CN110550863A - composition for manufacturing glass bottle, glass bottle and preparation method thereof - Google Patents
composition for manufacturing glass bottle, glass bottle and preparation method thereof Download PDFInfo
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- CN110550863A CN110550863A CN201910907925.7A CN201910907925A CN110550863A CN 110550863 A CN110550863 A CN 110550863A CN 201910907925 A CN201910907925 A CN 201910907925A CN 110550863 A CN110550863 A CN 110550863A
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- 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
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Abstract
A composition for manufacturing glass bottles, the glass bottles and a preparation method thereof belong to the technical field of glass bottle manufacturing. The composition for manufacturing the glass bottle comprises the following raw materials in parts by weight: 24-56 parts of glass slag, 20-50 parts of quartz sand, 0.2-2 parts of calcite, 1-15 parts of feldspar, 2-12 parts of dolomite, 0.2-4 parts of fluorite, 0.5-10 parts of sodium nitrate, 5-18 parts of soda ash, 2-8 parts of borax, 0.01-1 part of cobalt compound and 0.2-4 parts of clarifying agent. The raw materials are matched with each other, the light transmittance of the glass is enhanced through the clarification effect of the raw materials, the expansion coefficient of the glass is reduced through the raw materials, and the thermal stability, the chemical stability and the mechanical strength of the glass are improved, so that the blue glass bottle with high transparency, stable performance and small internal stress is prepared.
Description
Technical Field
The application relates to the technical field of glass bottle manufacturing, in particular to a composition for manufacturing a glass bottle, the glass bottle and a preparation method thereof.
background
Glass bottles are widely used in daily life because they are used for many purposes. With increasing demand, more and more diversified glass bottles enter the visual field of people, high-transparency glass is attractive, and the market demand is larger and larger.
on the other hand, glass bottles are generally manufactured through four steps of batching, melting, forming and annealing. In the forming process, molten glass stock solution is required to be injected into a forming die with a water cooling system, and the glass stock solution is rapidly cooled and formed, so that most of energy is stored in a glass bottle body to form so-called internal stress, the internal stress is too large to easily cause the bottle body to crack, and the glass bottle is required to be annealed to eliminate the internal stress, so that the internal stress in the glass bottle body is released. In the actual annealing process, especially in the annealing process of the high-transparency glass bottle, the internal stress in the bottle body can not be completely eliminated, thereby affecting the quality and the use safety of the glass bottle.
Disclosure of Invention
the application provides a composition for manufacturing a glass bottle, the glass bottle and a preparation method thereof, and the glass bottle can be manufactured into a glass bottle with high transparency and small internal stress.
the embodiment of the application is realized as follows:
In a first aspect, the present application provides a composition for making glass bottles, comprising the following raw materials in parts by weight:
24-56 parts of glass slag, 20-50 parts of quartz sand, 0.2-2 parts of calcite, 1-15 parts of feldspar, 2-12 parts of dolomite, 0.2-4 parts of fluorite, 0.5-10 parts of sodium nitrate, 5-18 parts of soda ash, 2-8 parts of borax, 0.01-1 part of cobalt compound and 0.2-4 parts of clarifying agent.
In the technical scheme, various raw materials are matched with each other, the light transmittance of the glass is enhanced through the clarification effect of the raw materials, the expansion coefficient of the glass is reduced through the raw materials, and the thermal stability, the chemical stability and the mechanical strength of the glass are improved, so that the blue glass bottle with high transparency and stable performance is prepared.
In a first possible example of the first aspect of the present application, in combination with the first aspect, the composition for making glass bottles comprises the following raw materials:
30-56 parts of glass slag, 30-50 parts of quartz sand, 0.8-2 parts of calcite, 5-15 parts of feldspar, 3-12 parts of dolomite, 1-4 parts of fluorite, 1-10 parts of sodium nitrate, 8-18 parts of soda ash, 3-8 parts of borax, 0.03-1 part of cobalt compound and 0.5-4 parts of clarifying agent.
In a second possible example of the first aspect of the present application in combination with the first aspect, the above-mentioned clarifying agent includes sodium sulfate and/or cerium oxide.
Alternatively, when the fining agent comprises sodium sulfate and cerium oxide, the mass ratio of sodium sulfate to cerium oxide in the fining agent is 1: 2-1: 8.
In the above examples, both sodium sulfate and cerium oxide are capable of decomposing at high temperatures, generating a large amount of gas dissolved in the molten glass to facilitate the removal of bubble species from the glass.
when the clarifying agent comprises sodium sulfate and cerium oxide, because the decomposition temperatures of the two substances are different, the clarifying effect in a wider temperature range can be increased by matching, and when the mass ratio of the sodium sulfate to the cerium oxide in the clarifying agent is 1: 2-1: the clarification effect is better when the content is 8.
