CN114933411A - Cobalt blue porcelain-like glass bottle and preparation method thereof - Google Patents
Cobalt blue porcelain-like glass bottle and preparation method thereof Download PDFInfo
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- CN114933411A CN114933411A CN202210431845.0A CN202210431845A CN114933411A CN 114933411 A CN114933411 A CN 114933411A CN 202210431845 A CN202210431845 A CN 202210431845A CN 114933411 A CN114933411 A CN 114933411A
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- blue porcelain
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- 239000011521 glass Substances 0.000 title claims abstract description 99
- 239000010941 cobalt Substances 0.000 title claims abstract description 52
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 52
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004040 coloring Methods 0.000 claims abstract description 29
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 23
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005751 Copper oxide Substances 0.000 claims abstract description 22
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 22
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 22
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004327 boric acid Substances 0.000 claims abstract description 16
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 235000019738 Limestone Nutrition 0.000 claims abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 13
- 239000010459 dolomite Substances 0.000 claims abstract description 13
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 13
- 239000010433 feldspar Substances 0.000 claims abstract description 13
- 239000006028 limestone Substances 0.000 claims abstract description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 13
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims description 55
- 239000003086 colorant Substances 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- 235000019353 potassium silicate Nutrition 0.000 claims description 29
- 239000006063 cullet Substances 0.000 claims description 28
- 238000002844 melting Methods 0.000 claims description 27
- 230000008018 melting Effects 0.000 claims description 27
- 238000000137 annealing Methods 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000009472 formulation Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000000465 moulding Methods 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- 238000009826 distribution Methods 0.000 description 11
- 238000007664 blowing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000110 cooling liquid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019990 fruit wine Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- 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
- C03B5/235—Heating the glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B9/00—Blowing glass; Production of hollow glass articles
-
- 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
- C03C1/002—Use of waste materials, e.g. slags
-
- 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
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
-
- 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
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The application relates to the technical field of glass bottle manufacturing, and particularly discloses a cobalt blue porcelain-like glass bottle and a preparation method thereof. The glass bottle comprises the following raw materials in parts by weight: 45-66 parts of sandstone, 10-15 parts of dolomite, 3-7 parts of limestone, 3-8 parts of feldspar, 15-20 parts of soda ash, 0.1-2 parts of cerium oxide and 3-10 parts of coloring material; the coloring material comprises the following raw materials in parts by weight based on the total amount of the coloring material: 10-20 parts of cobalt oxide, 10-20 parts of copper oxide, 1-3 parts of titanium dioxide, 2-5 parts of boric acid and 60-120 parts of solvent. The raw materials in the application are matched with each other, and the cobalt blue porcelain imitating glass bottle with uniform, elegant, pure and unique color can be prepared.
Description
Technical Field
The application relates to the technical field of glass bottle manufacturing, in particular to a cobalt blue porcelain-imitating glass bottle and a preparation method thereof.
Background
The glass bottle is a packaging container for food, beverage and many products, can quantitatively package, transport, store and contain various liquid, semi-liquid and solid articles, has wide application, and is a traditional beverage packaging container in China. Glass bottles have many advantages: the glass bottle can be used for multiple times, so that the packaging cost can be reduced; the coating has good barrier property, can well block invasion of gases such as oxygen and the like to contents, and can prevent volatile components in the contents from volatilizing; the glass bottle is safe and sanitary, has good corrosion resistance and is suitable for packaging acidic substances.
However, most of the existing glass bottles are white and transparent, and when the materials contained in the glass bottles are photosensitive, such as beer, fruit wine and the like, in order to prolong the quality guarantee period of the contained materials, the glass bottles are preferably made into colored glass bottles. The existing colored glass bottle preparation method generally comprises the following steps: mixing glass raw materials, a coloring agent, a clarifying agent and the like, and then sequentially carrying out melting, forming, heat treatment, inspection and the like. The inventor finds that the existing colored glass bottle has the phenomena of poor coloring effect and uneven finished product color.
