundary lines.
It achieves low-cost production of glazes, improves the hardness, wear resistance and transparency of glazes, and at the same time, the edges of the glaze layer naturally form metallic boundary lines, enhancing its decorative and artistic value.
Smart Images
Figure CN118063093B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of ceramic production technology, specifically relating to a black metallic crystallized glaze with naturally formed boundary lines and its preparation method. Background Technology
[0002] Porcelain, as an art form, primarily derives its aesthetic beauty from the body and glaze themselves. After bisque firing, the surface of the unglazed body is generally rough and dull, affecting its appearance. The addition of glaze not only alters the properties of the finished product but also greatly enhances its aesthetic appeal. Glaze is a substance applied to the unglazed body; it is extremely thin and melts at high temperatures, forming a glossy, vitreous layer on the surface. In short, glaze is essentially a colored or colorless thin glass layer with similar physicochemical properties to glass. Therefore, for porcelain, the beauty of the body lies in the shape, while the beauty of the glaze lies in the decoration.
[0003] Throughout the development of Chinese ceramics, porcelain glazes have had various names throughout history, but based on their structural essence, they can be divided into four categories: glassy glaze, crystalline glaze, phase-separated glaze, and crystalline-phase-separated glaze. Among them, crystalline glaze is named for the microcrystals that precipitate during the firing process. The Southern Song Dynasty's Jiaotan Official Kiln and the Longquan Ge Kiln are typical examples of crystalline glaze porcelain. The microcrystals commonly found in the glaze layer of traditional crystalline glaze porcelain are composed of anorthite, diopside, wollastonite, or hematite.
[0004] As ceramics have evolved from everyday necessities to aesthetically pleasing crafts and decorative items, and with in-depth research into the color-forming mechanism of ceramic glazes and the relationship between the microstructure and macroscopic patterns of glazes, the composition and preparation methods of traditional crystallized glazes have been gradually improved and iterated. In the process of improving the composition and preparation methods of glazes, our company accidentally developed a black metallic crystallized glaze with naturally formed boundary lines. Through research, we have gradually obtained a stable glaze formula and preparation method, aiming to enhance the ornamental and artistic value of crystallized glaze ceramic products. Summary of the Invention
[0005] The purpose of this invention is to provide a black metallic crystallized glaze with naturally formed boundary lines and its preparation method, aiming to improve the ornamental and artistic value of crystallized glaze ceramic products.
[0006] The objective of this invention can be achieved through the following technical solutions:
[0007] A black metallic crystallized glaze with naturally formed boundary lines, comprising the following raw materials in parts by weight:
[0008] Anhydrous borax 28-40 parts, iron oxide red 25-32 parts, tricalcium phosphate 8-15 parts, copper oxide 7-12 parts, fluorite 5-10 parts, bismuth oxide 4-8 parts, molybdenum oxide 4-8 parts.
[0009] Furthermore, the black metallic crystallized glaze with naturally formed boundary lines comprises the following raw materials in parts by weight: 30 parts anhydrous borax, 30 parts iron oxide red, 10 parts tricalcium phosphate, 10 parts copper oxide, 10 parts fluorite, 5 parts bismuth oxide, and 5 parts molybdenum oxide.
[0010] Furthermore, the preparation method of the black metallic crystallized glaze with naturally formed boundary lines includes the following steps:
[0011] Weigh each raw material according to the weight parts. Mix anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide and ball mill through a 300-mesh sieve to obtain a mixture. Place the mixture in an oven at 90-100℃ to dry to constant weight. Take it out and calcine it at 900-910℃ for 2-3 hours. Take it out, cool it to room temperature, and ball mill it through a 500-mesh sieve to obtain calcined material. Add a water-blocking agent to the calcined material and mix and stir for 30-50 minutes to obtain the black metallic crystallized glaze with naturally formed boundary lines.
[0012] Furthermore, the mass ratio of the calcined material to the water-blocking agent is 1:1.
[0013] Furthermore, the water-blocking agent is prepared by mixing the following raw materials in parts by weight:
[0014] 35-45 parts surfactant, 32-40 parts inorganic salt, 20-30 parts polymer, 0.5-2 parts dispersant, 0.1-1 part leveling agent, and 0.1-1 part defoamer.
