CN114195382A - Borosilicate glass composition, borosilicate glass preparation method and medicinal glass - Google Patents
Borosilicate glass composition, borosilicate glass preparation method and medicinal glass Download PDFInfo
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- CN114195382A CN114195382A CN202111651081.8A CN202111651081A CN114195382A CN 114195382 A CN114195382 A CN 114195382A CN 202111651081 A CN202111651081 A CN 202111651081A CN 114195382 A CN114195382 A CN 114195382A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
- C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
- C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
- C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
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- 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
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
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- 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
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
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Abstract
The invention discloses a borosilicate glass composition, a borosilicate glass preparation method and medicinal glass, wherein the borosilicate glass composition comprises the following components in percentage by weight: 69.6-71.4 wt% of silicon dioxide, 5.3-6.4 wt% of aluminum oxide, 8-10.4 wt% of boron oxide, 5.6-7.9 wt% of sodium oxide, 0.6-3.4 wt% of potassium oxide, 0.6-0.9 wt% of calcium oxide, 1.1-1.9 wt% of barium oxide, 0.6-1.4 wt% of ferric oxide, 2.5-4.8 wt% of titanium dioxide and 0.05-0.12 wt% of clarifying agent; according to the invention, the percentage content of each component in the borosilicate glass composition and the type of the clarifying agent are controlled, so that the temperature difference between the forming starting temperature and the crystallization temperature of the borosilicate glass composition is increased, the crystallization possibility is reduced, and the product yield is increased.
Description
Technical Field
The invention relates to the technical field of glass production, and particularly relates to a borosilicate glass composition, a borosilicate glass preparation method and medicinal glass.
Background
Neutral borosilicate medical container glass has excellent chemical stability and thermal stability, and is widely applied to the field of medicine packaging, the core barrier of a medium borosilicate glass tube bottle is a glass tube drawing technology, a glass tube belongs to a dieless forming process, and in the actual industrial production (drawing tube forming), the temperature difference between the forming starting temperature and the crystallization temperature of the medium borosilicate glass tube is not large enough, so that the glass crystallization defect is easily generated, and the product yield is reduced.
The forming start temperature of the medium borosilicate glass tube is usually set to an operating point temperature (Tw, glass viscosity of 10)4dpa · s), in actual production, the crystallization performance of the glass must be controlled, and a sufficient temperature difference (Δ Tw-x) is ensured between the crystallization upper limit temperature (Tx) and the production and forming start temperature (Tw) of the glass, so as to avoid the problem of poor product quality caused by glass crystallization.
Disclosure of Invention
The invention mainly aims to provide a borosilicate glass composition, and aims to solve the problem that the yield of finished products is low due to the fact that glass crystallization defects are easily generated in the glass production process.
In order to achieve the above purpose, the present invention provides a borosilicate glass composition, which comprises the following components by weight:
69.6-71.4 wt% of silicon dioxide, 5.3-6.4 wt% of aluminum oxide, 8-10.4 wt% of boron oxide, 5.6-7.9 wt% of sodium oxide, 0.6-3.4 wt% of potassium oxide, 0.6-0.9 wt% of calcium oxide, 1.1-1.9 wt% of barium oxide, 0.6-1.4 wt% of ferric oxide, 2.5-4.8 wt% of titanium dioxide and 0.05-0.12 wt% of clarifying agent.
Optionally, the borosilicate glass composition further comprises zirconium dioxide in a weight percentage of not higher than 0.1 wt%.
Alternatively, in the borosilicate glass composition,
the sum of the weight percentages of the silicon dioxide and the aluminum oxide is 75.1-76.5 wt%; and/or the presence of a gas in the gas,
the sum of the weight percentages of the sodium oxide and the potassium oxide is 8-8.4 wt%.
Alternatively, in the borosilicate glass composition,
the weight ratio of the sodium oxide to the potassium oxide is (6.1-6.9): 1.
optionally, the fining agent comprises a fluorine-containing compound.
