A kind of underglaze colorful bright red high temperature pigment and preparation method thereof

Abstract

The invention discloses an underglaze colorful bright red high temperature pigment and a preparation method thereof. The pigment is prepared from the following components in mass percentage: 75-83% aluminum oxide, 5-9% manganese carbonate, 3-6% sodium fluoride, 2-4% sodium chloride, 3-5% calcium fluoride and 2-7% red lead. The formula of the invention consists of a colorant and a mineralizer. By screening components and controlling the proportion, and adopting a medium-temperature oxidizing flame calcination and acid boiling process, a bright red high temperature pigment is prepared. The pigment is applied to various ceramic glaze decoration fields, especially in the production of Mao porcelain, and the obtained products are bright, gorgeous and pure in color.

Description

Technical Field

[0001] The invention belongs to the technical field of ceramic underglaze high-temperature pigments, and in particular relates to an underglaze colorful bright red high-temperature pigment and a preparation method thereof. Background Art

[0002] Red is the most common base color of underglaze colored porcelain. It has important applications in decorations such as figures, flowers, birds and animals, and has excellent artistic expression. The existing red coloring mechanism is basically to form an α-Al[Mn] interstitial solid solution with a manganese-containing compound and an aluminum-containing compound. However, after the obtained pigment is applied to the finished product of underglaze colored porcelain, the finished product has a light color, impure color, and low layering, which cannot meet the coloring requirement of 1380°C for underglaze colored porcelain. For example, the Chinese invention patent with publication number CN111646698A discloses a method for preparing a high-temperature manganese red ceramic glaze and the application of the glaze. The patent discloses that 5-15 parts by weight of aluminum hydroxide and 3-8 parts by weight of manganese carbonate are finely ground into a dry powder in advance with a dry pulverizer to be used as a colorant for the red glaze. However, its application temperature is only 1300-1350°C, which is lower than the firing temperature of underglaze colored porcelain, and the coloring cannot meet the coloring requirement of 1380°C for underglaze colored porcelain.

[0003] In view of this, the present invention proposes an underglaze colorful brilliant red high temperature pigment and a preparation method thereof to solve the above problems. Summary of the invention

[0004] The invention aims to provide an underglaze colorful brilliant red high temperature pigment and a preparation method thereof.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is: an underglaze colorful bright red high-temperature pigment is prepared from the following components in percentage by mass: 75-83% aluminum oxide, 5-9% manganese carbonate, 3-6% sodium fluoride, 2-4% sodium chloride, 3-5% calcium fluoride and 2-7% red lead.

[0006] The present invention also provides a method for preparing an underglaze colorful brilliant red high temperature pigment, comprising the following steps:

[0007] S1: Weigh 75-83% aluminum oxide, 5-9% manganese carbonate, 3-6% sodium fluoride, 2-4% sodium chloride, 3-5% calcium fluoride and 2-7% red lead according to mass percentage, dry mix them, and sieve the mixed powder.

[0008] S2: The sieved mixed powder is calcined at high temperature in an oxidizing flame atmosphere.

[0009] S3: The powder after high-temperature calcination is crushed and sieved, then rinsed, ball-milled, dried, and sieved again to obtain the finished product.

[0010] In a feasible implementation, the aluminum oxide, manganese carbonate, sodium fluoride, sodium chloride, and calcium fluoride are chemically pure, and the red lead is industrial grade.

[0011] In a feasible implementation, the high temperature calcination process in step S2 is: heating from room temperature to 1250-1260°C at 3-4°C / min, then keeping at 1250-1260°C for 1 hour, and then cooling naturally.

[0012] In a feasible implementation, the rinsing process in step S3 is: add a certain concentration of acid to the crushed and sieved powder and heat it to a slurry state. After cooling, pour it into a container filled with water and stir it. After settling for 6-8 hours, pour out the upper layer of yellow suspended matter, repeat this operation several times until the upper layer is clear water, and you can get a pigment that meets the requirements.

[0013] In a feasible implementation, the ball milling in step S3 uses water as the medium and wet ball milling is performed for 40 hours.

[0014] In a feasible implementation, the rinsing in step S3 is performed using one of sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid.