Disclosure of Invention
In order to improve the coloring effect and the color forming uniformity of a finished glass bottle product, the application provides a cobalt blue porcelain-imitating glass bottle and a preparation method thereof.
In a first aspect, the application provides a formula of a cobalt blue porcelain-like glass bottle, which adopts the following technical scheme:
the formula of the cobalt blue porcelain-like glass bottle comprises the following raw materials in parts by weight:
45-66 parts of sandstone, 10-15 parts of dolomite, 3-7 parts of limestone, 3-8 parts of feldspar, 15-20 parts of soda ash, 0.1-2 parts of cerium oxide and 3-10 parts of coloring material;
based on the total amount of the coloring material, the coloring material comprises the following raw materials in parts by weight:
10-20 parts of cobalt oxide, 10-20 parts of copper oxide, 1-3 parts of titanium dioxide, 2-5 parts of boric acid and 60-120 parts of solvent.
By adopting the technical scheme, the colorant prepared from cobalt oxide, copper oxide, titanium dioxide, boric acid and a solvent according to a certain proportion has good compatibility with other raw materials of the glass bottle, good coloring capability and uniform coloring, and is favorable for obtaining the cobalt blue porcelain-imitating glass bottle with uniform and elegant color.
The cobalt oxide and the copper oxide are matched with each other to prepare elegant cobalt blue, the addition of the titanium dioxide can improve the saturation of the cobalt blue color on one hand and the coloring capability of the colorant on the other hand, and the boric acid is used as a mineralizer to improve the color of the glass bottle and help to obtain the glass bottle with uniform coloring.
The solvent in the colorant is strong acid or partial weak acid, the strong acid can be hydrochloric acid, sulfuric acid or nitric acid, and the weak acid can be oxalic acid or acetic acid. The solvent in the present application is preferably acetic acid.
Preferably, the weight ratio of the cobalt oxide to the copper oxide is (1.25-1.67): 1, more preferably 1.34:1, 1.42:, 1.56: 1.
When cobalt blue is prepared by cobalt oxide and copper oxide, when the cobalt oxide is excessive, the obtained blue color is deep; when the copper oxide is in excess, a slightly pale blue color is obtained. In the present application, when the weight ratio of cobalt oxide to copper oxide is (1.25-1.67): 1, the cobalt blue obtained at this time is pure, elegant and beautiful.
Preferably, the colorant is prepared by the following preparation method:
according to the formula proportion, cobalt oxide, copper oxide, titanium dioxide and boric acid are uniformly mixed, then dissolved in a solvent, ball milled for 1-2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600-900 ℃, then kept warm for 5-10min, and naturally cooled to obtain the colorant.
Preferably, the undersize is calcined at a rate of 10-15 ℃/min to 600-750 ℃.
By adopting the technical scheme, the prepared colorant can be better compatible with other raw materials of the glass bottle, has better dispersibility and more uniform color. Applicants have found that increasing the firing temperature from 600 c to 900 c, the color gradually deepens, and transparency is affected to some extent. When the mixture is baked at a speed of 10-15 ℃/min to 600-750 ℃, the obtained color is uniform and limpid, and no blue-black appears.
Preferably, the formula of the cobalt blue porcelain imitating glass bottle also comprises recycled cullet, and the weight of the recycled cullet accounts for 24-37.7% of the weight of the sandstone. 10.8-24.8 parts of further preferable, when recycled cullet is added to the formulation, the amount of sandstone is reduced, and in this case, 30-50 parts of sandstone and 12.5-17.8 parts of cullet are added to the formulation.
By adopting the technical scheme, a proper amount of recovered cullet is added into the formula, and due to the potential activity of the cullet, the melting temperature in the production process can be reduced, the glass melting efficiency is improved, meanwhile, the consumption of raw materials and fuels for glass bottle production is saved, the waste discharge amount is reduced, and the environment protection is facilitated. In addition, the recycled cullet is used for producing glass bottles, so that the recycling of the waste glass is facilitated, the waste utilization is facilitated, and the waste is changed into valuable.
Preferably, the particle size of the recovered cullet is 0.2-0.4 mm.