Optionally, the fluorine element in the fluorine-containing compound accounts for 0.06-0.09 wt% of the borosilicate glass composition.
Optionally, the fluorine-containing compound comprises calcium fluoride.
Alternatively, in the borosilicate glass composition,
the ratio of the total weight of the aluminum oxide and the zirconium dioxide to the weight of the silicon dioxide is 1: (10.85-13.11); and/or the presence of a gas in the gas,
the weight ratio of the total weight of the calcium oxide and the barium oxide to the boron oxide is 1: (2.76-6.52).
The invention also provides a preparation method of the borosilicate glass, which comprises the following steps:
mixing a plurality of compositions, the compositions comprising the borosilicate glass composition of any of claims 1 to 8, and stirring the mixture to homogeneity to obtain a mixed batch;
melting the mixed ingredients for 5-7 h at 1580-1670 ℃ to obtain glass liquid;
and forming the molten glass, annealing at 600-615 ℃ for 0.4-0.6 h, and cooling to room temperature to obtain the borosilicate glass.
In addition, the invention also provides a medicinal glass which comprises the borosilicate glass composition described in any one of the above.
In the technical scheme of the invention, silicon dioxide is used as a substrate and is used as a core material for forming a glass network of the prepared borosilicate glass composition, the chemical property and the mechanical strength of the prepared borosilicate glass composition are controlled by controlling the content of the silicon dioxide, and meanwhile, in the weight proportion interval, the silicon dioxide not only can be completely melted, but also can inhibit the generation of glass crystallization in the manufacturing process; in order to avoid phase separation of the borosilicate glass composition in the manufacturing process, alumina is added according to the weight proportion, so that the phase separation of the prepared borosilicate glass composition can be inhibited, and the chemical stability and the mechanical strength of the prepared borosilicate glass composition can be improved; meanwhile, the boron oxide is added according to the weight proportion, so that the thermal expansion coefficient and the melting temperature can be reduced, and the chemical stability and the mechanical strength of the prepared borosilicate glass composition can be improved; the addition of sodium oxide and potassium oxide in a weight ratio can reduce the high temperature viscosity of the glass and increase the linear thermal expansion coefficient, but can reduce the chemical stability, particularly hydrolysis resistance, of the borosilicate glass composition prepared; the high-temperature viscosity of the glass can be reduced by adding the calcium oxide according to the weight ratio; the barium oxide is added according to the weight proportion, wherein in the barium oxide, because the ionic radius of barium ions is large and the polarity is strong, the phase separation of glass can be suppressed, and the stability of the chemical property of the prepared borosilicate glass composition is improved; ferric oxide and titanium dioxide are added according to the weight ratio, and the ferric oxide and the titanium oxide are used as coloring agents, so that the borosilicate glass composition prepared by the borosilicate glass composition can be colored, and the transmittance of the borosilicate glass composition in ultraviolet and visible light bands can be reduced; meanwhile, the clarifying agent is added according to the weight proportion, so that the clarifying effect of the prepared borosilicate glass composition is more obvious. The borosilicate glass composition prepared according to the above components can effectively increase the temperature difference between the molding start temperature and the crystallization temperature of the borosilicate glass composition, thereby reducing the possibility of glass crystallization and improving the product yield.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. 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. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Neutral borosilicate medical container glass has excellent chemical stability and thermal stability, and is widely applied to the field of medicine packaging, the core barrier of a medium borosilicate glass tube bottle is a glass tube drawing technology, a glass tube belongs to a dieless forming process, and in the actual industrial production (drawing tube forming), the temperature difference between the forming starting temperature and the crystallization temperature of the medium borosilicate glass tube is not large enough, so that the glass crystallization defect is easily generated, and the product yield is reduced.
