CN110713345A - Enamel color material, preparation method and application in repairing enamel cultural relics painted on porcelain body - Google Patents
Enamel color material, preparation method and application in repairing enamel cultural relics painted on porcelain body Download PDFInfo
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- CN110713345A CN110713345A CN201911264575.3A CN201911264575A CN110713345A CN 110713345 A CN110713345 A CN 110713345A CN 201911264575 A CN201911264575 A CN 201911264575A CN 110713345 A CN110713345 A CN 110713345A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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Abstract
The invention discloses an enamel color material, a preparation method and application thereof in repairing enamel cultural relics painted on a porcelain body, wherein the enamel color material comprises the following chemical components in percentage by mass: silicon dioxide: 33% -51%, aluminum oxide: 0% -3.8%, boron oxide: 8% -19%, lead oxide: 31% -53%, calcium oxide + magnesium oxide: 0% -6%, sodium oxide + potassium oxide: 0% -6.9%, bismuth trioxide: 0.5% -6%, tin oxide: 0% -7.2%, antimony trioxide: 0% -6.5%, ferric oxide: 0% -13%, copper oxide: 0% -4.2%, cobalt oxide: 0% -4%, manganese oxide: 0% -9%, silver oxide: 0-2%, gold oxide: 0 to 0.15 percent. Compared with the traditional enamel color porcelain, the enamel color material provided by the invention has a lower melting point, can be melted with an ancient enamel color pigment layer at a high temperature, can be matched with the thermal expansion coefficients of the surface glaze and the pigment layer of the traditional enamel color, has good adhesiveness, good adhesiveness before firing and easy dispersion, has moderate material surface tension in the firing and leveling process, meets the requirement of leveling property, and can keep a certain colored drawing three-dimensional shape.
Description
Technical Field
The invention relates to the technical field of cultural relic restoration, in particular to an enamel color material, a preparation method and application thereof in porcelain body painting enamel cultural relic restoration.
Background
The first monograph for appreciating cultural relics of China introduces enamel which is similar to Buddha's Lague by using copper as a body and burning five-color flowers with medicine, and the traditional enamel craft product is an enamel color material prepared by mixing silicate mineral quartz, minium, borax, feldspar and other raw materials according to a proper proportion, adding various colored metal oxides, roasting, cooling and grinding into powder. According to different colors and process methods, the enamel color material is filled and embedded or drawn on the surfaces of metal blanks, glass blanks, porcelain blanks and purple sand blanks, and then is sintered to form the enamel container, wherein the enamel container is named according to different matrix bodies, copper blank enamel is commonly called cloisonne, glass blank enamel is called material blank enamel, and porcelain blank enamel is called enamel color porcelain or enamel color for short. The enamel color porcelain is rare in quantity due to expensive enamel materials and complex manufacturing process, has extremely high artistic value, becomes the peak of the Chinese ceramic art aesthetics, has few products nowadays, and is mostly stored in Taibei and Beijing Story courts of China.
The aim of cultural relic repair is to protect and transmit cultural relics and cultural information carried by the cultural relics, and the repair process can be 'repaired' according to the original materials and the process. Ancient ceramics are the main products for repairing cultural relics, and the principle is 'repair as old as possible', wherein 'repair as old' refers to the process which is as close as possible to the original process of the cultural relics in the repairing process, and 'as old' refers to the process which uses the original materials as far as possible in the materials and achieves the original effect of the cultural relics in appearance, but is typically different from other cultural relic repairing materials and processes in that ceramics need to be fired at high temperature, the damage to the ceramic ware is irreversible when the repairing is unsuccessful, particularly, the repairing of enamel colored ceramics is always a difficult problem in the ancient ceramic world and the cultural relic world, because the observed physical specimens are few and extremely precious, even if there is an opportunity to repair, the repair of the enamel color can not be performed because the enamel color material is difficult to master, so the repair of the enamel color is mainly an archaeological repair process without secondary kiln return fire, namely, cementing, polishing and color filling repair, and the 'repair' process of the ceramic cannot be realized.