By adopting the technical scheme, the particle size of the cullet is 0.2-0.4mm, which is beneficial to melting the glass and obtaining uniform liquid glass (melt), thereby improving the color of the glass bottle.
Preferably, the sandstone has a silica content not exceeding 98% at the most.
The stability of the glass is a result of the interaction of various minerals (oxides) in the raw materials, wherein the most influential is silica, and the higher the silica content in the melt, the higher the viscosity of the melt and the slower the diffusion rate, and the poorer the homogeneity of the melt.
Preferably, the sandstone has a particle size of: at least 95% of the particles with a size of 0.1-0.7mm and at least 80% of the particles with a size of 0.2-0.5 mm.
By adopting the technical scheme, the sandstone particles at least account for 95% of particles with the particle size of 0.1-0.7mm and at least account for 80% of particles with the particle size of 0.2-0.5mm, so that the melting of the melt is facilitated, the generation of bubbles in the melt can be reduced, the clarification effect of the liquid glass is facilitated to be improved, the homogenization of the liquid glass is facilitated, and the homogeneous and stable glass bottle is facilitated to be obtained.
In a second aspect, the application provides a preparation method of a cobalt blue porcelain-imitating glass bottle, which adopts the following technical scheme: a preparation method of a cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: respectively crushing sandstone, dolomite, limestone, feldspar, soda ash, cerium oxide and a coloring material, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1550-;
s3, molding: cooling the liquid glass to 600-;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
Preferably, when the formula contains recycled cullet, the mixture is melted at 1450-1500 ℃ in step S2.
Preferably, the preparation method of the colorant comprises the following steps:
according to the formula proportion, cobalt oxide, copper oxide, titanium dioxide and boric acid are uniformly mixed, then dissolved in a solvent, ball milled for 1-2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600-900 ℃, then kept warm for 5-10min, and naturally cooled to obtain the colorant.
More preferably, the undersize is calcined at a rate of 10-15 ℃/min to 600-750 ℃, and most preferably at a rate of 10 ℃/min to 725 ℃.
Through adopting above-mentioned technical scheme, in this application, the in-process of preparation cobalt blue imitation porcelain glass bottle can not introduce new equipment, and the preparation cost is lower, does benefit to implementation operation, is favorable to batch production manufacturing.
In summary, the present application has the following beneficial effects:
1. the raw materials in the application are matched with each other, so that the cobalt blue porcelain imitating glass bottle with uniform, elegant, pure and beautiful color can be prepared;
2. in the application, the colorant prepared from cobalt oxide, copper oxide, titanium dioxide, boric acid and a solvent according to a certain proportion has good compatibility with other raw materials of a glass bottle, strong coloring capability and uniform coloring;
3. in the application, a certain amount of recovered cullet is added into the formula, so that the melting temperature of the raw materials can be reduced while waste utilization is realized, energy can be saved, and the cost can be saved.
Detailed Description
The present application will be described in further detail with reference to examples. Specifically, the following are described: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer; the starting materials used in the following examples are all those which are generally commercially available, except where specifically indicated.
Preparation of coloring Material
Preparation example 1
The preparation method of the colorant is as follows:
1kg of cobalt oxide, 2kg of copper oxide, 0.1kg of titanium dioxide and 0.2kg of boric acid are uniformly mixed, then dissolved in 6kg of acetic acid, ball-milled for 1h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 900 ℃, then kept warm for 5min, and naturally cooled to obtain the colorant 1.
Preparation example 2
The preparation method of the colorant is as follows:
uniformly mixing 2kg of cobalt oxide, 1kg of copper oxide, 0.3kg of titanium dioxide and 0.5kg of boric acid, dissolving in 12kg of acetic acid, carrying out wet ball milling for 2h, sieving with a sieve with the aperture of 0.065mm, roasting the undersize to 900 ℃, then preserving the temperature for 10min, and naturally cooling to obtain the colorant 2.
