Black color porcelain with white ground and preparation method thereof

Abstract

This invention provides a method for preparing black glaze on white-ground black-decorated porcelain. The raw materials for the black glaze on white-ground black-decorated porcelain include: a base glaze and auxiliary materials. By mass percentage, the base glaze consists of: 50%–65% of sloping soil, 14%–19% of black clay, 5%–8% of feldspar, 3%–6% of quartz, 5%–11% of talc, 1%–4% of manganese oxide, and 1%–4% of iron oxide. The auxiliary materials include sodium carboxymethyl cellulose and sodium polyphosphate. This invention uses high-iron-content sloping soil as the main coloring agent for the black color layer. The clay body is made from local black clay raw materials, dipped in colored paint to create patterns, and then a layer of transparent glaze is applied using the glazing method and fired once. During the glazing and firing process, at high temperature, the iron elements in the clay body exist in an ionic state and rise to the surface of the glaze layer under the influence of air bubbles. As the gas dissipates, the iron accumulates on the surface, resulting in a glossy black color. This invention utilizes the high iron content in the raw materials and the action of other fluxes to achieve the purpose of iron oxide coloring.

Description

Technical Field

[0001] This invention relates to the field of ceramic material manufacturing technology, and in particular to a black-painted porcelain with a white background and its preparation method. Background Technology

[0002] Yaozhou ware, with its white ground and black decoration, originated in the Tang Dynasty, developed rapidly during the Song Dynasty, flourished in the Yuan and Ming Dynasties, declined after the Qing Dynasty, but continued to be produced. Its porcelain-making techniques directly influenced kilns in many regions, such as the Cizhou kiln and Dangyangyu kiln in the Northern Song Dynasty. The Chenlu kiln flourished in the Ming Dynasty. Ming Dynasty Yaozhou ware with white ground and black decoration employed underglaze decoration techniques, featuring a darker body and a coarser texture. A slip was applied to the surface to refine the finish, and black glaze was used to paint the designs before a transparent glaze was applied and the piece was fired. Based on the specific decorative techniques, it is categorized into white ground with black sgraffito, white ground with incised decoration, and white ground with black decoration; however, variations in the iron content of the glaze, kiln temperature, and atmosphere can result in white ground with brown decoration, white ground with yellow decoration, and white ground with ochre decoration, among others.

[0003] The black glaze coloring process can be considered as follows: iron-rich droplets in the glaze rise to the glaze surface, enveloped by tiny bubbles generated by the reaction. There, they are oxidized to form iron oxide nuclei, which then absorb iron sources for further crystallization until the glaze solidifies on the surface. Due to the emphasis on official kilns over private kilns, and the influence of factors such as war and competition, there is a lack of records regarding the relevant production techniques. The techniques relied solely on the experience of kiln workers and oral traditions passed down through workshops. Furthermore, modern research is limited to archaeological records and analyses of the chemical composition of the body and glaze by a very few researchers. No public or analytical records exist regarding the specific preparation process and raw material formulas for white-ground black-decorated porcelain, thus limiting its widespread application in the traditional ceramics industry. Summary of the Invention

[0004] In order to overcome the shortcomings of the above-mentioned white-ground black-decorated porcelain preparation process, the purpose of this invention is to provide a black color for white-ground black-decorated porcelain and a preparation method thereof. This invention can provide a new method for the application of white-ground black-decorated porcelain in traditional ceramic decoration, lay the foundation for exploring the coloring mechanism of black color in ancient porcelain, and open up new ways for the efficient utilization of natural raw materials in ceramic bodies.

[0005] This invention is achieved through the following technical solution:

[0006] A type of white-ground black-decorated porcelain with black decoration, comprising, by weight percentage, a base glaze and auxiliary materials. The base glaze comprises, by weight percentage, 50%–65% of sloping soil, 14%–19% of black clay, 5%–8% of feldspar, 3%–6% of quartz, 5%–11% of talc, 1%–4% of manganese oxide, and 1%–4% of iron oxide. The auxiliary materials include sodium carboxymethyl cellulose and sodium polyphosphate.

[0007] Preferably, the auxiliary materials include sodium carboxymethyl cellulose at 0.8% of the mass of the base glaze and sodium polyphosphate at 0.3%.