The ancient traditional enamel color porcelain manufacturing process comprises the following steps: firstly preparing "PbO-B2O3-SiO2The low-temperature colored glass frits which take different metal elements as coloring agents are ground into fine powder to form pigments of various colors, oil or water is used as a mixing medium, and the pigments of various colors are drawn on a processed porcelain body and then are fired at low temperature. Because the enamel color material is manufactured at the inner-court manufacturing place in the early generation period, and the enamel color porcelain is completely fired from the Jingdezhen porcelain body or the Yixing purple sand body to the intrauterine enamel, the knowledge of the external world on the data and the process of the enamel color porcelain is very little, so that the enamel color porcelain process is lost in the late generation period.
There are also some china on the market today, known by itself as "enamel colored porcelain", three main types: a method for preparing "glass white" enamel color by "pastel" process includes such steps as coating a layer of pastel on the surface of enamel blank2O-SiO2-As2O3The system glass is used as a substrate, and then is put into a kiln 730-And (3) coating glass white for the second time, painting the glass white, rendering and coloring, and then putting the glass white into a kiln for sintering. The 'glass white' double firing method is thickened to generate the 'brightness' and 'stacking' feeling similar to enamel colored porcelain, but the 'glass white' does not have B in the method2O3The flux has the function of fluxing, can simultaneously reduce the texture, the refractive index and the luminosity of glass, and can not achieve the effect of the traditional enamel colored porcelain. Secondly, adopting the mode of 'fluxing of the low borosilicate glass and adding synthetic inorganic pigment' of the modern process method, wherein B in the low borosilicate glass2O3The content of (A) is low, usually less than 8%, which can cause two effect problems, namely, the colored drawing enamel is not transparent, the enamel is high in viscosity and poor in pigment dispersibility, and color particles can be seen under a magnifier to influence the effect; in addition, the low borosilicate glass has high softening temperature, and the temperature for sintering the low borosilicate glass as a cultural relic repair material is higher than the softening temperature of the original enamel glaze, so that other parts of the ancient ceramics can be cracked and melted, the ancient ceramics can not be repaired, and the ancient ceramics can be damaged. The third method is to use "Li2O-K2O-Na2O-SiO2The method is closest to the traditional process, the material of the system can be used for drawing the imitated enamel colored porcelain independently, but the formula temperature is obviously higher than that of 'PbO-B' of the original enamel color2O3-SiO2The system can not be similar to the color layer of the ancient ceramics due to different systems, and can not be used as a repairing material of the ancient enamel color ceramic ware.
Also, for example, chinese patent No. CN1055348A entitled glass composition discloses a glass flux composition for enamel, which is a decorative material prepared by mixing low-melting glass as a main solvent with inorganic pigments. The glass composition contains a large amount of alkali metal elements, has a loose glass structure, and has a thermal expansion coefficient of 80 x 10-7-95×10-7m/K, 65X 10 higher than that of ceramic-7-70×10-7m/K coefficient of thermal expansion, which leads to a tendency to glaze and crack after decorating the ceramicPeeling off, the decorative effect of daily utensils with more cold and hot changes such as tea sets, tableware and the like is easy to damage, and the daily utensils can not be used as ancient ceramic repairing materials.
A Chinese patent with patent number CN1093684A entitled cover layer of ceramic glaze pigment and its processing and products discloses a cover layer of ceramic glaze pigment for preventing lead from dissolving out at high temperature, wherein Al with 5% -8% of viscosity regulator is used2O3The purpose is to improve the high-temperature viscosity, the melting temperature is 1300-1350 ℃, so that lead is not easy to volatilize in the secondary sintering process, and the purpose of serving as an ancient ceramic repairing material cannot be realized unlike the low viscosity and low melting point required by the invention.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an enamel color material.
The invention aims to provide a preparation method of the enamel color material.
The invention also aims to provide an application of the enamel color material in repairing enamel cultural relics painted on a porcelain body.
In order to achieve the purpose, the invention adopts the following technical scheme.