Preparation example 3
The preparation method of the colorant is as follows:
1.63kg of cobalt oxide, 1.3kg of copper oxide, 0.2kg of titanium dioxide and 0.3kg of boric acid are uniformly mixed, then dissolved in 10kg of acetic acid, ball-milled for 2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600 ℃ at the speed of 10 ℃/min, then kept warm for 10min, and naturally cooled to prepare the colorant 3.
Preparation example 4
The preparation method of the colorant is as follows:
2kg of cobalt oxide, 1.2kg of copper oxide, 0.2kg of titanium dioxide and 0.3kg of boric acid are uniformly mixed, then dissolved in 10kg of acetic acid, ball-milled for 2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600 ℃ at the speed of 10 ℃/min, then kept warm for 10min, and naturally cooled to prepare the colorant 4.
Preparation example 5
The preparation method of the colorant is as follows:
1.63kg of cobalt oxide, 1.3kg of copper oxide, 0.2kg of titanium dioxide and 0.3kg of boric acid are uniformly mixed, then dissolved in 10kg of acetic acid, ball-milled for 2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600 ℃ at the speed of 15 ℃/min, then kept warm for 10min, and naturally cooled to prepare the colorant 5.
Preparation example 6
The preparation method of the colorant is as follows:
1.63kg of cobalt oxide, 1.3kg of copper oxide, 0.2kg of titanium dioxide and 0.3kg of boric acid are uniformly mixed, then dissolved in 10kg of acetic acid, ball-milled for 2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 725 ℃ at the speed of 10 ℃/min, then kept warm for 10min, and naturally cooled to prepare the colorant 6.
Examples
Example 1
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: respectively crushing 4.5kg of sandstone, 1.5kg of dolomite, 0.3kg of limestone, 0.8kg of feldspar, 2kg of soda ash, 0.01kg of cerium oxide and 0.3kg of coloring material 3, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1550 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling the liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and forming to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm.
Example 2
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: respectively crushing 6.6kg of sandstone, 1kg of dolomite, 0.7kg of limestone, 0.3kg of feldspar, 1.5kg of soda ash, 0.2kg of cerium oxide and 1kg of coloring material 3, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1600 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling liquid glass to 800 ℃, then placing the liquid glass into a bottle blowing mold, and forming to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm.
Example 3
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: respectively crushing 5.5kg of sandstone, 1.2kg of dolomite, 0.5kg of limestone, 0.4kg of feldspar, 1.7kg of soda ash, 0.11kg of cerium oxide and 0.6kg of coloring material 3, and then uniformly mixing according to the formula proportion to obtain a mixture;
s2, melting: melting the mixture at 1550 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and molding to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitated glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm.
Example 4
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: crushing 5.5kg of sandstone, 1.08kg of recycled cullet, 1.2kg of dolomite, 0.5kg of limestone, 0.4kg of feldspar, 1.7kg of soda ash, 0.11kg of cerium oxide and 0.6kg of coloring material 3 respectively, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1500 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling the liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and forming to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm; the particle size of the recovered cullet is 0.4-0.6 mm.
Example 5
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, blending: respectively crushing 5.5kg of sandstone, 2.48kg of recycled cullet, 1.2kg of dolomite, 0.5kg of limestone, 0.4kg of feldspar, 1.7kg of soda ash, 0.11kg of cerium oxide and 0.6kg of coloring material 3, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1450 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling the liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and forming to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm; the particle size of the recovered cullet is 0.4-0.6 mm.
Example 6
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: crushing 4kg of sandstone, 1.25kg of recycled cullet, 1.2kg of dolomite, 0.5kg of limestone, 0.4kg of feldspar, 1.7kg of soda ash, 0.11kg of cerium oxide and 0.6kg of coloring material 3 respectively, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1500 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling the liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and forming to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm; the particle size of the recovered cullet is 0.4-0.6 mm.
Example 7
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: respectively crushing 3.2kg of sandstone, 1.78kg of recycled cullet, 1.2kg of dolomite, 0.5kg of limestone, 0.4kg of feldspar, 1.7kg of soda ash, 0.11kg of cerium oxide and 0.6kg of coloring material 3, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1470 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and molding to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm; the particle size of the recovered cullet is 0.4-0.6 mm.
