Method for producing ceramic pigment based on natural minerals

IPC classes for russian patent Method for producing ceramic pigment based on natural minerals (RU 2255911):

C03C1/04 - CHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS

Another patents in same IPC classes:

Blend for preparing ceramic orange-brown-color pigment / 2255056

Invention concerns manufacture of ceramic pigments for decorating porcelain-faience and majolica articles. Blend for ceramic pigment contains SiO₂, Al₂O₃, V₂O₅, and K₂O in the form of baked diatomite-supported sulfovanadate catalyst composed of, wt %: SiO₂ 73.81, V₂O₅ 8.33, Al₂O₃ 5.95, K₂O 11.91. Blend additionally contains 5-15% MnO. Synthesis temperature of pigment is 800-950°C. Pigment is recommended for use in overglaze ceramic paints and to color glazes.

Brown ceramic pigment / 2248333

Claimed pigment contains (mass %): Fe₂O₃ 21.90-23.10; ZnO 33.04-38.56; SiO₂ 1.10-2.4; Al₂O₃ 0.89-1.08; TiO₂ 9.30-11.01; CaO 0.99-1.14; MnO 1.04-1.20; MgO 0.40-0.62; K₂O 0.24-0.36; FeO 22.70-27.00; Na₂O 0.32-0.54; P₂O₅ 0.21-0.41; V₂O₅ 0.25-0.30. Titanomagnetite concentrate and zinc oxide are used as raw materials. Pigment composition of present invention makes it possible to reduce synthesis temperature up to 750-1100⁰C and increase color purity up to 31.5-33.1 %.

Blend for preparing ceramic orange-brown-color pigment / 2255056

Brown ceramic pigment / 2248333

Method of preparing glassmaking mixture / 2246453

In order to increase homogeneity and chemical activity of glass mixtures for manufacturing building and other kinds of glass, mixture components are ground, sieved, transported, stirred, and granulated. Kaolin and soda are preliminarily mixed at weight ratio 3:7. moistened to 5-7%, and granulated on rotary blade granulator. Granules up to 0.5 mm in size are characterized by strength 10.5 kg/cm² and moisture content 4.5%.

Method of preparing raw concentrate for glass manufacture / 2244691

In manufacture of packaging, sheet, and other types of glasses, starting concentrate is supplemented by zircon-ilmenite ore concentration by-products and native soda at ratio (55-65):(15-25):(15-20), respectively. Concentrate preparation comprises dosage, stirring of raw components, moistening, and compaction on roll press with roll diameter 350 mm and rotation speed 22 rpm. Gap between rolls in compaction zone is 0.5 mm. Compaction is performed at as low pressure as 10-15 MPa with 5% of water added to concentrate. Compacted product is characterized by that by strength 1.2-1.6 MPa and density 2130 kg/m³.

Method of preparing raw concentrate for glass manufacture / 2244691

Method of preparing glassmaking mixture / 2246453

Brown ceramic pigment / 2248333

Blend for preparing ceramic orange-brown-color pigment / 2255056

Method for producing ceramic pigment based on natural minerals / 2255911

Invention relates to a method for producing ceramic pigments for decoration of porcelain and faience articles and for staining ceramic masses and glazes. Mixture of mineral powder and chromophore solution in the concentration 4.0-15.6 g-ions/100 g of solution is subjected for hydrothermal treatment (autoclaving) at temperature 170-190°C and under pressure 0.8-1.2 MPa. Deposit is squeezed out, dried and roasted at temperature 950-1100°C. Mineral is taken among the group: diopside, wollastonite, tremolite and zeolite. Metal salts of 3-d subgroup of periodic system are used as chromophores. This method provides reducing the roast temperature of pigments as compared with the conventional one by 200-300°C and to enhanced their brightness due to the more intensive penetration of chromophore ions into mineral structure being at the stage of hydrothermal treatment. Prepared pigments are resistant to effect of high temperatures and melted glaze.

Method for production of ammonium alum-based pigments / 2270176

Claimed method includes application of ammonium alum Al₂(SO₄)₃(NH₄)₂SO₄.24H₂O and transition metal Ti, V, Cr, Mn, Fe, Co, Ni salts or salts of metals with chromophore properties (e.g., lanthanides) as starting components. Mixture containing dehydrated ammonium alum and one dissoluble chromophore metal salt is placed in corundum crucible, heated to 200°C and hold at the said temperature for 120 min to release crystalline water from alum. Then solution is heated and boiled, metals is decomposed to pure oxides and conditioned at 800°C for 60 min. After that product is heated up to final synthesis temperature, namely o 1250-1500°C and hold at this temperature for 60-90 min.