[0015] In a feasible implementation, in step S3, hydrochloric acid with a concentration of 15-25 wt% is used and the heating temperature is 700-800°C.

[0016] In a feasible implementation, the finished product particle size D50 in step S3 is 3-10 μm.

[0017] Experimental principle of the present invention:

[0018] In the formula, MnCO3 and α-Al2O3 are colorants. MnCO3 is decomposed into Mn2O3 and Mn 3+ Through the action of mineralizers such as CaF2, NaF, and NaCl, it enters the α-Al2O3 lattice to form an α-Al[Mn] interstitial solid solution, which is bright red. This corundum-type solid solution is resistant to high temperatures, stable, and not affected by reducing atmospheres; NaF, NaCl, Pb3O4 (red lead), and CaF2 are mineralizers, and low-melting-point compounds NaF (Ts=993°C), NaCl (Ts=801°C), and Pb3O4 (Ts=500°C) are selected for fluxing, and CaF2 is selected for coloring; Among them, if Mn 3+ Too much, the corundum structure is destroyed, Mn 3+ Too little and the color will be too light.

[0019] In the preparation process, calcination in an oxidizing flame at a medium temperature of 1250-1260℃ is beneficial to color stability. The oxidizing flame inhibits the formation of Mn3O4 to avoid impure color. If the temperature is too high, the pigment will easily agglomerate and become inconvenient for subsequent use. High-temperature boiling with hydrochloric acid washes away the unreacted MnCO3. Otherwise, the remaining MnCO3 will decompose at high temperature during subsequent use of the pigment, causing impure color. In addition, the particle size of the pigment must be strictly controlled to avoid being too fine. Fenshui painting will be too thick, causing the blank surface to flip up or warp, or the surface to crack easily after sintering.

[0020] Beneficial effects of the present invention:

[0021] The formula of the present invention is composed of a colorant and a mineralizer. By screening the components and controlling the proportion, and adopting a medium-temperature oxidizing flame calcination and acid boiling process, a bright red high-temperature pigment is prepared. It can be used in an oxidizing flame, a reducing flame, or an oxidizing-reducing flame atmosphere, and after sintering at 1280-1380°C, the color can still be bright, pure, stable, and widely applicable. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a real picture of a teacup made of high temperature pigment in Example 1 of the present invention.

[0023] Figure 2 This is a real picture of a teacup made of high temperature pigment according to comparative example 1 of the present invention.

[0024] Figure 3 This is a real picture of a teacup made of high temperature pigment according to comparative example 2 of the present invention. DETAILED DESCRIPTION

[0025] The invention provides a brilliant red high temperature pigment, which is prepared from the following components in percentage by mass: 75-83% of aluminum oxide, 5-9% of manganese carbonate, 3-6% of sodium fluoride, 2-4% of sodium chloride, 3-5% of calcium fluoride and 2-7% of red lead.

[0026] The preparation method of the above-mentioned brilliant red high temperature pigment comprises the following steps:

[0027] S1: First, the ball mill and the balls are dried thoroughly, and then 75-83% aluminum oxide, 5-9% manganese carbonate, 3-6% sodium fluoride, 2-4% sodium chloride, 3-5% calcium fluoride and 2-7% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mix for 24 hours, and the mixed powder is sieved.

[0028] S2: The mixed and sieved powder is placed in a refractory container, and then placed in a high-temperature fired refractory tank, and then placed in a high-temperature electric furnace under an oxidizing flame atmosphere for high-temperature calcination.

[0029] S3: The powder after high-temperature calcination is crushed and sieved, then rinsed, ball-milled, dried, and sieved with 200 meshes to obtain a finished product.

[0030] The preparation method of the underglaze five-color 2657 brilliant red high-temperature pigment of the present invention is further described below in conjunction with specific embodiments.

[0031] Embodiment 1

[0032] S1: First, the ball mill and the balls are dried thoroughly, and then 78% aluminum oxide, 7% manganese carbonate, 4% sodium fluoride, 2.5% sodium chloride, 4.5% calcium fluoride and 4% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0033] S2: Place the mixed and sieved powder in a refractory container, and then place it in a high-temperature fired refractory container, and calcine it at high temperature in an oxidizing flame atmosphere of a natural gas kiln. The temperature is increased from room temperature to 1250°C at a rate of 3.5°C / min, and kept at 1250°C for 1 hour, and then cooled naturally.