Example 8
Example 8 differs from example 7 only in that in example 8, the recovered cullet has a particle size of 0.2-0.4mm, and the remainder is the same as example 7.
Example 9
Example 9 differs from example 7 only in that in example 9, the properties of sandstone are different, the silica content in sandstone is 96.2%, and the particle size distribution: 95% of particles with 0.1-0.7mm and 80% of particles with 0.2-0.5 mm; the rest of the process was the same as in example 7.
Example 10
Example 9 differs from example 7 only in that in example 9, the properties of sandstone are different, the silica content in sandstone is 96.2%, and the particle size distribution: 98% of particles with 0.1-0.7mm, and 90% of particles with 0.2-0.5 mm; the rest of the process was the same as in example 7.
Examples 11 to 15
Examples 11-15 differ from example 10 only in that the colorants in examples 11-15 are different and remain the same as in example 7. The colorants in examples 11-15 are specifically shown in Table 1 below.
TABLE 1
| Examples | Coloring agent |
| Example 10 | Colorant 3 |
| Example 11 | Colorant 1 |
| Example 12 | Colorant 2 |
| Example 13 | Colorant 4 |
| Example 14 | Colorant 5 |
| Example 15 | Colorant 6 |
Comparative example
Comparative example 1
The preparation method of the cobalt blue porcelain-like glass bottle comprises the following steps:
s1, batching: respectively crushing 3.2kg of sandstone, 1.78kg of recycled cullet, 1.2kg of dolomite, 0.5kg of limestone, 0.4kg of feldspar, 1.7kg of soda ash, 0.11kg of cerium oxide, 0.33kg of cobalt oxide and 0.27kg of copper oxide, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1550 ℃ to obtain uniform bubble-free liquid glass;
s3, molding: cooling the liquid glass to 600 ℃, then placing the liquid glass into a bottle blowing mold, and forming to obtain a prefabricated glass bottle;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
In this example, the silica content in sandstone is 99.4%, and the particle size distribution: 80% of particles with 0.1-0.7mm, and 70% of particles with 0.2-0.5 mm; the particle size of the recovered cullet is 0.4-0.6 mm.
Performance detection
The sensory properties, specific indexes and sensory evaluation of the cobalt blue porcelain-imitating glass bottles prepared in examples 1 to 15 and comparative example 1 were measured as shown in table 2 below, and the higher the score, the better the color and the more uniform the color of the cobalt blue porcelain-imitating glass bottle.
TABLE 2
| Evaluation index | Score of |
| The cobalt blue is bright, the color is very uniform, | 8-10 |
| cobalt blue is slightly light or bluish black, and has uniform color | 5-7 |
| Color unevenness | 2-4 |
TABLE 3
| Sample (I) | Score of |
| Example 1 | 7.2 |
| Example 2 | 7.4 |
| Example 3 | 7.6 |
| Example 4 | 7.8 |
| Example 5 | 7.9 |
| Example 6 | 8.1 |
| Example 7 | 8.3 |
| Example 8 | 8.6 |
| Example 9 | 8.9 |
| Example 10 | 9.2 |
| Example 11 | 6.7 |
| Example 12 | 6.5 |
| Example 13 | 9.3 |
| Example 14 | 9.4 |
| Example 15 | 9.5 |
| Comparative example 1 | 3.5 |
As can be seen by combining examples 1-3 with tables 2 and 3, the glass bottles made according to the formulations and methods of the present application are uniform in color and elegant in color.
As can be seen by combining example 3 with examples 4-7 and tables 2 and 3, the addition of recycled cullet to the formulation improves the color formation of the glass bottles to some extent while lowering the melting temperature.
As can be seen by combining examples 7 and 8 with tables 2 and 3, the particle size of the recovered cullet also affects the color formation of the glass bottle, and the color formation of the glass bottle is better when the particle size of the recovered cullet is 0.2 to 0.4 mm.