The enamel color material is characterized by comprising the following chemical components in percentage by mass: silicon dioxide: 33% -51%, aluminum oxide: 0% -3.8%, boron oxide: 8% -19%, lead oxide: 31% -53%, calcium oxide + magnesium oxide: 0% -6%, sodium oxide + potassium oxide: 0% -6.9%, bismuth oxide: 0.5% -6%, tin oxide: 0% -7.2%, antimony trioxide: 0% -6.5%, ferric oxide: 0% -13%, copper oxide: 0% -4.2%, cobalt oxide: 0% -4%, manganese oxide: 0% -9%, silver oxide: 0-2%, gold oxide: 0 to 0.15 percent. The formula of the enamel color material provided by the invention can be prepared from the following raw materials: lead silicate, anhydrous boric acid, bismuth trioxide, potassium nitrate, calcite, and one or more of quartz, calcined kaolin, sodium tetraborate, dolomite, tin oxide, antimony trioxide, ferric oxide, copper oxide, cobalt oxide, manganese oxide, silver oxide, and gold chloride solution containing gold oxide.
As a further explanation of the above scheme, the enamel color material is carmine color enamel pigment, which comprises the following raw materials in parts by mass: 53 parts of lead silicate, 34 parts of quartz, 12 parts of anhydrous boric acid, 14 parts of potassium nitrate, 3.5 parts of bismuth trioxide, 0.12 part of silver oxide, 1.2 parts of tin oxide, 8 parts of calcined kaolin, 4.5 parts of calcite and a gold chloride solution containing 0.096 part of gold oxide;
the raw materials comprise the following chemical components in percentage by mass: silicon dioxide: 37.8%, boron oxide: 9.8%, lead oxide: 37.12%, bismuth trioxide: 2.89%, aluminum oxide: 2.84%, sodium oxide + potassium oxide: 6.3%, tin oxide: 0.99%, silver oxide: 0.10%, calcium oxide + magnesium oxide: 2.08%, gold oxide: 0.08 percent.
As a further explanation of the above scheme, the enamel color material is a black enamel color pigment, which comprises the following raw materials in parts by mass: 41 parts of lead silicate, 28 parts of quartz, 10 parts of anhydrous boric acid, 2.5 parts of bismuth trioxide, 13 parts of potassium nitrate, 2 parts of calcite, 9.5 parts of ferric oxide, 3.5 parts of manganese oxide, 0.5 part of cobalt oxide and 0.06 part of copper oxide;
the raw materials comprise the following chemical components in percentage by mass: silicon dioxide: 33.4%, boron oxide: 9.7%, lead oxide: 33.5%, bismuth trioxide: 2.4%, cobalt oxide: 0.49%, sodium oxide + potassium oxide: 6.8%, magnesium oxide + calcium oxide: 1.05%, ferric oxide: 9.2%, manganese oxide: 3.4%, copper oxide: 0.06 percent.
As a further explanation of the above scheme, the enamel color material is a yellow enamel color pigment, which comprises the following raw materials in parts by mass: 52 parts of lead silicate, 33 parts of quartz, 8 parts of anhydrous boric acid, 4 parts of bismuth trioxide, 2 parts of potassium nitrate, 2 parts of calcite, 5.5 parts of antimony trioxide, 3.1 parts of tin oxide, 1.7 parts of iron oxide, 4 parts of sodium tetraborate and 0.04 part of copper oxide;
the raw materials comprise the following chemical components in percentage by mass: silicon dioxide: 36.96%, boron oxide: 9.5%, lead oxide: 39.9%, bismuth trioxide: 3.52%, tin oxide: 2.73%, calcium oxide + magnesium oxide: 1.0%, ferric oxide: 1.50%, copper oxide: 0.04%, antimony trioxide: 4.85 percent.
For further explanation of the scheme, the enamel color material is a turquoise blue enamel color pigment, and comprises the following raw materials in parts by weight: 62 parts of lead silicate, 33 parts of quartz, 11 parts of anhydrous boric acid, 3 parts of bismuth trioxide, 15 parts of potassium nitrate, 2.4 parts of cobalt oxide, 2 parts of calcite and 4.5 parts of iron oxide;
the raw materials comprise the following chemical components in percentage by mass: silicon dioxide: 34.3%, boron oxide: 9.0%, lead oxide: 41.0%, bismuth trioxide: 2.44%, ferric oxide: 3.69%, sodium oxide + potassium oxide: 6.7%, cobalt oxide: 1.97%, calcium oxide + magnesium oxide: 0.90 percent.