[0015] Furthermore, the surfactant is nonylphenol polyoxyethylene ether or alkyl sulfate.
[0016] Furthermore, the inorganic salt is calcium chloride or magnesium sulfate.
[0017] Furthermore, the polymer is polyethylene glycol diacrylate or polyurethane.
[0018] Further, the dispersant is dispersant BYK163 or dispersant EFKA4400; the leveling agent is leveling agent BYK306 or leveling agent BYK333; and the defoamer is defoamer BYK051 or defoamer BYK052.
[0019] The beneficial effects of this invention are:
[0020] This invention provides a formula for a black metallic crystallized glaze that naturally forms boundary lines. The formula includes anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide, and molybdenum oxide. This invention also provides a method for preparing the glaze, in which the prepared glaze is applied to a blank body via a screen, dried, and then glazed and fired, ultimately forming metallic boundary lines at the edge between the glaze and the blank body.
[0021] The anhydrous borax (Na2B4O7; melting point 742.5℃), bismuth oxide (Bi2O3; melting point 825℃), and molybdenum oxide (MoO3; melting point 795℃) in the formula promote melting and flow of the glaze by lowering the glazing firing temperature, thus helping to reduce production costs. Furthermore, anhydrous borax helps improve the hardness, wear resistance, and corrosion resistance of the glaze; bismuth oxide helps improve the stability of the glaze; and molybdenum oxide helps improve the viscosity and surface tension of the glaze. Finally, the selected non-metallic anhydrous borax and metallic bismuth oxide and molybdenum oxide have similar melting points, which helps to... To improve the uniformity of the glaze; tricalcium phosphate and copper oxide in the formula serve as colorants, which can improve the gloss and coloring effect of the glaze; fluorite in the formula is used to improve the transparency of the glaze; iron oxide red in the formula precipitates a large amount of α-Fe2O3 crystals during the cooling process of glazing and firing, forming black metal crystals. The glaze has good fluidity during glazing and firing, and iron elements migrate and diffuse with the molten glaze. The thicker the glaze layer, the higher the iron concentration. At the junction of the glaze edge and the body, iron precipitates rapidly, forming the boundary lines of α-Fe2O3 crystal precipitation.
[0022] The crystallization glaze formula provided by this invention has the advantages of low cost and lead-free. At the same time, compared with the traditional process of using metal powder to draw gold to form metal edges, the glaze provided by this invention can naturally form boundary lines, which are more decorative and have stronger boundary lines, and have higher ornamental and artistic value. Attached Figure Description
[0023] The present invention will now be further described with reference to the accompanying drawings.
[0024] Figure 1 This is a front view of the ceramic product in Embodiment 7 of the present invention;
[0025] Figure 2 This is a partial enlarged view of the ceramic product in Embodiment 7 of the present invention. Detailed Implementation
[0026] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0027] Example 1
[0028] Preparation of water-blocking agent:
[0029] The water-blocking agent is made by mixing the following raw materials in parts by weight:
[0030] The ingredients are: 35 parts surfactant, 32 parts inorganic salt, 20 parts polymer, 0.5 parts dispersant, 0.1 parts leveling agent, and 0.1 parts defoamer.
[0031] The surfactant is nonylphenol polyoxyethylene ether (Sinopharm Reagent); the inorganic salt is calcium chloride; the polymer is polyethylene glycol diacrylate (Mn≈400); the dispersant is dispersant BYK163; the leveling agent is leveling agent BYK306; and the defoamer is defoamer BYK051.
[0032] Example 2
[0033] Preparation of water-blocking agent:
[0034] The water-blocking agent is made by mixing the following raw materials in parts by weight:
[0035] The ingredients are: 40 parts surfactant, 35 parts inorganic salt, 25 parts polymer, 1 part dispersant, 0.5 parts leveling agent, and 0.5 parts defoamer.
[0036] The surfactant is an alkyl sulfate ( AES25 (BASF); inorganic salt is magnesium sulfate; polymer is polyethylene glycol diacrylate (Mn≈400); dispersant is dispersant BYK163; leveling agent is leveling agent BYK333; defoamer is defoamer BYK052.