[0008] Preferably, the black clay material is composed of 50% sandy loam soil, 20% Dongshan soil, and 30% Yuzhai soil by mass percentage.

[0009] The method for preparing the black-painted porcelain with white background includes:

[0010] S1, take black clay raw material and shape it, dry it to obtain the blank; brush a layer of slip on the surface of the blank;

[0011] S2, take raw materials such as slope soil, black clay, feldspar, quartz, talc, manganese oxide, iron oxide, sodium carboxymethyl cellulose and sodium polyphosphate and mix them to obtain a mixed glaze;

[0012] S3, the mixed glaze obtained in S2 is subjected to wet ball milling to obtain black glaze slurry;

[0013] S4. Apply the black glaze obtained in S3 to the body obtained in S1 using the brush glazing method, and let it dry to obtain the glazed body.

[0014] S5, Apply a layer of transparent glaze to the colored blank obtained in S4 using the dipping glaze method, and let it dry;

[0015] S6, the colored blank with transparent glaze obtained in S5 is fired once in a neutral atmosphere to prepare black-painted porcelain with white ground and black decoration on black body.

[0016] Preferably, in S1, the black tire material is first repeatedly pounded to remove excess gas before molding.

[0017] Preferably, in S1, the thickness of the brushed slip is 0.5-1mm.

[0018] Preferably, in S3, the rotation speed of the wet ball mill is 300 r / min, the milling time is 40-45 min, and the mass ratio of material, balls and water is 1:2:1.

[0019] Preferably, in S4, the glaze thickness is controlled between 0.5 mm and 0.8 mm.

[0020] Preferably, before S4, the surface of the blank obtained in S1 is wetted with water.

[0021] Preferably, in S5, the firing process is as follows: the temperature is increased from room temperature to 300°C at a heating rate of 4.5–5°C / min, then increased from 300°C to 900°C at a heating rate of 3.3–3.5°C / min, and then increased from 900°C to 1250°C at a heating rate of 1.2–1.4°C / min; the temperature is held at 1250°C for 30 minutes, and then cooled with the furnace.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] This invention uses high-iron-content local sloping soil as the main coloring agent for the black glaze layer. The clay body is made from local black porcelain raw materials, dipped in colored pigments for design, and then coated with a layer of transparent glaze using a dipping method before a single firing. During the glazing and firing process, at high temperatures, the iron elements in the clay body exist in an ionic state. These ions rise to the glaze surface under the influence of air bubbles, accumulating on the surface as the gases dissipate, resulting in a glossy black glaze appearance. This utilizes the high iron content in the raw materials and the action of other fluxes to achieve the purpose of iron oxide coloring. Compared with ancient porcelain shard samples, this invention has a smooth and glossy surface. The addition of trace amounts of manganese oxide increases the blackness; the addition of iron oxide increases the iron content of the pigments, which rise to the surface under the influence of glaze bubbles, facilitating the formation of iron oxide crystals after surface oxidation, thus improving the color. This invention also adds sodium carboxymethyl cellulose and sodium polyphosphate to the raw materials to improve the viscosity and fluidity of the pigments, facilitating vivid and smooth painting. This invention provides a new method for the application of black glaze on white-ground black-flower porcelain from Yaozhou kiln in traditional ceramic decoration, and can also open up new avenues for the efficient utilization of natural raw materials in ceramic bodies. Attached Figure Description

[0024] Figure 1 The image shows a super-depth-of-field photograph of a white porcelain piece with black decoration on a black background, without transparent glaze and with transparent glaze, under ring lighting.

[0025] Figure 2 An optical micrograph of the cross-section of a white porcelain sample with black floral design under ring light illumination;

[0026] Figure 3 Raman image of the black-painted area of ​​the white-ground black-decorated porcelain produced by this invention. Detailed Implementation

[0027] To further understand the present invention, the present invention will be described below with reference to embodiments. These descriptions are only for further explaining the features and advantages of the present invention and are not intended to limit the claims of the present invention.