A preparation method of the enamel color material is characterized by comprising the following steps:
1) preparing materials according to the raw materials and the mass parts of the raw materials;
2) drying the raw materials, grinding uniformly until all the raw materials pass through a 20-40-mesh sieve, and then filling the raw materials into a dried aluminum oxide crucible with a cover;
3) opening the cover of the alumina crucible filled with the materials, putting the alumina crucible into a heating device, uniformly heating to 650 ℃, covering the cover of the alumina crucible, continuously heating to 1050 and 1280 ℃ of the highest melting temperature, and preserving the heat at the highest melting temperature for 5-10 minutes to obtain uniformly clarified glass liquid;
4) and pouring the glass liquid into cold water for water quenching to obtain glass frit, putting the glass frit into a grinding device, adding water to grind the slurry until the slurry passes through a sieve of 250-325 meshes, and drying the sieved slurry to obtain the powdery enamel color porcelain pigment.
As a further illustration of the above scheme, the heating device in step 3 is a frit furnace, and the temperature of the frit furnace is uniformly increased at a temperature increasing rate of 10 ℃/min.
As a further illustration of the above scheme, the 20-40 mesh sieve is passed twice in step 2; in step 4 the milling apparatus is an alumina lined ball mill.
The application of the enamel color material in repairing enamel cultural relics painted on a porcelain blank is characterized by comprising the following steps:
1) adding butter oil or water into the enamel material to be painted according to the color and the pattern of the enamel colored porcelain to be repaired, adjusting the viscosity to be proper for color painting, filling color with a writing brush, and washing and dyeing the surface of the enamel colored porcelain to be repaired;
2) and (3) putting the repaired or decorated ceramic into a kiln, heating to the maximum temperature of 620-780 ℃ in an oxidizing atmosphere, preserving the heat for 5-15 minutes after reaching the maximum temperature, and keeping the total firing time for 4-6 hours.
The invention has the beneficial effects.
Firstly, compared with the traditional enamel color porcelain, the enamel color material provided by the invention is PbO-B2O3-SiO2The system has lower melting point and good high-temperature quick leveling property, can be melted with the ancient enamel color pigment layer at high temperature similarly, can be matched with the thermal expansion coefficient of the surface glaze and the pigment layer of the traditional enamel color, can be well adhered to the ancient enamel color porcelain body, can be used for secondary color filling on the originally drawn enamel color material, has good adhesion property before sintering and easy dispersion, has moderate material surface tension in the sintering leveling process, meets the leveling property and can keep a certain colored drawing three-dimensional shape.
The enamel color material provided by the invention can also be used for manufacturing enamel color porcelain, the color and luster of the fired enamel are bright, the enamel has the characteristic of translucence or transparency of the traditional enamel color porcelain glaze, the change of light and shade of decorative patterns can be effectively expressed, and the glaze is not easy to crack when being heated or cooled.
And thirdly, the enamel color material provided by the invention is simple in production process and beneficial to popularization and use.
Detailed Description
In the description of the present invention, it should be noted that, for the terms of orientation, there are terms of orientation such as "central", "lateral", "longitudinal", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise" and the like, which are used for convenience of description and simplification of the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and should not be construed as limiting the specific scope of protection of the present invention.
Furthermore, if the terms "first" and "second" are used for descriptive purposes only, they are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features. Thus, a definition of "a first" or "a second" feature may explicitly or implicitly include one or more of the feature, and in the description of the invention, "at least" means one or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "assembled", "connected", and "connected" are to be construed broadly, e.g., as meaning fixedly connected, detachably connected, or integrally connected; or may be a mechanical connection; the two elements can be directly connected or connected through an intermediate medium, and the two elements can be communicated with each other. The specific meanings of the above terms in the present invention can be understood by those of ordinary skill in the art according to specific situations.