In a second aspect, the present application provides a method for preparing a glass bottle, which comprises mixing, by weight, 24 to 56 parts of glass slag, 20 to 50 parts of quartz sand, 0.2 to 2 parts of calcite, 1 to 15 parts of feldspar, 2 to 12 parts of dolomite, 0.2 to 4 parts of fluorite, 0.5 to 10 parts of sodium nitrate, 5 to 18 parts of soda ash, 2 to 8 parts of borax, 0.01 to 1 part of cobalt compound and 0.2 to 4 parts of a clarifier, melting to form a glass liquid, molding, and annealing to prepare the glass bottle.
In the technical scheme, the preparation method is simple and convenient, and the prepared glass bottle has small internal stress and is very safe to use.
in a first possible example of the second aspect of the present application in combination with the second aspect, the above-mentioned glass slag, quartz sand, calcite, feldspar, dolomite, fluorite, sodium nitrate, soda ash, borax, cobalt compounds and fining agent are all in powder form;
Wherein the grain size of the quartz sand is less than or equal to 1.00mm, the grain size of the calcite is less than or equal to 2.80mm, the grain size of the feldspar is less than or equal to 2.00mm, the grain size of the dolomite is less than or equal to 2.00mm, the grain size of the fluorite is less than or equal to 2.00mm, the grain size of the soda ash is less than or equal to 0.18mm, the grain size of the borax is less than or equal to 2.00mm, the grain size of the cobalt compound is less than or equal to 0.15mm, and the grain size of the.
In the above examples, the raw material in powder form is advantageous for the molding of glass, and for the formation of glass with high transparency.
In a second possible example of the first aspect of the present application in combination with the first aspect, the pressure during melting is 0 to 5Pa, the liquid level fluctuation is-2 to 2mm, and the melting temperature is 1450 to 1550 ℃.
in the above example, the glass is melt-formed under the above process parameters, which is beneficial to forming a blue glass bottle with high transparency and stable performance.
In a third possible example of the second aspect of the present application in combination with the second aspect, the annealing includes heating to an annealing temperature, holding at the annealing temperature for a predetermined time, and cooling to room temperature.
In the above example, the internal stress in the glass bottle can be more completely eliminated by the above annealing process.
In a fourth possible example of the second aspect of the present application in combination with the second aspect, the annealing temperature is 560 to 570 ℃, and the predetermined time is 15 to 25 min.
In the above example, heating to the annealing temperature re-raises the temperature of the glass bottle to a level that allows for mass point adjustment and stress relaxation, and the heat preservation is beneficial to eliminating the temperature difference generated when the glass bottle is heated rapidly and eliminating the inherent internal stress.
In a fifth possible example of the second aspect of the present application, in combination with the second aspect, the cooling includes performing a second cooling after the first cooling to the target temperature, where a cooling rate of the first cooling is 1 to 2 ℃/min, and a cooling rate of the second cooling is 10 to 15 ℃/min.
In the above example, the cooling rate of the first cooling is slow, mainly to prevent the secondary stress generated due to the temperature difference in the cooling process, and the cooling rate of the second cooling is fast, at this time, the glass bottle structure is already solidified, and no new permanent stress is generated.
In a second aspect, the present application provides a glass bottle, which is produced according to the above-described method for producing a glass bottle.
According to the technical scheme, the prepared glass bottle is high in transparency and small in internal stress.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
fig. 1 is an annealing temperature profile provided herein.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following is a detailed description of the composition for making glass bottles, the glass bottles and the preparation method thereof according to the embodiments of the present application:
The application provides a composition for manufacturing glass bottles, which comprises the following raw materials in parts by weight:
24-56 parts of glass slag, 20-50 parts of quartz sand, 0.2-2 parts of calcite, 1-15 parts of feldspar, 2-12 parts of dolomite, 0.2-4 parts of fluorite, 0.5-10 parts of sodium nitrate, 5-18 parts of soda ash, 2-8 parts of borax, 0.01-1 part of cobalt compound and 0.2-4 parts of clarifying agent.
Optionally, it comprises the following raw materials:
30-56 parts of glass slag, 30-50 parts of quartz sand, 0.8-2 parts of calcite, 5-15 parts of feldspar, 3-12 parts of dolomite, 1-4 parts of fluorite, 1-10 parts of sodium nitrate, 8-18 parts of soda ash, 3-8 parts of borax, 0.03-1 part of cobalt compound and 0.5-4 parts of clarifying agent.
optionally, it comprises the following raw materials:
30-40 parts of glass slag, 30-40 parts of quartz sand, 0.8-1.5 parts of calcite, 5-12 parts of feldspar, 3-8 parts of dolomite, 1-3 parts of fluorite, 1-5 parts of sodium nitrate, 8-12 parts of soda ash, 3-5 parts of borax, 0.03-0.05 part of cobalt compound and 0.5-1 part of clarifying agent.
the glass slag is prepared according to the preparation method of the glass bottle in the application, and comprises any one or more of qualified glass bottles, unqualified glass bottles, broken glass slag and glass fragments obtained by quenching glass liquid in water. The glass cullet includes, but is not limited to, glass bottles and/or glass cullet produced during the production process. When any one or more of unqualified glass bottles, broken glass slag and glass fragments obtained by quenching glass liquid in water are adopted, not only can waste be utilized, but also under the condition of reasonable proportion, the melting process of glass can be accelerated by adding finished glass fragments, the heat consumption of glass melting is reduced, and therefore the production cost of the glass bottles is reduced and the yield is increased.