[0028] The white-ground black-flower porcelain with black enamel of the present invention comprises the following raw materials: a base glaze and auxiliary materials. By mass percentage, the base glaze consists of: 50%–65% of soil from the local slope, 14%–19% of black clay, 5%–8% of feldspar, 3%–6% of quartz, 5%–11% of talc, 1%–4% of manganese oxide, and 1%–4% of iron oxide. The auxiliary materials include sodium carboxymethyl cellulose and sodium polyphosphate.

[0029] Preferably, the auxiliary materials include sodium carboxymethyl cellulose at 0.8% of the mass of the base glaze and sodium polyphosphate at 0.3%.

[0030] The black clay material formula, by weight percentage, is: 50% Shaliang clay, 20% Dongshan clay, and 30% Yuzhai clay. The Lidipo clay, Shaliang clay, Dongshan clay, and Yuzhai clay were all sourced from the vicinity of Yaozhou Kiln in Tongchuan City, Shaanxi Province.

[0031] The preparation method for Yaozhou ware white-ground black-decorated porcelain includes the following steps;

[0032] S1. The black clay material taken from Wangjia Porcelain Workshop in Chenlu Ancient Town, Shaanxi Province is used to make blanks: the black clay material is repeatedly pounded by hand to remove excess gas, shaped, and dried to obtain the blank; a layer of slip with a thickness of 0.5-1mm is brushed on the surface of the blank, and it is left to dry and set aside for later use.

[0033] S2, weigh the raw materials according to the following proportions: slope soil, black clay, feldspar, quartz, talc, manganese oxide, iron oxide, sodium carboxymethyl cellulose and sodium polyphosphate, and mix them to obtain a mixed glaze.

[0034] S3, the mixed glaze obtained in S2 is wet ball milled to obtain the black glaze slurry required for firing black glaze;

[0035] S4. Apply the black glaze obtained in S3 to the body obtained in S1 using the brush glazing method. The glaze thickness is controlled between 0.5mm and 0.8mm to obtain the glazed body. Let it air dry for later use.

[0036] S5, apply a layer of transparent glaze to the colored blank obtained in S4 using the dipping glaze method, and let it air dry naturally;

[0037] S6, the colored blank with transparent glaze obtained in S5 is fired once in a neutral atmosphere, that is, a white-ground black-decorated porcelain with black decoration is prepared on a black body.

[0038] In S3 of this invention, the rotation speed of the wet ball mill is 300 r / min, the ball milling time is 40-45 min, and the mass ratio of material, balls and water is 1:2:1.

[0039] Before step S4, the present invention uses a sponge or a soft, large brush to lightly wet the surface of the clay body with a small amount of water to enhance the bonding effect with the paint, while preventing the dry clay body from quickly absorbing the moisture from the paint and causing the paint to curl up.

[0040] In S5 of this invention, the firing process is as follows: heating from room temperature to 300°C at a rate of 4.5–5°C / min for 60 min; heating from 300°C to 900°C at a rate of 3.3–3.5°C / min for 180 min; heating from 900°C to 1250°C at a rate of 1.2–1.4°C / min for 300 min; holding at 1250°C for 30 min; and then cooling in the furnace.

[0041] Example 1

[0042] Step 1: Manually pound the black clay raw material repeatedly to remove excess gas, roll and flatten it into a square sheet of 20cm*15cm*0.6cm. When it is slightly dry and still plastic, cut it into square blanks of 3cm*5cm*0.6cm, let it dry and polish for later use.

[0043] Step 2: Apply a layer of laboratory slip about 0.8mm thick to the upper side of the blank made from the black clay material, leaving the lower side as is for reference.

[0044] Step 3: Weigh out 65% of the site slope soil, 15% of the black clay, 7% of the feldspar, 5.6% of the quartz, 5% of the talc, 1.2% of the manganese oxide, and 1.2% of the iron oxide according to the mass ratio. Add 0.8% sodium carboxymethyl cellulose and 0.3% sodium polyphosphate by mass of the base glaze to prepare the mixed glaze.

[0045] Step 4: Grind the mixed glaze obtained in Step 3 using a planetary ball mill to obtain the black glaze slurry required for firing the black glaze; wherein, the ball mill speed is 300 r / min, the ball milling time is 40 min, and the material:ball:water ratio is 1:2:1.