In the present invention, unless otherwise specified and limited, "above" or "below" a first feature may include the first and second features being in direct contact, and may also include the first and second features not being in direct contact but being in contact with each other through another feature therebetween. Also, the first feature being "above," "below," and "above" the second feature includes the first feature being directly above and obliquely above the second feature, or simply an elevation which indicates a level of the first feature being higher than an elevation of the second feature. The first feature being "above", "below" and "beneath" the second feature includes the first feature being directly below or obliquely below the second feature, or merely means that the first feature is at a lower level than the second feature.
The following further describes the embodiments of the present invention, so that the technical solutions and the advantages thereof of the present invention are more clear and definite. The following examples are illustrative and are intended to illustrate the invention and are not to be construed as limiting the invention.
The first embodiment is as follows: and repairing the black color shortage and the yellow pistil part of the enamel color ancient porcelain plate with the black bottom.
(1) Preparing black enamel color pigment:
1) weighing the following raw materials in parts by weight: 41 parts of lead silicate, 28 parts of quartz, 10 parts of anhydrous boric acid, 2.5 parts of bismuth trioxide, 13 parts of potassium nitrate, 2 parts of calcite, 9.5 parts of ferric oxide, 3.5 parts of manganese oxide, 0.5 part of cobalt oxide and 0.06 part of copper oxide;
table 1 shows the main chemical components of the black enamel color pigment and the mass percentages of the chemical components:
2) mixing the weighed raw materials, placing the mixture into a ceramic mortar, grinding the mixture until the mixture passes through a 30-mesh sieve twice, and placing the mixture into an alumina crucible with a cover;
3) placing the alumina crucible with the cover in a frit furnace in an open manner, uniformly heating the frit furnace to 650 ℃ at a heating rate of 10 ℃/min, covering the cover of the alumina crucible, continuously heating to the highest melting temperature of 1210 ℃, and preserving heat for 10 minutes to obtain clear molten glass;
4) and pouring the glass liquid into cold water for water quenching to obtain glass frits, putting the glass frits into an alumina lining ball mill, grinding until all the slurry passes through a 250-mesh sieve, and drying after sieving to obtain the black enamel color pigment.
(2) Preparing yellow enamel color pigment:
1) the following raw materials are weighed and taken in parts by weight: 52 parts of lead silicate, 33 parts of quartz, 8 parts of anhydrous boric acid, 4 parts of bismuth trioxide, 2 parts of potassium nitrate, 2 parts of calcite, 5.5 parts of antimony trioxide, 3.1 parts of tin oxide, 1.7 parts of iron oxide, 4 parts of sodium tetraborate and 0.04 part of copper oxide;
table 2 shows the main chemical components of the yellow enamel color pigment and the mass percentages of the chemical components:
2) mixing the weighed raw materials, placing the mixture into a ceramic mortar, grinding the mixture until the mixture passes through a 30-mesh sieve twice, and placing the mixture into an alumina crucible with a cover;
3) placing the alumina crucible with the cover in a frit furnace after opening the cover, uniformly heating the frit furnace to 650 ℃ at the heating rate of 10 ℃/min, then covering the cover of the alumina crucible, continuously heating to the maximum melting temperature of 1250 ℃, and preserving the heat for 10 minutes to obtain clear molten glass;
4) and pouring the glass liquid into cold water for water quenching to obtain glass frits, putting the glass frits into an alumina lining ball mill, grinding until all the slurry passes through a 250-mesh sieve, and drying after sieving to obtain the yellow enamel color pigment.
(3) Repairing the black enamel color ancient porcelain plate:
adding water into the prepared black enamel color pigment, uniformly mixing, placing the mixture into a porcelain dish to be repaired, dropping a small amount of clear water on one side of the pigment according to the pigment concentration standard that the pigment is piled into a dam shape when the pigment is in a non-flowing state, filling a color stroke with soft goat hair, stirring to a viscosity suitable for color filling, and filling the color stroke into the repaired porcelain according to the contour of the original ancient porcelain missing color material part. And adding water into the yellow enamel color pigment, uniformly mixing, using a similar method to dot the pigment on the missing yellow flower core part in the plate according to the original pattern by using a writing brush, standing and drying, putting the porcelain into a furnace, carrying out color baking in an oxidizing atmosphere, heating to the maximum temperature of 750 ℃, and then carrying out heat preservation for 15 minutes, wherein the total baking time is 5 hours, thus obtaining the repaired black-bottom enamel color porcelain plate.