Combining examples 7 and 9-10 with tables 2 and 3, it can be seen that the silica content in sandstone and the sandstone particle size distribution also affect the colour formation of the glass bottle, and that it is advantageous to obtain a glass bottle with more uniform colour formation when the silica content in sandstone does not exceed 98%, the particles of 0.1-0.7mm account for at least 95%, and the particles of 0.2-0.5mm account for at least 80%.
As can be seen by combining examples 7, 11-15 and comparative example 1 with tables 2 and 3, the coloring agent has a great influence on the coloring of the glass bottle, and the cobalt blue porcelain-imitating glass bottle prepared according to the formulation and preparation method of the present application has uniform coloring and elegant color.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The formula of the cobalt blue porcelain-like glass bottle is characterized in that: the feed comprises the following raw materials in parts by weight:
45-66 parts of sandstone, 10-15 parts of dolomite, 3-7 parts of limestone, 3-8 parts of feldspar, 15-20 parts of soda ash, 0.1-2 parts of cerium oxide and 3-10 parts of coloring material;
the coloring material comprises the following raw materials in parts by weight based on the total amount of the coloring material:
10-20 parts of cobalt oxide, 10-20 parts of copper oxide, 1-3 parts of titanium dioxide, 2-5 parts of boric acid and 60-120 parts of solvent.
2. The cobalt blue porcelain imitating glass bottle formulation according to claim 1, wherein: the weight ratio of the cobalt oxide to the copper oxide is (1.25-1.67): 1.
3. the cobalt blue porcelain imitating glass bottle formulation according to claim 2, wherein: the colorant is prepared by the following preparation method:
according to the formula proportion, cobalt oxide, copper oxide, titanium dioxide and boric acid are uniformly mixed, then dissolved in a solvent, ball milled for 1-2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600-900 ℃, then kept warm for 5-10min, and naturally cooled to obtain the colorant.
4. The cobalt blue porcelain-like glass bottle formulation according to claim 3, wherein: when the undersize material is roasted, the undersize material is roasted to 600-750 ℃ at the speed of 10-15 ℃/min.
5. The cobalt blue porcelain imitating glass bottle formulation according to any one of claims 1 to 4, wherein: the formula of the cobalt blue porcelain imitating glass bottle also comprises recycled cullet, and the weight of the recycled cullet accounts for 24-37.7% of the weight of the sandstone.
6. The cobalt blue porcelain imitating glass bottle formulation according to claim 5, wherein: the particle size of the recovered cullet is 0.2-0.4 mm.
7. The cobalt blue porcelain imitating glass bottle formulation according to claim 1, wherein: the sandstone contains no more than 98% of silica at most.
8. The cobalt blue porcelain imitating glass bottle formulation according to claim 7, wherein: the particle size of the sandstone is as follows: at least 95% of the particles with a size of 0.1-0.7mm and at least 80% of the particles with a size of 0.2-0.5 mm.
9. The method of manufacturing a cobalt blue porcelain imitating glass bottle as claimed in any one of claims 1 to 8, wherein: the method comprises the following steps:
s1, batching: respectively crushing sandstone, dolomite, limestone, feldspar, soda ash, cerium oxide and a coloring material, and then uniformly mixing according to a formula ratio to obtain a mixture;
s2, melting: melting the mixture at 1550-;
s3, molding: cooling the liquid glass to the temperature of 600-;
s4, annealing: and (4) annealing the prefabricated glass bottle, and naturally cooling to normal temperature when the temperature is lower than 150 ℃ to obtain the cobalt blue porcelain-imitating glass bottle.
10. The cobalt blue porcelain imitating glass bottle formulation according to claim 9, wherein: the preparation method of the colorant comprises the following steps:
according to the formula proportion, cobalt oxide, copper oxide, titanium dioxide and boric acid are uniformly mixed, then dissolved in a solvent, ball milled for 1-2h by a wet method, sieved by a sieve with the aperture of 0.065mm, roasted to 600-900 ℃, then kept warm for 5-10min, and naturally cooled to obtain the colorant.
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