Sol-gel method for preparation of large-size dry gels and modified glasses / 2278079

Invention enables preparation of dry gels and corresponding dense glasslike compositions having larger size as compared to similar known methods. Sol-gel method for preparation of three-dimensional dry gels having dimensions along all three axes larger than about 2 cm includes following process operations: (i) preparation of composition A comprising pyrogenic silica and aqueous acid solution, molar ratio H₂O/SiO₂ in composition A being equal to or less than 20 and its pH equal to or less than 1.5; (ii) preparation of composition B comprising silica and aqueous solution of base containing no metal cations, molar ratio H₂O/SiO₂ in composition B being in the range of 6 to 40 and its pH ranging from 10.5 to 13; (iii) preparation of mixture C by mixing composition A and composition B at such a ratio, at which molar ratio of silica from composition A to silica from composition B is in the range between 1:1 and 3:1, pH of mixture C ranging from 1 to 5 and molar ratio H₂O/SiO₂ being in the range of about 5 to 15; (iv) gelation of mixture C; (v) replacement of water present in gel pores and in vessel with gel by an aprotonic liquid capable of being mixed with water; and (vi) drying of gel either by evaporating it or by performing supercritical extraction of aprotonic liquid.

Charge for production of the blue color ceramic pigment / 2283291

The invention is pertaining to ceramic industry, in particular to the field of production of the ceramic pigments for decoration of the whiteware and majolica products. The technical result of the invention is reduction of the temperature of the pigment synthesis and improvement of its color properties. The charge for production of the ceramic pigment contains: talcum,Al₂О₃, SiO₂, CoO, and additionally contains the topaz concentrate at the following contents of the components (in mass %): Talcum - 41.0-42.9; Al₂О₃ - 23.0-30.8;SiO₂ - 23.1-23.7; CoO - 2.1-8.4; the topaz concentrate - 2.0-3.0. The pigment synthesis temperature is 1100-1200°С. The pigment is recommended for production of the underglaze and overglaze ceramic paints used for the ceramic masses coloring.

Method of production of synthetic raw material for manufacture of glass / 2291114

Proposed method makes it possible to produce synthetic raw material in one cycle and separately in form of silicates and compounded silicates of preset elements, synthetic raw materials of glass charges for manufacture of colorless and tinted glass. Synthetic raw material is produced through interaction of silicate and/or hydro-silicate of sodium with aqueous solution of salts and/or suspensions of hydroxides of at least one of glass-forming elements, modifying agents, special additives, dyeing agents or their mixtures at temperature of 20-100°C followed by settling, washing and separation of silicates of respective elements or their mixture in form of pulp or paste.

Method of production of synthetic raw material for glass making / 2291115

Silicates of alkaline and alkaline-earth metals are obtained in single cycle through interaction of aqueous solution of alkaline metal hydroxide with silica-containing material, mainly quartz sand at temperature of 130-240°C and excessive pressure arising at this temperature at presence of hydroxide of alkaline-earth metal. Production of silicates may be also performed at presence of compounds of glass-forming elements and/or dyeing elements, and/or modifying elements, and/or gas-forming agents. Besides that, proposed method includes introduction of the same or other elements into synthetic raw material after obtaining silicates of alkaline or alkaline-earth metals at temperature of 50-120°C. After drying and/or granulation, synthetic raw material is obtained in form of powder or granulated product. Proposed method considerably facilitates procedure of production of synthetic raw material due to simultaneous synthesis of main silicates carried out in one reactor at lower temperatures.

Brown ceramic pigment / 2248333

Blend for preparing ceramic orange-brown-color pigment / 2255056

Method for producing ceramic pigment based on natural minerals / 2255911

Glaze / 2255921

Invention relates to the glaze composite used in manufacturing facade plates and glazed brick. Glaze comprises components taken in the following ratio, wt.-%: SiO₂, 46.0-52.0; Al₂O₃, 7.0-14.0; B₂O₃, 12.0-14.0; MgO, 1.5-2.5; Na₂O, 6.0-7.5; K₂O, 5.0-6.0; SrO, 8.0-12.0. Glaze can comprise additionally pigments, for example, Co₃O₄ in the amount 1.2-2.0 wt.-% or CuO in the amount 2.5-3.5 wt.-%. Glaze shows high fluidity coefficient and good covering power. Invention provides preparing strontium-magnesium-boron glaze showing relatively low roasting temperature (700-750°C), high resistance to cold and thermal stability that allows its using for manufacturing glazed bricks that endure large temperature drops and reducing its cost also.