Example two: and repairing the blue colored drawing part of the enamel dark-red enameled pottery.
(1) Preparing turquoise blue enamel color pigment:
1) weighing the following raw materials in parts by weight: 62 parts of lead silicate, 33 parts of quartz, 11 parts of anhydrous boric acid, 3 parts of bismuth trioxide, 15 parts of potassium nitrate, 2.4 parts of cobalt oxide, 2 parts of calcite and 4.5 parts of iron oxide;
table 3 shows the main chemical components of the turquoise blue enamel color pigment and the mass percentages of the chemical components:
2) mixing the weighed raw materials, placing the mixture into a ceramic mortar, grinding the mixture until the mixture passes through a 30-mesh sieve twice, and placing the mixture into an alumina crucible with a cover;
3) placing the alumina crucible with the cover into a frit furnace, opening the cover of the alumina crucible, uniformly heating the frit furnace to 650 ℃ at the heating rate of 10 ℃/min, covering the cover of the alumina crucible, continuously heating to the maximum melting temperature of 1250 ℃, and preserving the heat for 10 minutes to obtain clear molten glass;
4) and pouring the glass liquid into cold water to be quenched into water to obtain glass frits, putting the glass frits into an alumina lining ball mill, grinding until all the slurry passes through a 250-mesh sieve, and drying after sieving to obtain the turquoise blue enamel color pigment.
(2) Repairing the painted enamel dark-red enameled pottery:
1) blending the prepared turquoise blue enamel color pigment and frankincense oil to proper color painting viscosity, putting the dark-red enameled pottery to be repaired in a hot air drying furnace at 120 ℃, preserving the heat for 30 minutes, and cooling to room temperature;
2) rendering colored drawings for multiple times by using a writing brush according to the lack of blue colored material parts of the original purple clay ware, drying the colored drawing part on the surface of the purple clay pot by using a hot air blower until the colored drawing part is dry, putting the purple clay pot into an electric furnace for colored baking, heating to the maximum temperature of 710 ℃, keeping the temperature for 5 minutes, then cooling, and carrying out total firing in an oxidizing atmosphere for 4 hours to obtain the enamel purple clay pot with repaired pictures.
Example three: and manufacturing the carmine enamel colored porcelain.
(1) Preparation of carmine color enamel pigment:
1) weighing 53 parts of lead silicate, 34 parts of quartz, 12 parts of anhydrous boric acid, 14 parts of potassium nitrate, 3.5 parts of bismuth trioxide, 0.12 part of silver oxide, 1.2 parts of tin oxide, 8 parts of calcined kaolin and 4.5 parts of calcite;
table 4 shows the main chemical components of the carmine enamel color pigment and the mass percentages of the components:
2) mixing the weighed raw materials, adding the mixture into a ceramic mortar, grinding the mixture evenly, adding a gold chloride solution containing 0.08 percent of gold oxide, and stirring the mixture evenly, wherein the mass percent of 0.08 percent of the gold chloride solution containing 0.08 percent of gold oxide is the mass percent of the whole formula;
3) pouring into a stainless steel plate, washing the mortar with distilled water for 2-3 times, pouring the washed solution into the stainless steel plate, drying the materials in the stainless steel plate, sieving the dried materials with a 30-mesh sieve twice, and placing the sieved materials into an alumina crucible;
4) placing the alumina crucible into a frit furnace, uniformly heating the frit furnace to 1150 ℃ of the highest melting temperature at the heating rate of 10 ℃/min, and preserving the temperature for 10 minutes to obtain clear molten glass;
5) and pouring the glass liquid into cold water for water quenching to obtain glass frits, putting the glass frits into an alumina lining ball mill, grinding until the slurry passes through a 325-mesh sieve, and drying the sieved glaze slurry to obtain the carmine red enamel color pigment, wherein the residual content of the sieved glaze slurry is less than 0.3%.