[0046] Step 5: Apply the black glaze obtained in Step 4 to the prepared body using the brush glazing method. Control the glaze thickness to 0.5-0.8 mm to obtain the glazed body. Let it air dry naturally for later use.

[0047] Step Six: Apply a layer of transparent glaze to the colored blank obtained in Step Five and let it air dry naturally at room temperature;

[0048] Step 7: Place the black-painted blank with transparent glaze obtained in Step 6 into an electric furnace and fire it under a neutral atmosphere. The temperature is raised from room temperature to 300°C in 60 minutes, then to 900°C in 180 minutes, then to 1250°C in 263 minutes and held for 30 minutes. Finally, it is cooled in the furnace, thus preparing a white-ground black-painted porcelain with black decoration on a black body.

[0049] Example 2:

[0050] Step 1: Manually pound the black clay raw material repeatedly to remove excess gas, roll and flatten it into a square sheet of 20cm*15cm*0.6cm. When it is slightly dry and still plastic, cut it into square blanks of 3cm*5cm*0.6cm, let it dry and polish for later use.

[0051] Step 2: Brush a layer of laboratory slip about 0.5 mm thick onto the upper side of the blank prepared in Step 1, leaving the lower side as is for reference.

[0052] Step 3: Weigh out 50% of the site slope soil, 15.6% of the black clay, 15% of the feldspar, 12% of the quartz, 5% of the talc, 1.2% of the manganese oxide, and 1.2% of the iron oxide according to the mass ratio. Add 0.8% sodium carboxymethyl cellulose and 0.3% sodium polyphosphate by mass of the base glaze to prepare the mixed glaze.

[0053] Step 4: Grind the mixed glaze obtained in Step 3 using a planetary ball mill to obtain the slurry required for firing the black glaze; wherein, the ball mill speed is 300 r / min, the ball milling time is 40 min, and the material:ball:water ratio is 1:2:1;

[0054] Step 5: Apply the black glaze obtained in Step 4 to the prepared body using the brush glazing method. Control the glaze thickness to 0.5-0.8 mm to obtain the glazed body. Let it air dry naturally for later use.

[0055] Step Six: Apply a layer of transparent glaze to one side of the colored blank obtained in Step Five using the glazing method and let it dry;

[0056] Step 7: Place the colored blank with transparent glaze obtained in Step 6 into a box furnace and fire it under a neutral atmosphere. The temperature is raised from room temperature to 300℃ in 60 minutes, then to 900℃ in 180 minutes, then to 1250℃ in 263 minutes and held for 30 minutes. Finally, it is cooled in the furnace, thus preparing black-painted porcelain with white ground on black body.

[0057] Example 3:

[0058] Step 1: Manually pound the black clay raw material repeatedly to remove excess gas, roll and flatten it into a square sheet of 20cm*15cm*0.6cm. When it is slightly dry and still plastic, cut it into square blanks of 3cm*5cm*0.6cm, let it dry and polish for later use.

[0059] Step 2: Apply a layer of laboratory slip about 0.5mm thick to the upper side of the blank made from the black clay material, leaving the lower side as is for reference.

[0060] Step 3: Weigh out 60% of the site slope soil, 15.6% of the black clay, 7.5% of the feldspar, 5.6% of the quartz, 7.5% of the talc, 1.9% of the manganese oxide, and 1.9% of the iron oxide according to the mass ratio, and add 0.8% sodium carboxymethyl cellulose and 0.3% sodium polyphosphate according to the mass of the base glaze to prepare the mixed glaze.

[0061] Step 4: Grind the mixed glaze obtained in Step 3 using a planetary ball mill to obtain the black glaze slurry required for firing the black glaze; wherein, the ball mill speed is 300 r / min, the ball milling time is 45 min, and the material:ball:water ratio is 1:2:1;

[0062] Step 5: Apply the black glaze obtained in Step 4 to the prepared body using the brush glazing method. Control the glaze thickness to 0.5-0.8 mm to obtain the glazed body. Let it air dry naturally for later use.