The forming start temperature of the medium borosilicate glass tube is usually set to an operating point temperature (Tw, glass viscosity of 10)4dpa · s), in actual production, the crystallization performance of the glass must be controlled, and a sufficient temperature difference (Δ Tw-x) is ensured between the crystallization upper limit temperature (Tx) and the production and forming start temperature (Tw) of the glass, so as to avoid the problem of poor product quality caused by glass crystallization.
In view of this, the present invention provides a borosilicate glass composition, which comprises the following components by weight: 69.6-71.4 wt% of silicon dioxide, 5.3-6.4 wt% of aluminum oxide, 8-10.4 wt% of boron oxide, 5.6-7.9 wt% of sodium oxide, 0.6-3.4 wt% of potassium oxide, 0.6-0.9 wt% of calcium oxide, 1.1-1.9 wt% of barium oxide, 0.6-1.4 wt% of ferric oxide, 2.5-4.8 wt% of titanium dioxide and 0.05-0.12 wt% of clarifying agent.
In the technical scheme of the invention, silicon dioxide is used as a substrate and is used as a core material for forming a glass network of the prepared borosilicate glass composition, the chemical property and the mechanical strength of the prepared borosilicate glass composition are controlled by controlling the content of the silicon dioxide, and meanwhile, in the weight proportion interval, the silicon dioxide not only can be completely melted, but also can inhibit the generation of glass crystallization in the manufacturing process; in order to avoid phase separation of the borosilicate glass composition in the manufacturing process, alumina is added according to the weight proportion, so that the phase separation of the prepared borosilicate glass composition can be inhibited, and the chemical stability and the mechanical strength of the prepared borosilicate glass composition can be improved; meanwhile, the boron oxide is added according to the weight proportion, so that the thermal expansion coefficient and the melting temperature can be reduced, and the chemical stability and the mechanical strength of the prepared borosilicate glass composition can be improved; the addition of sodium oxide and potassium oxide in a weight ratio can reduce the high temperature viscosity of the glass and increase the linear thermal expansion coefficient, but can reduce the chemical stability, particularly hydrolysis resistance, of the borosilicate glass composition prepared; the high-temperature viscosity of the glass can be reduced by adding the calcium oxide according to the weight ratio; the barium oxide is added according to the weight proportion, wherein in the barium oxide, because the ionic radius of barium ions is large and the polarity is strong, the phase separation of glass can be suppressed, and the stability of the chemical property of the prepared borosilicate glass composition is improved; ferric oxide and titanium dioxide are added according to the weight ratio, and the ferric oxide and the titanium oxide are used as coloring agents, so that the borosilicate glass composition prepared by the borosilicate glass composition can be colored, and the transmittance of the borosilicate glass composition in ultraviolet and visible light bands can be reduced; meanwhile, the clarifying agent is added according to the weight proportion, so that the clarifying effect of the prepared borosilicate glass composition is more obvious. The borosilicate glass composition prepared according to the above components can effectively increase the temperature difference between the molding start temperature and the crystallization temperature of the borosilicate glass composition, thereby reducing the possibility of glass crystallization and improving the product yield.
Further, in order to improve the structural stability of the prepared borosilicate glass composition, zirconium dioxide can be optionally added, and the weight percentage of the zirconium dioxide is not higher than 0.1 wt%; in addition, Zr4+In the glass structure in a cubic structure [ ZrO8]Is present because of Zr4+Has high field strength and free oxygen O around2-It is necessary to arrange the glass according to its coordination number so that the free oxygen content in the glass is reduced, which makes it possible to produce borosilicate glass compositions with a more compact structure, but it is noted that zirconium dioxide has a higher melting point, which leads to a significant increase in the glass melting temperature if an excess of zirconium dioxide is added, and that the percentage of zirconium dioxide in the present invention is controlled to be not higher than 0.1 wt.%.