(2) Glazing:
1) mixing the prepared carmine color enamel pigment with water according to the proportion of 1:1, and then carrying out ball milling uniformly;
2) preheating the porcelain white blank to 60 ℃, applying the porcelain white blank on the porcelain white blank for a few times by a glaze blowing method, wherein the thickness of a glaze layer is 0.15-0.2mm, and wiping off the splash glaze at the mouth and the bottom of the porcelain after standing and drying;
3) and putting the glazed porcelain into a decoration firing furnace for color firing, heating to the maximum temperature of 780 ℃, and preserving the heat for 5 minutes in an oxidizing atmosphere to obtain the enamel color carmine porcelain.
It will be appreciated by those skilled in the art from the foregoing description of construction and principles that the invention is not limited to the specific embodiments described above, and that modifications and substitutions based on the teachings of the art may be made without departing from the scope of the invention as defined by the appended claims and their equivalents. The details not described in the detailed description are prior art or common general knowledge.
Claims (9)
1. The enamel color material is characterized by comprising the following chemical components in percentage by mass:
silicon dioxide: 33% -51%, aluminum oxide: 0% -3.8%, boron oxide: 8% -19%, lead oxide: 31% -53%, calcium oxide + magnesium oxide: 0% -6%, sodium oxide + potassium oxide: 0% -6.9%, bismuth trioxide: 0.5% -6%, tin oxide: 0% -7.2%, antimony trioxide: 0% -6.5%, ferric oxide: 0% -13%, copper oxide: 0% -4.2%, cobalt oxide: 0% -4%, manganese oxide: 0% -9%, silver oxide: 0-2%, gold oxide: 0 to 0.15 percent.
2. The enamel color material according to claim 1, wherein the enamel color material is carmine red enamel color pigment, and comprises the following raw materials in parts by weight:
53 parts of lead silicate, 34 parts of quartz, 12 parts of anhydrous boric acid, 14 parts of potassium nitrate, 3.5 parts of bismuth trioxide, 0.12 part of silver oxide, 1.2 parts of tin oxide, 8 parts of calcined kaolin, 4.5 parts of calcite and a gold chloride solution containing 0.096 part of gold oxide;
the raw materials comprise the following chemical components in percentage by mass:
silicon dioxide: 37.8%, boron oxide: 9.8%, lead oxide: 37.12%, bismuth trioxide: 2.89%, aluminum oxide: 2.84%, sodium oxide + potassium oxide: 6.3%, tin oxide: 0.99%, silver oxide: 0.10%, calcium oxide + magnesium oxide: 2.08%, gold oxide: 0.08 percent.
3. The enamel color material according to claim 1, wherein the enamel color material is a black enamel color pigment, and comprises the following raw materials in parts by weight:
41 parts of lead silicate, 28 parts of quartz, 10 parts of anhydrous boric acid, 2.5 parts of bismuth trioxide, 13 parts of potassium nitrate, 2 parts of calcite, 9.5 parts of ferric oxide, 3.5 parts of manganese oxide, 0.5 part of cobalt oxide and 0.06 part of copper oxide;
the raw materials comprise the following chemical components in percentage by mass:
silicon dioxide: 33.4%, boron oxide: 9.7%, lead oxide: 33.5%, bismuth trioxide: 2.4%, cobalt oxide: 0.49%, sodium oxide + potassium oxide: 6.8%, magnesium oxide + calcium oxide: 1.05%, ferric oxide: 9.2%, manganese oxide: 3.4%, copper oxide: 0.06 percent.
4. The enamel color material according to claim 1, wherein the enamel color material is a yellow enamel color pigment, and comprises the following raw materials in parts by weight:
52 parts of lead silicate, 33 parts of quartz, 8 parts of anhydrous boric acid, 4 parts of bismuth trioxide, 2 parts of potassium nitrate, 2 parts of calcite, 5.5 parts of antimony trioxide, 3.1 parts of tin oxide, 1.7 parts of iron oxide, 4 parts of sodium tetraborate and 0.04 part of copper oxide;
the raw materials comprise the following chemical components in percentage by mass:
silicon dioxide: 36.96%, boron oxide: 9.5%, lead oxide: 39.9%, bismuth trioxide: 3.52%, tin oxide: 2.73%, calcium oxide + magnesium oxide: 1.0%, ferric oxide: 1.50%, copper oxide: 0.04%, antimony trioxide: 4.85 percent.