The quartz sand is also called silica sand, the main component of the quartz sand is silicon dioxide (chemical formula SiO 2), and the quartz sand also contains substances such as aluminum oxide (chemical formula Al 2 O 3), magnesium oxide (chemical formula MgO), calcium oxide (chemical formula CaO), sodium oxide (chemical formula Na 2 O), ferric oxide (chemical formula Fe 2 O 3), potassium oxide (chemical formula K 2 O) and the like, and the content of SiO 2 in the quartz sand is more than 96%.
In general, the glass includes a network-forming oxide, and an intermediate oxide.
The network-forming oxide can form a glass independently, and can form a network system which is respectively unique in the glass and forms a continuous network or a framework, the F-O (F is a network-forming oxide ion) bond of the oxide is a mixed bond of a covalent bond and an ionic bond, the single bond energy is larger, the coordination number of F is 3 or 4, the coordination number of O 2- is 2, and the coordination polyhedron FO 4 or FO 3 is generally connected with an apex angle.
The extranet oxide can not generate glass independently, does not participate in a grid, is generally positioned outside the network, cations of the oxide have larger ionic radius and higher coordination number, the coordination number is more than or equal to 6, the oxides are filled in gaps of a silicon-oxygen tetrahedral framework, M-O (M is extranet oxide ions) bonds of the oxides are mainly ionic bonds, and the electric field intensity is very low.
The intermediate oxide generally cannot generate glass, the function of the intermediate oxide is between that of a network generating oxide and that of a network exo-oxide, an I-O (I is intermediate oxide ion) bond has certain valence supplying property, but the ionicity is mainly, the coordination number of I is 6, but the coordination number can be changed into 4 after oxygen is abstracted, and the intermediate oxide can participate in the network and the network generating oxide function (network supplementing function) of the intermediate oxide.
the raw materials are added with quartz sand mainly for introducing SiO 2 2 which is an important glass forming oxide and is a main body for forming a silicate glass framework, and the silicon-oxygen tetrahedron SiO4 is used as a structural unit to form an irregular continuous network structure which develops to a three-dimensional space and becomes the framework of the glass, SiO 2 can improve the hardness, the mechanical strength, the chemical stability, the thermal stability (reducing the expansion coefficient) and the ultraviolet transmittance of the glass, but SiO 2 can also improve the viscosity and the melting temperature of the glass, possibly causes devitrification and influences the melting glass quality of the glass.
The main component of calcite is calcium carbonate (chemical formula CaCO 3), CaCO 3 can be decomposed into calcium oxide (chemical formula CaO) and carbon dioxide (chemical formula CO 2) to overflow at high temperature, the calcite is added into the raw materials mainly for introducing CaO, CaO is a divalent network exo-oxide, and the main function of the calcite in the glass is to act as a stabilizer, namely to increase the chemical stability and mechanical strength of the glass.
However, it should be noted that when the temperature of the molten glass containing CaO is lowered, the viscosity of the molten glass increases rapidly, the forming is difficult, and the annealing process needs to be controlled to prevent the glass bottle from bursting. In addition, the amount of calcite in the glass needs to be strictly controlled because the higher content of CaO causes the glass to have a greater tendency to crystallize and tends to embrittle the glass, and generally, the content of CaO in the glass does not exceed 12.5 mass percent.
in the sodium silicate glass, Al 3+ exists in tetrahedron to form AlO 4 and forms a continuous structural network with silicon-oxygen tetrahedron when the molar ratio of Na 2 O to Al 2 O 3 is more than 1, and Al 2 O 3 can reduce the crystallization tendency of the glass, improve the chemical stability, thermal stability, mechanical strength, hardness and refractive index of the glass, reduce the corrosion of the glass to refractory materials and contribute to the opalescence of fluorides when the molar ratio of Na 2 O to Al 2 O 3 is less than 1, Al 2 O 3 can improve the viscosity of Al 2O 826955, the general mass fraction of introduced Al 2O is 863-863.863-863%.
meanwhile, the feldspar also contains other alkali metal oxides, so that the use amount of the soda ash can be reduced.
The dolomite is a double salt of calcium carbonate and magnesium carbonate, the molecular formula of which is CaCO 3. MgCO 3 3, and can be decomposed into magnesium oxide (chemical formula MgO) and carbon dioxide (chemical formula CO 2) to overflow at high temperature, the dolomite is added into the raw materials mainly for introducing MgO, the MgO is an intermediate oxide, the MgO has two coordination states (4 or 6), the single most of the MgO is positioned in an octahedron and belongs to the outside of a network body, in the soda-lime-silica glass, MgO is usually used for replacing part of CaO to reduce the crystallization capacity of the glass and adjust the material property of the glass, so that the hardening speed of the glass can be slowed down, and the forming performance of the glass can be improved.