[0037] Example 3
[0038] Preparation of water-blocking agent:
[0039] The water-blocking agent is made by mixing the following raw materials in parts by weight:
[0040] 45 parts surfactant, 40 parts inorganic salt, 30 parts polymer, 2 parts dispersant, 1 part leveling agent, and 1 part defoamer.
[0041] The surfactant is an alkyl sulfate ( AES25 (BASF); Inorganic salt is magnesium sulfate; Polymer is polyurethane; Dispersant is EFKA4400; Leveling agent is BYK333; Defoamer is BYK052.
[0042] Example 4
[0043] Preparation of a black metallic crystallized glaze with naturally formed boundary lines:
[0044] First, the crystallized glaze comprises the following raw materials in parts by weight:
[0045] 28 parts anhydrous borax, 25 parts iron oxide red, 8 parts tricalcium phosphate, 7 parts copper oxide, 5 parts fluorite, 4 parts bismuth oxide, and 4 parts molybdenum oxide.
[0046] Then, the method for preparing the crystallized glaze includes the following steps:
[0047] Weigh each raw material according to the weight parts. Mix anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide and ball mill through a 300-mesh sieve to obtain a mixture. Place the mixture in a 90°C oven to dry to constant weight, take it out and calcine it at 900°C for 2 hours. Take it out, cool it to room temperature, and ball mill it through a 500-mesh sieve to obtain calcined material. Add the water-blocking agent prepared in Example 1 to the calcined material at a mass ratio of 1:1, mix and stir for 30 minutes to obtain the black metallic crystallized glaze with naturally formed boundary lines.
[0048] Example 5
[0049] Preparation of a black metallic crystallized glaze with naturally formed boundary lines:
[0050] First, the crystallized glaze comprises the following raw materials in parts by weight:
[0051] 35 parts anhydrous borax, 30 parts iron oxide red, 10 parts tricalcium phosphate, 8 parts copper oxide, 6 parts fluorite, 5 parts bismuth oxide, and 5 parts molybdenum oxide.
[0052] Then, the method for preparing the crystallized glaze includes the following steps:
[0053] Weigh each raw material according to the weight parts. Mix anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide and ball mill through a 300-mesh sieve to obtain a mixture. Place the mixture in a 100℃ oven to dry to constant weight, take it out and calcine it at 910℃ for 3 hours. Take it out, cool it to room temperature, and ball mill it through a 500-mesh sieve to obtain calcined material. Add the water-blocking agent prepared in Example 2 to the calcined material at a mass ratio of 1:1, mix and stir for 40 minutes to obtain the black metallic crystallized glaze with naturally formed boundary lines.
[0054] Example 6
[0055] Preparation of a black metallic crystallized glaze with naturally formed boundary lines:
[0056] First, the crystallized glaze comprises the following raw materials in parts by weight:
[0057] 40 parts anhydrous borax, 32 parts iron oxide red, 15 parts tricalcium phosphate, 12 parts copper oxide, 10 parts fluorite, 8 parts bismuth oxide, and 8 parts molybdenum oxide.
[0058] Then, the method for preparing the crystallized glaze includes the following steps:
[0059] Weigh each raw material according to the weight proportions. Mix anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide and ball mill through a 300-mesh sieve to obtain a mixture. Place the mixture in a 100℃ oven to dry to constant weight, take it out, and calcine it at 910℃ for 3 hours. Take it out, cool it to room temperature, and ball mill it through a 500-mesh sieve to obtain a calcined material. Add the water-blocking agent prepared in Example 3 to the calcined material at a mass ratio of 1:1, mix and stir for 50 minutes to obtain the black metallic crystallized glaze with naturally formed boundary lines.