5. The enamel color material according to claim 1, wherein the enamel color material is a turquoise blue enamel color pigment, and comprises the following raw materials in parts by weight:
62 parts of lead silicate, 33 parts of quartz, 11 parts of anhydrous boric acid, 3 parts of bismuth trioxide, 15 parts of potassium nitrate, 2.4 parts of cobalt oxide, 2 parts of calcite and 4.5 parts of iron oxide;
the raw materials comprise the following chemical components in percentage by mass:
silicon dioxide: 34.3%, boron oxide: 9.0%, lead oxide: 41.0%, bismuth trioxide: 2.44%, ferric oxide: 3.69%, sodium oxide + potassium oxide: 6.7%, cobalt oxide: 1.97%, calcium oxide + magnesium oxide: 0.90 percent.
6. A process for the preparation of an enamel coloring material according to any one of claims 1 to 5, comprising the steps of:
1) preparing the raw materials according to the mass parts of the raw materials;
2) drying the raw materials, grinding uniformly until all the raw materials pass through a 20-40-mesh sieve, and then filling the raw materials into a dried aluminum oxide crucible with a cover;
3) after uncovering the alumina crucible filled with the materials, putting the alumina crucible into a heating device, uniformly heating to 650 ℃, covering the cover of the alumina crucible, continuously heating to 1050-;
4) and pouring the glass liquid into cold water for water quenching to obtain glass frit, putting the glass frit into a grinding device, adding water to grind the slurry until the slurry passes through a sieve with 325 meshes, and drying the sieved slurry to obtain the powdery enamel color porcelain pigment.
7. The method according to claim 6, wherein said heating means in step 3 is a frit furnace, and said frit furnace is heated uniformly at a heating rate of 10 ℃/min.
8. The method of making enamel color according to claim 6 wherein the passing through the 20-40 mesh screen in step 2 is twice the passing through the 20-40 mesh screen; in step 4 the milling apparatus is an alumina lined ball mill.
9. Use of an enamel paint according to any one of claims 1 to 5 for repairing enamel relics painted on a porcelain body, comprising the following steps:
1) adding butter oil or water into the enamel material to be painted according to the color and the pattern of the enamel colored porcelain to be repaired to adjust the viscosity to be suitable for colored painting, filling and washing and dyeing the enamel material on the surface of the enamel colored porcelain to be repaired by a writing brush;
2) and (3) putting the repaired or decorated ceramic into a kiln, heating to the maximum temperature of 620-780 ℃ in an oxidizing atmosphere, preserving the heat for 5-15 minutes after reaching the maximum temperature, and keeping the total firing time for 4-6 hours.
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| CN113666663A (en) * | 2021-10-20 | 2021-11-19 | 佛山市天工嘉荟文化科技有限公司 | Large-area reparation ceramic defect material and ancient ceramic repair process |
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| US4618538A (en) * | 1984-09-12 | 1986-10-21 | Saint-Gobain Vitrage | Colored enamel composition for obtaining decorative layers of float glass sheets |
| CN1093684A (en) * | 1993-04-14 | 1994-10-19 | 山东省硅酸盐研究设计院 | Cover-coat for colour on glazed ceramics and processing thereof and goods |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4618538A (en) * | 1984-09-12 | 1986-10-21 | Saint-Gobain Vitrage | Colored enamel composition for obtaining decorative layers of float glass sheets |
| CN1093684A (en) * | 1993-04-14 | 1994-10-19 | 山东省硅酸盐研究设计院 | Cover-coat for colour on glazed ceramics and processing thereof and goods |
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|---|---|---|---|---|
| CN113666663A (en) * | 2021-10-20 | 2021-11-19 | 佛山市天工嘉荟文化科技有限公司 | Large-area reparation ceramic defect material and ancient ceramic repair process |
| CN113666663B (en) * | 2021-10-20 | 2021-12-21 | 佛山市天工嘉荟文化科技有限公司 | Large-area reparation ceramic defect material and ancient ceramic repair process |
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