Fluorite mainly becomes calcium fluoride (chemical formula CaF 2), and CaF 2 is used as an intensive flux, plays a role in fluxing and reducing viscosity, and plays a great role in clarifying molten glass.
The sodium nitrate (chemical formula NaNO 3) is colorless or light yellow hexagonal crystal, absorbs water in humid air, deliquesces and dissolves in water, and the NaNO 3 is heated to 340-360 ℃ to perform the following chemical reaction:
2NaNO3＝2NaNO2+O2↑
When the heating is continued, the generated sodium nitrite (chemical formula NaNO 2) is decomposed again to release nitrogen (chemical formula N 2) and oxygen (chemical formula O 2), and the chemical reaction is as follows:
4NaNO2＝2N2O+2N2↑+3O2↑
The sodium nitrate releases O 2, which not only plays the role of clarifying agent, but also plays the role of oxidizing agent and decoloring agent, and can replace a part of soda ash.
the main component of soda ash is sodium carbonate (chemical formula Na 2 CO 3), Na 2 CO 3 can be decomposed into sodium oxide (chemical formula Na 2 O) and carbon dioxide (chemical formula CO 2) to overflow at high temperature, the soda ash is added into raw materials mainly for introducing Na 2 O, Na 2 O is an extranet oxide, Na + has small field strength and weaker bonding force with oxygen, Na + is positioned in a cavity of a glass structure network, free oxygen can be provided to increase the O/Si ratio in the glass structure, and the net breaking effect is mainly played in the structure, so that the viscosity of the glass can be reduced, the glass is easy to melt, and the soda ash is a good cosolvent.
However, Na 2 O breaks the silica network, loosens the structure of the glass, weakens the structure, increases the thermal expansion coefficient of the glass, and reduces the thermal stability, chemical stability and mechanical strength of the glass, so the introduction amount is not too much, and generally not more than 18% of the mass fraction.
Borax (chemical formula Na 2 B 4 O 7.10H 2 O) is a boron-containing mineral and a boron compound, borax is added into raw materials mainly for introducing B 2 O 3, B 2 O 3 is a glass forming oxide, B 2 O 3 takes BO 3 and BO 4 as structural units to form a structural network, and the structural network plays a role of a glass skeleton in the glass, B 2 O 3 can reduce the thermal expansion coefficient of the glass, improve the thermal stability of the glass, increase the refractive index of the glass, improve the gloss of the glass and improve the mechanical property of the glass, meanwhile, B 2 O 3 can reduce the viscosity of the glass at high temperature, B 2 O 3 also can play a role of a cosolvent, accelerate the clarification of the glass and reduce the crystallization capacity of the glass, B 2 O 3 is volatilized with water vapor, and a crystallization coating rich in SIO 2 is generated on the liquid level of the glass due to the reduction of B 2 O 3.
However, it should be noted that B 2 O 3 increases the viscosity of the glass at low temperature, so that the glass with a high B 2 O 3 content has a narrow forming temperature range and requires an increase in forming rate, in general, the mass fraction of B 2 O 3 in the glass is not more than 14%, and when the B 2 O 3 content is high, the thermal expansion coefficient of the glass is increased due to the increase of boron oxygen trigones, and the abnormal phenomenon of boron occurs.
Cobalt compounds are stable and strong colorants, including but not limited to cobaltous oxide (formula CoO), cobalt oxide (formula Co 2 O 3), cobaltosic oxide (formula Co 3 O 4), cobalt carbonate and cobalt nitrate, and in a high temperature environment, the cobalt compounds are converted into CoO, which makes the glass obtain a reddish blue color, and is not affected by the atmosphere.
the fining agent can be decomposed or gasified at high temperature to generate gas in the glass melting process, or the viscosity of the glass liquid is reduced to promote the elimination of bubbles in the glass liquid. The glass fining agent decomposes at high temperature to generate a large amount of gas dissolved in the molten glass, which is supersaturated in the glass, increases the partial pressure of the gas in the molten glass, separates the gas into bubbles remaining in the molten glass, reduces the partial pressure of other gases existing in the bubbles, and re-strengthens the capacity of the glass fining agent to extract the gas from the molten glass. The gas generated by the clarifying agent and the original gas in the bubbles are separated out together, so that the diameter of the bubbles is increased, and the rising of the bubbles is accelerated. The rising of the bubbles causes small bubbles to rise and bring a part of the small bubbles out, thereby accelerating the clarification process.
In the present application, the fining agent comprises sodium sulfate and/or cerium oxide.
the clarifying agent may be sodium nitrate, cerium oxide, or a mixture of sodium sulfate and cerium oxide.
When the clarifying agent is a mixture of sodium sulfate and cerium oxide, the mass ratio of the sodium sulfate to the cerium oxide in the clarifying agent is 1: 2-1: 8.
the sodium sulfate can release a large amount of sulfur dioxide gas in high-temperature decomposition, plays a role in high-temperature clarification, and belongs to a high-temperature clarifying agent.