[0034] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (20% HCl aqueous solution, heated to 800°C), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain the finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after manual Fenshui painting is shown in Table 1.

[0035] Embodiment 2

[0036] S1: First, the ball mill and the balls are dried thoroughly, and then 82% aluminum oxide, 6% manganese carbonate, 3% sodium fluoride, 3% sodium chloride, 3% calcium fluoride and 3% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0037] S2: Place the mixed and sieved powder in a refractory container, and then place it in a high-temperature fired refractory container, and calcine it at high temperature in an oxidizing flame atmosphere of a natural gas kiln. The temperature is increased from room temperature to 1260°C at a rate of 3.5°C / min, and kept at 1260°C for 1 hour, and then cooled naturally.

[0038] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (20% HCl aqueous solution, heated to 800°C), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain the finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after manual Fenshui painting is shown in Table 1.

[0039] Embodiment 3

[0040] S1: First, the ball mill and the balls are dried thoroughly, and then 76% aluminum oxide, 9% manganese carbonate, 4% sodium fluoride, 4% sodium chloride, 4% calcium fluoride and 3% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0041] S2: Place the mixed and sieved powder in a refractory container, and then put it into a high-temperature refractory tank, and calcine it at a high temperature of 1250°C in an oxidizing flame atmosphere of a natural gas kiln, heating it from room temperature to 1250°C at a rate of 3.5°C / min, and keep it warm for 1 hour, and then cool it naturally.

[0042] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (20% HCl aqueous solution, heated to 800°C), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain the finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after manual Fenshui painting is shown in Table 1.

[0043] Comparative Example 1

[0044] S1: First, the ball mill and the balls are dried thoroughly, and then 74% aluminum oxide, 12% manganese carbonate, 4% sodium fluoride, 2% sodium chloride, 4% calcium fluoride and 4% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0045] S2: Place the mixed and sieved powder in a refractory container, and then place it in a high-temperature fired refractory container, and calcine it at a high temperature of 1250°C in an oxidizing flame atmosphere of a natural gas kiln, heating from room temperature to 1250°C at a rate of 3.5°C / min, and keep it warm for 1 hour, and then cool it naturally.

[0046] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (20% HCl aqueous solution, heated to 800°C), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain the finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after hand-painted Fenshui pigment is shown in Table 1.

[0047] Comparative Example 2

[0048] S1: First, the ball mill and the balls are dried thoroughly, and then 78% aluminum oxide, 7% manganese carbonate, 4% sodium fluoride, 2.5% sodium chloride, and 4.5% calcium fluoride are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0049] S2: Place the mixed and sieved powder in a refractory container, and then place it in a high-temperature fired refractory container, and calcine it at a high temperature of 1250°C in an oxidizing flame atmosphere of a natural gas kiln, heating from room temperature to 1250°C at a rate of 3.5°C / min, and keep it warm for 1 hour, and then cool it naturally.

[0050] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (20% HCl aqueous solution, heated to 800°C), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain the finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after manual Fenshui painting is shown in Table 1.

[0051] Comparative Example 3

[0052] S1: First, the ball mill and the balls are dried thoroughly, and then 78% aluminum oxide, 7% manganese carbonate, 4% sodium fluoride, 2.5% sodium chloride, 4.5% calcium fluoride and 4% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0053] S2: Place the mixed and sieved powder in a refractory container, and then place it in a high-temperature fired refractory container, and place it into a natural gas kiln for high-temperature calcination at 1320°C in an oxidizing flame atmosphere, heating from room temperature to 1320°C at a rate of 3.5°C / min, and keep it warm for 1 hour, and then cool naturally.

[0054] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (20% HCl aqueous solution, heated to 800°C), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain the finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after manual Fenshui painting is shown in Table 1.

[0055] Comparative Example 4

[0056] S1: First, the ball mill and the balls are dried thoroughly, and then 78% aluminum oxide, 7% manganese carbonate, 4% sodium fluoride, 2.5% sodium chloride, 4.5% calcium fluoride and 4% red lead are weighed according to the mass percentage and put into the ball mill, and dry-mixed for 24 hours, and the mixed powder is sieved.