[0063] Step Six: Apply a layer of transparent glaze to the colored blank obtained in Step Five and let it dry;

[0064] Step 7: Place the colored blank with transparent glaze obtained in Step 6 into an electric furnace and fire it under a neutral atmosphere. The temperature is raised from room temperature to 300°C in 60 minutes, then to 900°C in 180 minutes, then to 1250°C in 263 minutes and held for 30 minutes. Finally, it is cooled in the furnace, thus preparing black-painted porcelain with white ground on black body.

[0065] like Figure 1 As shown, the images are ultra-depth-of-field photographs of white porcelain with black decoration on a white background without transparent glaze (a) and with transparent glaze (b) under ring light illumination. The images demonstrate the effect of applying transparent glaze on the color rendering of the black decoration on the surface of white porcelain with black decoration, which can enhance the color rendering of the black decoration.

[0066] Figure 2 This is an optical micrograph of the cross-section of a white-ground black-decorated porcelain sample under ring light illumination. The cross-section shows a four-layer structure: body, slip, black decoration, and transparent glaze. The boundary between the black decoration and the transparent glaze is not obvious.

[0067] Figure 3 The image shows the Raman diagram of the black glaze on the white-ground black-decorated porcelain obtained by this invention, indicating that the precipitated crystals on its surface are α-Fe2O3.

[0068] Example 4:

[0069] Step 1: Manually pound the black clay raw material repeatedly to remove excess gas, roll and flatten it into a square sheet of 20cm*15cm*0.6cm. When it is slightly dry and still plastic, cut it into square blanks of 3cm*5cm*0.6cm, let it dry and polish for later use.

[0070] Step 2: Apply a layer of laboratory slip about 0.5mm thick to the upper side of the blank made from the black clay material, leaving the lower side as is for reference.

[0071] Step 3: Weigh out 65% of the original slope soil, 15% of the black clay, 5% of feldspar, 3.7% of quartz, 7.5% of talc, 1.9% of manganese oxide, and 1.9% of iron oxide according to the mass ratio, and add 0.8% sodium carboxymethyl cellulose and 0.3% sodium polyphosphate according to the mass of the base glaze to prepare the mixed glaze.

[0072] Step 4: Grind the mixed glaze obtained in Step 3 using a planetary ball mill to obtain the black glaze slurry required for firing the black glaze; wherein, the ball mill speed is 300 r / min, the ball milling time is 45 min, and the material:ball:water ratio is 1:2:1;

[0073] Step 5: Apply the black glaze obtained in Step 4 to the prepared body using the brush glazing method. Control the glaze thickness to 0.5-0.8 mm to obtain the glazed body. Let it air dry naturally for later use.

[0074] Step Six: Apply a layer of transparent glaze to the colored blank obtained in Step Five and let it dry;

[0075] Step 7: Place the colored blank with transparent glaze obtained in Step 6 into an electric furnace and fire it under a neutral atmosphere. The temperature is raised from room temperature to 300°C in 60 minutes, then to 900°C in 180 minutes, then to 1270°C in 265 minutes and held for 30 minutes. Finally, it is cooled in the furnace, thus preparing black-painted porcelain with white ground and black decoration on a black body.

[0076] Comparative Example 1

[0077] A raw material formula for black-glazed white porcelain with black decoration: 70% slab soil, 12.5% ​​black clay, 10% feldspar, and 7.5% quartz are weighed out according to the following mass ratio, with the addition of sodium carboxymethyl cellulose (0.8%) and sodium polyphosphate (0.3%) as the base glaze. The preparation method is the same as in Example 3. The color is lighter where the glaze layer is thinner, and the sample without talc, manganese oxide, and iron oxide also has a lighter color. Although this method uses only pure natural raw materials, the fired product is not black enough and lacks high artistic and economic value. The appropriate addition of flux and the thickness of the glaze layer are closely related to the yield of the product.

[0078] Comparative Example 2

[0079] A raw material formula for black-glazed white porcelain with black decoration: 70% slab soil, 12.5% ​​black clay, 10% feldspar, and 7.5% quartz are weighed out according to the following mass ratio, with the addition of sodium carboxymethyl cellulose (0.8% by mass of the base glaze) and sodium polyphosphate (0.3% by mass). The preparation method is the same as in Example 3, except that the temperature is changed from 1250℃ to 1270℃. Because talc, manganese oxide, and iron oxide were not introduced, the firing temperature was increased, and although the color of the sample deepened, it was not as good as in Example 3.