Cerium oxide can decompose at high temperatures to release oxygen, accelerate clarification, and also be a strong oxidant. Moreover, the cerium oxide can improve the ultraviolet light absorption capacity of the glass, and the glass containing the cerium oxide does not change color under the irradiation of strong radiation. However, it is essential that the content of cerium oxide in the glass is not so high that exceeding 0.7% by mass causes blisters.
The sodium sulfate and cerium oxide are matched to use in the glass bottle, so that substances of bubbles in the glass can be discharged, and the prepared glass bottle can be guaranteed not to be discolored.
Optionally, the fining agent also includes antimony oxide, nitrates, and the like.
The application also provides a glass bottle and a preparation method thereof, and the glass bottle comprises the steps of mixing 24-56 parts of glass slag, 20-50 parts of quartz sand, 0.2-2 parts of calcite, 1-15 parts of feldspar, 2-12 parts of dolomite, 0.2-4 parts of fluorite, 0.5-10 parts of sodium nitrate, 5-18 parts of soda ash, 2-8 parts of borax, 0.01-1 part of cobalt compound and 0.2-4 parts of clarifying agent, melting to form glass liquid, forming and annealing to prepare the glass bottle.
Wherein the glass slag, the quartz sand, the calcite, the feldspar, the dolomite, the fluorite, the sodium nitrate, the soda ash, the borax, the cobalt compound and the clarifying agent are powdery raw materials.
The powdery raw materials are beneficial to uniformly mixing various different raw materials, so that the later-stage uniform molding is realized, and the glass with high transparency is formed.
Alternatively, the particle size distribution of the quartz sand is as follows: the quartz sand with the particle size of more than 1.00mm (screened by a sieve with 18 meshes) does not exist, the quartz sand with the particle size of 0.85-1.00 mm (screened by the sieve with 18 meshes and 20 meshes) is less than or equal to 0.5 percent, the quartz sand with the particle size of 0.125-0.85 mm (screened by the sieve with 20 meshes and 120 meshes) is more than or equal to 97.5 percent, and the quartz sand with the particle size of 0-0.125 mm (screened by the sieve with 120 meshes) is less than or equal to 2 percent.
Alternatively, the particle size distribution of calcite is as follows: the calcite with the grain size of more than 2.80mm (screened by a 7-mesh sieve) is not contained, the calcite with the grain size of 0.85-2.80 mm (screened by 7-mesh and 20-mesh sieves) is not more than 25 percent, the calcite with the grain size of 0.125-0.85 mm (screened by 20-mesh and 120-mesh sieves) is not less than 50 percent, and the calcite with the grain size of 0-0.125 mm (screened by a 120-mesh sieve) is not more than 25 percent.
Alternatively, the particle size distribution of feldspar is as follows: the feldspar with the grain size of more than 2.00mm (screened by a 10-mesh sieve) is not contained, the feldspar with the grain size of 0.85-2.00 mm (screened by the 10-mesh sieve and the 20-mesh sieve) is less than or equal to 3 percent, the feldspar with the grain size of 0.125-0.85 mm (screened by the 20-mesh sieve and the 120-mesh sieve) is more than or equal to 37 percent, and the feldspar with the grain size of 0-0.125 mm (screened by the 120-mesh sieve) is less than or equal to 60 percent.
Alternatively, the particle size distribution of dolomite is as follows: dolomite with the grain size of more than 2.00mm (screened by a 10-mesh sieve) does not exist, dolomite with the grain size of 0.85-2.00 mm (screened by 10-mesh and 20-mesh sieves) is less than or equal to 25 percent, dolomite with the grain size of 0.125-0.85 mm (screened by 20-mesh and 120-mesh sieves) is more than or equal to 50 percent, and dolomite with the grain size of 0-0.125 mm (screened by a 120-mesh sieve) is less than or equal to 25 percent.
Alternatively, the particle size distribution of fluorite is as follows: fluorite with the particle size of more than 2.00mm (screened by a 10-mesh sieve) is not contained, fluorite with the particle size of 0.85-2.00 mm (screened by 10-mesh and 20-mesh sieves) is less than or equal to 25 percent, fluorite with the particle size of 0.125-0.85 mm (screened by 20-mesh and 120-mesh sieves) is more than or equal to 50 percent, and fluorite with the particle size of 0-0.125 mm (screened by a 120-mesh sieve) is less than or equal to 25 percent.
Alternatively, the particle size of the soda ash is less than 0.18mm (screened with an 80 mesh screen).
Alternatively, the particle size distribution of borax is as follows: the borax with the grain size of more than 2.00mm (screened by a 10-mesh sieve) is absent, the borax with the grain size of 0.85-2.00 mm (screened by 10-mesh and 20-mesh sieves) is less than or equal to 5 percent, the borax with the grain size of 0.125-0.85 mm (screened by 20-mesh and 120-mesh sieves) is more than or equal to 90 percent, and the borax with the grain size of 0-0.125 mm (screened by a 120-mesh sieve) is less than or equal to 5 percent.
Alternatively, the cobalt compound has a particle size of less than 0.15mm (screened using a 100 mesh screen).