Compound for making protective coat / 2264367

Proposed compound contains the following constituents, mass-%: quartz-containing component, 15.0-65.0; boron-containing component, 1.0-30.0; lead monoxide and/or ferric oxide, 0.01-40.0; alkaline, 0.05-2.0; the remainder being water glass. If necessary, the compound may additionally contain the following components, mass-%: polyorganosiloxane, 0.05-2.0; deflocculant, 0.1-2.0; adhesion modifying agent, 0.01-5.0; thixotropic additive, 0.01-3.0. It is preferable that water glass has density of 1.18-1.45 g/cm³ and silicate modulus of 2.1-4.0; quartz-containing component contains at least 55 mass-% of silicon oxide at dispersity not exceeding 200 mcm; boron-containing component contains no less than 40 mass-% of boron oxide, lead monoxide and/or ferric oxide at dispersity not exceeding 200 mcm and specific density no less than 3.0 g/cm³; composition is characterized by density of 1.75-2.2 g/cm³, viscosity of 6-13 s, time of complete drying on surface being protected of 20-30 min, spreading temperature not exceeding 600°C and thickness of coat after spreading of 0.1-0.3 mm.

FIELD: ceramics.

SUBSTANCE: invention relates to a method for producing ceramic pigments for decoration of porcelain and faience articles and for staining ceramic masses and glazes. Mixture of mineral powder and chromophore solution in the concentration 4.0-15.6 g-ions/100 g of solution is subjected for hydrothermal treatment (autoclaving) at temperature 170-190°C and under pressure 0.8-1.2 MPa. Deposit is squeezed out, dried and roasted at temperature 950-1100°C. Mineral is taken among the group: diopside, wollastonite, tremolite and zeolite. Metal salts of 3-d subgroup of periodic system are used as chromophores. This method provides reducing the roast temperature of pigments as compared with the conventional one by 200-300°C and to enhanced their brightness due to the more intensive penetration of chromophore ions into mineral structure being at the stage of hydrothermal treatment. Prepared pigments are resistant to effect of high temperatures and melted glaze.

EFFECT: improved method for producing, improved properties of pigments.

3 tbl, 1 ex

The invention relates to the field of production of ceramic pigments for decorating porcelain and earthenware products.

A method of obtaining heat-resistant pigments for ceramic materials with the use of Mechanochemistry [RGH, 1999 - No. 21. Chaikina M.V., Vinokurova O., Avvakumov Mrs x, //Conference “Materials of Siberia, Barnaul, 1998]. It allows you to replace many hours of grinding suspensions starting materials in conventional mills activation within 2-10 hours in a planetary mill and other heavy machines. In the process of mechanical activation of the mixture of the initial components is a partial amorphization of materials and formation of clusters, which reduces the temperature of the subsequent firing 200-250° C. the Disadvantage of this method is the necessity of using pure chemical substances, use of energy efficient equipment. In addition, this method is not really used in industrial environments for the production of pigments in large quantities.

According to another method of obtaining inorganic pigments [USSR Author's certificate No. 1353787, CL 09 With 1/02, 1987], which is used as a prototype for the present invention, natural diopside is subjected to boiling in 25-50%solution of a salt of coloring metal at 90-120° C for 15-60 minutes After that, the suspension is filtered, the precipitate is arenasat in a ceramic container and dried at 120-180° C to constant weight. The disadvantage of this method is that staining occurs mainly in the surface layer of the grains of diopside, so the resulting pigments during firing mostly lose their color. For this reason, these pigments are recommended as inorganic (i.e. unburned).

The task of the invention is to increase the brightness of ceramic pigments derived from natural minerals (diopside, wollastonite, tremolite, zeolite) due to the complex effects of temperature 170-190° and pressure 0.8-1.2 MPa in the process of hydrothermal treatment (autoclaving) of a mixture of mineral powder and salt solution of coloring metal. Natural minerals are crushed to a residue on sieve No. 0063 less than 2%. Solutions of salts of chromophores are prepared from the calculation that the ion concentration of chromophores corresponded to the solubility limit that ranges from 4.0 to 15.6 g-ion/100 g of the solution (PL. 1) depending on the type of salt. Loading autoclave is performed in accordance with a volume ratio of 1:1-1:4 (powder mineral: the solution of the chromophore). The mixture is subjected to autoclaving for 1-3 hours, then the liquid is separated, and the residue is dried and fired at a temperature of 950-1100° C.