[0080] Comparative Example 3

[0081] A raw material formula for black-glazed white porcelain: 45% slab soil, 15% black clay, 7% feldspar, 6% quartz, 15% talc, 6% manganese oxide, and 6% iron oxide are weighed out according to the following mass ratio. Additionally, 0.8% sodium carboxymethyl cellulose and 0.3% sodium polyphosphate (by mass of the base glaze) are added. The preparation method is the same as in Example 3. Due to the excessive addition of talc, manganese oxide, and iron oxide, which has a fluxing effect, the sample exhibits a deeper color, but lacks vibrancy.

[0082] This invention, by adjusting the content of each component in the formula, the thickness of the glaze layer, and the firing process, determines the optimal ratio, effectively improving the glaze color and quality of black enamel on white-based black-decorated porcelain. This broadens the application range of underglaze decoration in traditional ceramics, achieving a yield rate of over 75%. Furthermore, the use of low-quality raw materials significantly reduces production costs, while also offering good environmental and social benefits. Therefore, this invention not only provides innovative improvements for ceramic enterprises in the preparation of black enamel on white-based black-decorated porcelain, offering an effective experimental basis for energy-saving and environmentally friendly production in the ceramic industry, but also lays the foundation for research on the color-growth mechanism of ancient porcelain samples.

Claims

1. A method for preparing white ground black flower porcelain black color, characterized in that, The raw materials for the black-glazed porcelain with white background and black decoration, by weight percentage, include: a base glaze and auxiliary materials. The base glaze consists of: 50%~65% slab soil, 14%~19% black clay, 5%~8% feldspar, 3%~6% quartz, 5%~11% talc, 1%~4% manganese oxide, and 1%~4% iron oxide. The auxiliary materials include sodium carboxymethyl cellulose at 0.8% of the base glaze and sodium polyphosphate at 0.3%. The black clay consists of: 50% sandy loam, 20% Dongshan loam, and 30% Yuzhai loam. The preparation method includes: S1, take black clay raw material and shape it, dry it to obtain the blank; brush a layer of slip on the surface of the blank; S2, take raw materials such as slope soil, black clay, feldspar, quartz, talc, manganese oxide, iron oxide, sodium carboxymethyl cellulose and sodium polyphosphate and mix them to obtain a mixed glaze; S3, the mixed glaze obtained in S2 is subjected to wet ball milling to obtain black glaze slurry; S4. Apply the black glaze obtained in S3 to the body obtained in S1 using a brush glazing method, and let it dry to obtain a colored body; the glaze thickness is controlled between 0.5 mm and 0.8 mm. S5, Apply a layer of transparent glaze to the colored blank obtained in S4 using the dipping glaze method, and let it dry; S6, the colored blank with transparent glaze obtained in S5 is fired once in a neutral atmosphere to prepare black-painted porcelain with white ground and black decoration on black body.

2. The method for preparing black-painted porcelain with white background according to claim 1, characterized in that, In S1, the black tire material is first repeatedly pounded to remove excess gas before being shaped.

3. The method for preparing black-painted porcelain with white background according to claim 1, characterized in that, In S1, the thickness of the slip layer is 0.5-1mm.

4. The method for preparing black-painted porcelain on a white background according to claim 1, characterized in that, In S3, the wet ball milling speed is 300 r / min, the ball milling time is 40~45 min, and the mass ratio of material, balls and water is 1:2:

1.

5. The method for preparing black-painted porcelain with white background according to claim 1, characterized in that, Before S4, wet the surface of the blank obtained in S1 with water.

6. The method for preparing black-painted porcelain on a white background according to claim 1, characterized in that, In S6, the firing process is as follows: the temperature is increased from room temperature to 300℃ at a heating rate of 4.5~5℃ / min, then increased from 300℃ to 900℃ at a heating rate of 3.3~3.5℃ / min, and then increased from 900℃ to 1250℃ at a heating rate of 1.2~1.4℃ / min; the temperature is held at 1250℃ for 30 minutes, and then cooled with the furnace.

7. The black-painted porcelain with white background and black decoration obtained by the preparation method according to any one of claims 1 to 6.

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