Optionally, the particle size of the fining agent is less than 0.85mm (screened with a 20 mesh screen).
Optionally, the sodium nitrate is white fine crystal without agglomeration, and the loose degree is more than or equal to 90%.
According to parts by weight, the preparation method of the glass bottle comprises the steps of mixing 0.5-10 parts of sodium nitrate, 0.2-2 parts of calcite, 0.2-4 parts of fluorite, 0.2-4 parts of clarifying agent and 0.01-1 part of cobalt compound to obtain a first mixture; and then adding 20-50 parts of quartz sand, 5-18 parts of soda ash, 1-15 parts of feldspar, 2-8 parts of borax and 2-12 parts of dolomite into the first mixture to be mixed to obtain a second mixture, and finally adding 24-56 parts of glass slag into the second mixture to be uniformly mixed to obtain a mixed raw material.
And (3) putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1450-1550 ℃, the kiln pressure is 0-5 Pa, and the liquid level fluctuation is-2 mm.
and after the glass liquid is melted to form uniform bubble-free glass liquid, converting the glass liquid into a glass bottle with a preset shape.
the present application is not limited to the manner of converting the molten glass into a glass bottle having a predetermined shape. In the present application, an automatic bottle-making machine may be used to convert the molten glass into a glass bottle of a predetermined shape.
Referring to fig. 1, the formed glass bottle is annealed, and the annealing includes heating, heat preservation and cooling, wherein the AB section is a heating stage, the BC section is a heat preservation stage, and the CE section is a cooling stage.
The heating comprises heating the glass bottle to 560-570 ℃ at a rate of 5-10 ℃/min. The formed glass bottle is cooled before annealing, and the glass bottle needs to be heated to an annealing temperature range, so that the temperature of the glass bottle is raised to a degree that mass points and stress can be adjusted.
The heat preservation comprises the step of preserving the heat of the heated glass bottle for 10-25 min at the temperature of 560-570 ℃. The main purpose of heat preservation is to eliminate the temperature difference generated when the glass bottle is heated rapidly and eliminate the inherent internal stress.
The cooling includes a first cooling and a second cooling, the first cooling being in the CD section and the second cooling being in the DE section of FIG. 1.
The first cooling reduces the temperature of the glass bottle from 560-570 ℃ to 480-500 ℃, and the cooling rate of the first cooling is 1-2 ℃/min. The first cooling ensures that after the original stress in the glass is eliminated, secondary stress due to temperature differences during the cooling process must be prevented.
And cooling for the second time to reduce the temperature of the glass bottle from 480-500 ℃ to room temperature, wherein the cooling rate of the second cooling is 10-15 ℃/min. Since the glass structure is now cured, no new permanent internal stresses are generated.
The prepared glass bottle has high transparency and small internal stress.
the following examples are provided to further illustrate the composition for making glass bottles, the glass bottles, and the method of making the same according to the present application.
Example 1
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Preparation of glass slag
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture to be mixed to obtain a second mixture, and finally 30.74 parts by weight of cullet which is obtained by crushing a transparent glass bottle produced by Chengdu plain Nipple pharmaceutical industry packaging company Limited is added into the second mixture to be uniformly mixed to obtain a mixed raw material;
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
Heating the formed glass bottle to 570 ℃ at the speed of 7 ℃/min, preserving heat for 20min, cooling to 490 ℃ at the speed of 1.5 ℃/min, cooling to room temperature at the speed of 13 ℃/min to obtain the glass bottle, and crushing to obtain glass slag.
2. Mixing material
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the step 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
3. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
4. annealing
heating the formed glass bottle to 570 ℃ at the speed of 7 ℃/min, preserving heat for 20min, cooling to 490 ℃ at the speed of 1.5 ℃/min, and cooling to room temperature at the speed of 13 ℃/min to obtain the glass bottle.
Example 2
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
firstly, mixing 10 parts by weight of sodium nitrate, 2 parts by weight of calcite, 4 parts by weight of fluorite, 1 part by weight of sodium sulfate, 3 parts by weight of cerium oxide and 1 part by weight of cobaltous oxide to obtain a first mixture; then adding 50 parts by weight of quartz sand, 18 parts by weight of soda ash, 15 parts by weight of feldspar, 8 parts by weight of borax and 12 parts by weight of dolomite into the first mixture, mixing to obtain a second mixture, and finally adding 56 parts by weight of the glass slag prepared in the embodiment 1 into the second mixture, and uniformly mixing to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1450 ℃, the kiln pressure is 0Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. annealing
Heating the formed glass bottle to 560 ℃ at the speed of 5 ℃/min, preserving heat for 10min, cooling to 480 ℃ at the speed of 1 ℃/min, and cooling to room temperature at the speed of 10 ℃/min to obtain the glass bottle.