The brightness of the color can be adjusted as time, temperature, and concentration of the Oli in solution.

Pressure less than 0.8 MPa is inefficient because it does not provide sufficient introduction of ions of chromophores in the crystal lattice of the mineral and does not give the desired color pigments. The increase of pressure above 1.2 MPa is impractical as it does not lead to a visible improvement of color.

In a volume ratio of the powder of the mineral and the solution of the chromophore increasing volume fraction of the solution is greater than 4 is inefficient because it does not improves the color and leads to waste of raw materials; reduction in the volume fraction of the solution of the chromophore less than 1 does not provide the necessary concentration of the dye ion in the mixture.

The hydrothermal processing less than 1 hour does not provide for the introduction of ions of chromophores in the mineral structure, autoclaving more than 3 hours is inappropriate.

The firing temperature of the pigments depends on the type of structure of the mineral melting temperature of the mineral. The obtained pigments were tested as underglaze paints for decorating majolica products.

Example

To prepare the solution take at 26.58 g of salt FeSO₄·7H₂About 100 ml of water (based on the marginal solubility of salt). The concentration of Fe²⁺the resulting solution is 4.23 g-ion/100 g of solution. For ceramic pigment in the autoclave load it the wollastonite and the prepared solution in about yumnam ratio of 1:4. Autoclaving is carried out at a temperature of 190° and a pressure of 1.2 MPa for 2 hours. The liquid is separated in the centrifuge, the residue is dried and calcined at a temperature of 1000° C. the Obtained sintered pulverized to pass through a sieve No. 0063 (10 000 resp/cm²), causing the baked product, which is then Glasurit and re-calcined at a temperature of 1050° C. the resulting pigment has the following properties: the dominant wavelength of 650 nm, the purity of tone 15 % (table. 3).

The examples of the preparation of pigments of the proposed method are shown in table 2.

Obtained in this method, the pigments based on the chromophore are pink, light blue, red and yellow-brown, olive color. They are resistant to high temperatures and molten glaze and can be used to obtain underglaze, overglaze paints, painting ceramics and glazes.

METHOD of manufacturing CERAMIC PIGMENTS BASED ON NATURAL MINERALS

Table 1. The content of ions of chromophores in salt solutions, g-ion/100 g solution
Fe²⁺	With²⁺	Cr³⁺	Mn²⁺	C²⁺
4.0-4.2	4.0-10.0	4.0-9.2	4.0-8.8	4.0-15.6

Table 2.
Mineral	View dye ion	The content of ions of chromophores in salt solutions, g-ion/100 g solution	The pressure in the hydrothermal treatment, MPa	The temperature during the hydrothermal treatment, °	T_OBG,°
the Wallace will set the	With²⁺	7.0	8	170	950
zeolite	CR³⁺	8.0	10	180	950
diopside	Mn²⁺	5.0	12	190	1000
tremolite	C²⁺	15.0	12	190	1000

td align="left">

Table 3. The color characteristics of pigments
Pigment	Coordinates color	wavelength, nm λ	The purity of tone, P %	Color pigments
X	Y
T_{life safety}=950° C.
^*In-MP	0.36	0.36	580	20	brown
In-SG	0.33	0.34	550	3	olive
D-Fe	0.37	0.36	584	21	brick
Tobi-1000°
D-MP	0.34	0.34	600	7	coffee
C-Fe	0.38	0.34	602	15	arrire-cor
In-Co	0.21	0.22	478	27	blue
B-Fe	0.40	0.32	650	15	arcres-cor
T-Fe	0.35	0.33	620	5	kr.-max
In-the-sea	0.30	0.31	480	8	turquoise
^*In - wollastonite, D - diopside, C - zeolite, T - tremolite

the procedure of obtaining ceramic pigments based on natural minerals, includes treatment of the powder is a natural mineral salt solutions of metals 3-d subgroups, sludge separation, drying, characterized in that the mixture of the mineral from the group of diopside, wollastonite, tremolite and zeolite and salt solution with a concentration of ion-chromophore of 4.0-15.6 g-ion/100 g of the solution subjected to autoclaving for 1-3 hours at a temperature of 170-190°and a pressure of 0.8 to 1.2 MPa, the residue is calcined at a temperature of 950-1100°C.