[0060] Example 7
[0061] Preparation of ceramic products:
[0062] The crystallized glaze prepared in Example 6 was used. After drying on the body using a wire brush, the glaze was applied and fired at 1350°C. After cooling to room temperature, the ceramic product was obtained. The appearance of the ceramic product is shown in the attached figure. Figure 1-2 As shown in the figure, it can be observed with the naked eye that the surface of the prepared ceramic product has naturally formed boundary lines. Compared with the traditional process of using metal powder to create metal edges, the surface of the ceramic product prepared in this embodiment has naturally formed boundary lines, which are more decorative and have higher aesthetic and artistic value.
[0063] It should be noted that, in this document, terms such as “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0064] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A black metallic crystallized glaze with naturally formed boundary lines, characterized in that, Including the following parts by weight of raw materials: Anhydrous borax 28-40 parts, iron oxide red 25-32 parts, tricalcium phosphate 8-15 parts, copper oxide 7-12 parts, fluorite 5-10 parts, bismuth oxide 4-8 parts, molybdenum oxide 4-8 parts; Includes the following steps: Weigh each raw material according to the weight parts. Mix anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide and ball mill through a 300-mesh sieve to obtain a mixture. Place the mixture in an oven at 90-100℃ and dry it to constant weight. Take it out and calcine it at 900-910℃ for 2-3 hours. Take it out and cool it to room temperature. Then ball mill it through a 500-mesh sieve to obtain a calcined material. Add a water-blocking agent to the calcined material and mix and stir for 30-50 minutes to obtain the black metallic crystallized glaze with naturally formed boundary lines. The water-blocking agent is prepared by mixing the following raw materials in parts by weight: 35-45 parts surfactant, 32-40 parts inorganic salt, 20-30 parts polymer, 0.5-2 parts dispersant, 0.1-1 part leveling agent, and 0.1-1 part defoamer.
2. The black metallic crystallized glaze with naturally formed boundary lines according to claim 1, characterized in that, The raw materials include the following parts by weight: 30 parts anhydrous borax, 30 parts iron oxide red, 10 parts tricalcium phosphate, 10 parts copper oxide, 10 parts fluorite, 5 parts bismuth oxide, and 5 parts molybdenum oxide.
3. A method for preparing a ferrous metallic crystallized glaze with naturally formed boundary lines according to any one of claims 1-2, characterized in that, Includes the following steps: Weigh each raw material according to the weight parts. Mix anhydrous borax, iron oxide red, tricalcium phosphate, copper oxide, fluorite, bismuth oxide and molybdenum oxide and ball mill through a 300-mesh sieve to obtain a mixture. Place the mixture in an oven at 90-100℃ to dry to constant weight. Take it out and calcine it at 900-910℃ for 2-3 hours. Take it out, cool it to room temperature, and ball mill it through a 500-mesh sieve to obtain calcined material. Add a water-blocking agent to the calcined material and mix and stir for 30-50 minutes to obtain the black metallic crystallized glaze with naturally formed boundary lines.
4. The method for preparing a black metallic crystallized glaze with naturally formed boundary lines according to claim 3, characterized in that, The mass ratio of the calcined material to the water-blocking agent is 1:
1.
5. The method for preparing a black metallic crystallized glaze with naturally formed boundary lines according to claim 3, characterized in that, The water-blocking agent is prepared by mixing the following raw materials in parts by weight: 35-45 parts surfactant, 32-40 parts inorganic salt, 20-30 parts polymer, 0.5-2 parts dispersant, 0.1-1 part leveling agent, and 0.1-1 part defoamer.
6. The method for preparing a black metallic crystallized glaze with naturally formed boundary lines according to claim 5, characterized in that, The surfactant is nonylphenol polyoxyethylene ether or alkyl sulfate.
7. The method for preparing a black metallic crystallized glaze with naturally formed boundary lines according to claim 5, characterized in that, The inorganic salt is calcium chloride or magnesium sulfate.
8. The method for preparing a black metallic crystallized glaze with naturally formed boundary lines according to claim 5, characterized in that, The polymer is polyethylene glycol diacrylate or polyurethane.
9. The method for preparing a black metallic crystallized glaze with naturally formed boundary lines according to claim 5, characterized in that, The dispersant is dispersant BYK163 or dispersant EFKA4400; the leveling agent is leveling agent BYK306 or leveling agent BYK333; the defoamer is defoamer BYK051 or defoamer BYK052.