Example 3
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
firstly, mixing 0.5 weight part of sodium nitrate, 0.2 weight part of calcite, 4 weight parts of fluorite, 0.05 weight part of sodium sulfate, 0.15 weight part of cerium oxide and 0.01 weight part of cobaltous oxide to obtain a first mixture; then adding 20 parts by weight of quartz sand, 5 parts by weight of soda ash, 1 part by weight of feldspar, 2 parts by weight of borax and 2 parts by weight of dolomite into the first mixture to be mixed to obtain a second mixture, and finally adding 24 parts by weight of the glass slag prepared in the embodiment 1 into the second mixture to be uniformly mixed to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1550 ℃, the kiln pressure is 5Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
Heating the formed glass bottle to 570 ℃ at the speed of 10 ℃/min, preserving heat for 25min, cooling to 500 ℃ at the speed of 2 ℃/min, and cooling to room temperature at the speed of 15 ℃/min to obtain the glass bottle.
example 4
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.77 part by weight of sodium sulfate and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the embodiment 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
Heating the formed glass bottle to 570 ℃ at the speed of 7 ℃/min, preserving heat for 20min, cooling to 490 ℃ at the speed of 1.5 ℃/min, and cooling to room temperature at the speed of 13 ℃/min to obtain the glass bottle.
Comparative example 1
the embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the embodiment 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1400 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
Heating the formed glass bottle to 570 ℃ at the speed of 7 ℃/min, preserving heat for 20min, cooling to 490 ℃ at the speed of 1.5 ℃/min, and cooling to room temperature at the speed of 13 ℃/min to obtain the glass bottle.
Comparative example 2
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the embodiment 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-5 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
Heating the formed glass bottle to 570 ℃ at the speed of 7 ℃/min, preserving heat for 20min, cooling to 490 ℃ at the speed of 1.5 ℃/min, and cooling to room temperature at the speed of 13 ℃/min to obtain the glass bottle.
comparative example 3
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the embodiment 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
2. Melt forming
putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
the formed glass bottle is cooled to room temperature at the speed of 5 ℃/min to prepare the glass bottle.
Comparative example 4
the embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the embodiment 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
the formed glass bottle is heated to 570 ℃ at the speed of 7 ℃/min, cooled to 490 ℃ at the speed of 1.5 ℃/min and then cooled to room temperature at the speed of 13 ℃/min, thus obtaining the glass bottle.
Comparative example 5
The embodiment of the application provides a composition for manufacturing glass bottles, the glass bottles and a preparation method thereof, and the composition comprises the following steps:
1. Mixing material
Firstly, mixing 2.66 parts by weight of sodium nitrate, 0.83 part by weight of calcite, 1.47 parts by weight of fluorite, 0.11 part by weight of sodium sulfate, 0.66 part by weight of cerium oxide and 0.03 part by weight of cobaltous oxide to obtain a first mixture; 33.71 parts by weight of quartz sand, 9.34 parts by weight of soda ash, 11.82 parts by weight of feldspar, 3.96 parts by weight of borax and 4.67 parts by weight of dolomite are added into the first mixture and mixed to obtain a second mixture, and finally 30.74 parts by weight of the glass slag prepared in the embodiment 1 is added into the second mixture and uniformly mixed to obtain a mixed raw material;
2. Melt forming
Putting the mixed raw materials into a kiln, heating the kiln to melt the mixed raw materials in the kiln, wherein the melting temperature is 1500 ℃, the kiln pressure is 3Pa, the liquid level fluctuation is-2 mm, and after the mixed raw materials are melted to form uniform bubble-free glass liquid, the glass liquid is converted into a glass bottle with a preset shape;
3. Annealing
Heating the formed glass bottle to 570 ℃ at the speed of 7 ℃/min, preserving the heat for 20min, and cooling to room temperature at the speed of 13 ℃/min to obtain the glass bottle.
Test example 1
The glass bottles prepared in examples 1 to 4 and comparative examples 1 to 5 were observed in a bright place under natural light to see whether the surfaces thereof were smooth and flat, whether there were significant glass defects, and whether there were cracks, and the linear thermal expansion coefficient of the glass bottles at 20 to 300 ℃ was tested, and the internal stress of the glass bottles was tested according to the method of YBB00162003-2015, and the test results are shown in table 1:
TABLE 1 Properties of glass bottles obtained in examples 1 to 4 and comparative examples 1 to 5
as can be seen from the comparison between examples 1 and 4, the clarifying effect is better when the mixture of sodium sulfate and cerium oxide is used as the clarifying agent, and the obtained glass bottle has no obvious defects. The glass bottle prepared by only adopting the sodium sulfate clarifying agent has obvious glass defects such as stripes, bubble lines and the like; the optical path of the internal stress is larger, which shows that the internal structure is not uniform and the internal stress is larger; the thermal expansion coefficient is large, the explosion and cracking are easy to occur due to expansion, and the use safety factor is low.
as can be seen from comparison between example 1 and comparative example 1, the surface of the glass bottle obtained by the melt molding process at a lower melting temperature was not smooth and flat; and obvious glass defects such as calculus, crystal point, bubble line and the like appear; the optical path of the internal stress is larger, which indicates that the internal stress of the glass bottle is larger; the thermal expansion coefficient is large, the explosion and cracking are easy to occur due to expansion, and the use safety factor is low.