[0057] S2: Place the mixed and sieved powder in a refractory container, and then put it into a high-temperature refractory tank, and calcine it at a high temperature of 1250°C in an oxidizing flame atmosphere of a natural gas kiln, heating from room temperature to 1250°C at a rate of 3.5°C / min, and keep it warm for 1 hour, and then cool it naturally.

[0058] S3: The high-temperature calcined powder is crushed and sieved, then rinsed (water, room temperature), ball-milled (wet milled for 40 hours), dried, and sieved through 200 mesh to obtain a finished product. The finished product is prepared into Fenshui pigment, and the appearance of the finished underglaze colored porcelain after manual Fenshui painting is shown in Table 1.

[0059] Table 1 Appearance of finished underglaze colored porcelain

[0060]

[0061] The 2657 brilliant red in this embodiment is an underglaze color pigment code, which refers to the common red base material of Mao porcelain in Liling area, and is used for underglaze colorful porcelain painting decoration.

[0062] It can be seen from the above test examples that the present invention uses manganese carbonate and α-Al2O3 as colorants, selects other additives, and obtains a pigment composition after calcination in an oxidizing flame at a medium temperature of 1250-1260°C and pickling. The pigment composition is then applied to underglaze 2657 brilliant red multicolored porcelain painting for decoration. The fired finished product maintains a bright red color, has high repeatability, and maintains consistent product color, and has extremely high application value.

[0063] The above are only preferred embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent structure or equivalent process transformation made using the contents of the present invention specification and drawings, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. An underglaze colorful bright red high temperature pigment, characterized in that: The invention is prepared from the following components in the following mass percentages: 75-83% of aluminum oxide, 5-9% of manganese carbonate, 3-6% of sodium fluoride, 2-4% of sodium chloride, 3-5% of calcium fluoride and 2-7% of red lead.

2. A method for preparing an underglaze colorful bright red high temperature pigment, characterized in that: The following steps are involved: S1: Weigh 75-83% aluminum oxide, 5-9% manganese carbonate, 3-6% sodium fluoride, 2-4% sodium chloride, 3-5% calcium fluoride and 2-7% red lead according to mass percentage, dry mix them, and sieve the mixed powder; S2: calcining the sieved mixed powder at high temperature in an oxidizing flame atmosphere; S3: The powder after high-temperature calcination is crushed and sieved, then rinsed, ball-milled, dried, and sieved again to obtain the finished product.

3. The method for preparing the underglaze colorful brilliant red high temperature pigment according to claim 2, characterized in that: The aluminum oxide, manganese carbonate, sodium fluoride, sodium chloride and calcium fluoride are chemically pure, the aluminum oxide is α-Al2O3, and the red lead is industrial grade.

4. The method for preparing the underglaze colorful brilliant red high temperature pigment according to claim 2, characterized in that: The high temperature calcination process in step S2 is: heating from room temperature to 1250-1260°C at 3-4°C / min, then keeping at 1250-1260°C for 1h, and then cooling naturally.

5. The method for producing underglaze colorful brilliant red high temperature pigment according to claim 4, characterized in that: The rinsing process in step S3 is as follows: the crushed and sieved powder is heated with acid to a slurry state, and after cooling, it is poured into a container filled with water and stirred. After settling for 6-8 hours, the upper layer of yellow suspended matter is poured out, and the operation is repeated several times until the upper layer is clear water, and a pigment that meets the requirements can be obtained.

6. The method for producing underglaze colorful brilliant red high temperature pigment according to claim 5, characterized in that: The ball milling process in step S3 is: using water as the medium, wet ball milling for 40 hours.

7. The method for producing underglaze colorful brilliant red high temperature pigment according to claim 6, characterized in that: The acid used in the rinsing process is sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid.

8. The method for producing underglaze colorful brilliant red high temperature pigment according to claim 7, characterized in that: The rinsing in step S3 is performed using a 15-25 wt % hydrochloric acid solution at a heating temperature of 700-800° C.

9. The method for producing underglaze colorful brilliant red high temperature pigment according to claim 8, characterized in that: The finished product particle size D50 is 3-10μm.

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