As can be seen from the comparison between example 1 and comparative example 2, the surface of the glass bottle produced by the melt molding with large fluctuation of the liquid level was not smooth and flat; and obvious glass defects such as stones, large deviation of the outer diameter and the wall thickness of the glass tube and the like occur; the optical path of the internal stress is larger, which indicates that the internal stress of the glass bottle is larger; the thermal expansion coefficient is large, the explosion and cracking are easy to occur due to expansion, and the use safety factor is low.
As can be seen from the comparison between example 1 and comparative example 3, the conventional annealing process directly causes the body of the glass bottle to burst due to excessive internal stress.
As can be seen from the comparison between example 1 and comparative example 4, the glass bottle prepared without the heat preservation process in the annealing process has hidden cracking due to large internal stress.
As can be seen from the comparison between example 1 and comparative example 5, the glass bottle prepared without the slow cooling process in the annealing process has hidden cracking due to large internal stress.
in summary, the composition for manufacturing glass bottles in the embodiments of the present application has the advantages that various raw materials are matched with each other, the light transmittance of the composition is enhanced through the clarification effect of the various raw materials, the expansion coefficient of the glass is reduced through the various raw materials, and the thermal stability, the chemical stability and the mechanical strength of the glass are improved, so that the blue glass bottles with high transparency and stable performance are manufactured. The preparation method of the glass bottle is simple and convenient, the prepared glass bottle has small internal stress, and the use is very safe.
The foregoing is illustrative of the present application and is not to be construed as limiting thereof, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. the composition for manufacturing the glass bottle is characterized by comprising the following raw materials in parts by weight:
24-56 parts of glass slag, 20-50 parts of quartz sand, 0.2-2 parts of calcite, 1-15 parts of feldspar, 2-12 parts of dolomite, 0.2-4 parts of fluorite, 0.5-10 parts of sodium nitrate, 5-18 parts of soda ash, 2-8 parts of borax, 0.01-1 part of cobalt compound and 0.2-4 parts of clarifying agent.
2. The composition for making glass bottles of claim 1, wherein the composition for making glass bottles comprises the following raw materials in parts by weight:
30-56 parts of glass slag, 30-50 parts of quartz sand, 0.8-2 parts of calcite, 5-15 parts of feldspar, 3-12 parts of dolomite, 1-4 parts of fluorite, 1-10 parts of sodium nitrate, 8-18 parts of soda ash, 3-8 parts of borax, 0.03-1 part of cobalt compound and 0.5-4 parts of clarifying agent.
3. the composition for making glass bottles of claim 1, wherein said fining agent comprises sodium sulfate and/or cerium oxide;
Optionally, when the fining agent comprises sodium sulfate and cerium oxide, the mass ratio of sodium sulfate to cerium oxide in the fining agent is 1: 2-1: 8.
4. the preparation method of the glass bottle is characterized by comprising the steps of mixing 24-56 parts of glass slag, 20-50 parts of quartz sand, 0.2-2 parts of calcite, 1-15 parts of feldspar, 2-12 parts of dolomite, 0.2-4 parts of fluorite, 0.5-10 parts of sodium nitrate, 5-18 parts of soda ash, 2-8 parts of borax, 0.01-1 part of cobalt compound and 0.2-4 parts of clarifying agent, melting to form glass liquid, forming and annealing to obtain the glass bottle.
5. The method for producing glass bottles of claim 4, wherein said glass slag, said quartz sand, said calcite, said feldspar, said dolomite, said fluorite, said sodium nitrate, said soda ash, said borax, said cobalt compound, and said fining agent are all in the form of powders;
The particle size of the quartz sand is less than or equal to 1.00mm, the particle size of the calcite is less than or equal to 2.80mm, the particle size of the feldspar is less than or equal to 2.00mm, the particle size of the dolomite is less than or equal to 2.00mm, the particle size of the fluorite is less than or equal to 2.00mm, the particle size of the soda ash is less than or equal to 0.18mm, the particle size of the borax is less than or equal to 2.00mm, the particle size of the cobalt compound is less than or equal to 0.15mm, and the particle size of the clarifier is less than or equal to 0.85.
6. The method for producing glass bottles according to claim 4, wherein the pressure during melting is 0 to 5Pa, the fluctuation of the liquid surface is-2 to 2mm, and the melting temperature is 1450 to 1550 ℃.
7. The method of claim 4, wherein the annealing comprises heating to an annealing temperature, holding at the annealing temperature for a predetermined time and cooling to room temperature.
8. The method for manufacturing a glass bottle according to claim 7, wherein the annealing temperature is 560 to 570 ℃, and the predetermined time is 15 to 25 min.
9. The method for preparing glass bottles according to claim 7, wherein the cooling comprises a first cooling to a target temperature and then a second cooling, wherein the cooling rate of the first cooling is 1-2 ℃/min, and the cooling rate of the second cooling is 10-15 ℃/min.
10. A glass bottle produced by the method for producing a glass bottle according to any one of claims 4 to 9.
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Application publication date: 20191210 |