Further, in the borosilicate glass composition, the sum of the weight percentages of silica and alumina is 75.1 to 76.5 wt%; in this embodiment, silica is used as a core material of the glass network of the borosilicate glass composition, and alumina is used as a glass intermediate, so that when entering the glass network, it can reduce non-bridge oxygen to make the structure more compact, therefore, silica and alumina need to be added in proportion to prepare the borosilicate glass composition, but it should be noted that the content of silica and alumina affects the chemical stability of the prepared borosilicate glass composition and the probability of glass devitrification; after repeated test and research, the inventor finds that the silicon dioxide and the aluminum oxide are most suitable when the sum of the weight percentages of the silicon dioxide and the aluminum oxide is 75.1-76.5 wt%. When the sum of the weight percentages of silica and alumina is less than 75.1 wt%, the borosilicate glass composition produced has a chemical stability that does not meet the requirements for a neutral pharmaceutical container glass; when the sum of the weight percentages of silica and alumina is higher than 76.5 wt%, the temperature requirements during the preparation process will increase and higher temperatures will be required to completely melt the silica and alumina. Therefore, when the total weight percentage of silica and alumina is 75.1-76.5 wt%, the chemical stability of the prepared borosilicate glass composition meets the requirement of neutral medicinal container glass, and the energy consumption is not increased too much due to higher melting temperature.
In addition, in the borosilicate glass composition, the sum of the weight percentages of sodium oxide and potassium oxide is 8 to 8.4 wt.%. The purpose of adding sodium oxide is to reduce the high-temperature viscosity of the glass of the borosilicate glass composition and increase the linear expansion coefficient, if the content of the added sodium oxide is too small in the preparation process, the temperature reduction of the glass in the preparation process is not obvious, and the content of the added sodium oxide is too high, the chemical stability, particularly the hydrolysis resistance, of the prepared borosilicate glass composition is reduced, so that the prepared borosilicate glass composition does not meet the requirement of neutral medicinal container glass; the purpose of adding potassium oxide is to reduce the high-temperature viscosity and increase the linear thermal expansion coefficient of the glass of the borosilicate glass composition, if the content of the added potassium oxide is too small in the preparation process, the temperature reduction of the glass in the preparation process is not obvious, and the content of the added potassium oxide is too high, the chemical stability, particularly the hydrolysis resistance, of the prepared borosilicate glass composition is reduced, so that the prepared borosilicate glass composition does not meet the requirement of neutral medicinal container glass; in addition, it should be noted that when the total weight percentage of potassium oxide and sodium oxide is less than 8 wt%, the borosilicate glass composition prepared has poor acid resistance and is easily corroded by acidic substances; when the sum of the weight percentages of potassium oxide and sodium oxide is greater than 8.4 wt%, the borosilicate glass composition prepared has poor hydrolysis resistance. Therefore, through repeated research and tests of the inventor, the borosilicate glass composition prepared by the method is more stable in chemical property, especially optimal in acid resistance and hydrolysis resistance and meets the requirements of neutral medicinal container glass when the sum of the weight percentages of sodium oxide and potassium oxide is 8-8.4 wt%.
Further, in the borosilicate glass composition, the weight ratio of sodium oxide to potassium oxide is (6.1 to 6.9): 1. it is noted that the chemical stability of sodium oxide is superior to that of potassium oxide, and thus it is practically used for pharmaceutical purposesThe monovalent alkali metal oxide in the container glass is mainly sodium oxide, and in the embodiment, the purpose of introducing a small amount of potassium oxide is to utilize K+Filling larger holes in the glass network (wherein the larger holes are due to Na)+Small ionic radius and is easily leached), making the structure of the produced silicate glass composition more compact. When the sodium and potassium content in the glass is not changed, and the potassium oxide is gradually substituted for the sodium oxide, the property of the glass does not change linearly but shows an obvious extreme value, and the effect is called as mixed alkali effect and also called as neutralization effect; the inventor finds that, under the same conditions, when the weight ratio of the sodium oxide to the potassium oxide is (6.1-6.9): 1, the melting temperature of the glass can be reduced to the lowest value, so that when the weight ratio of the sodium oxide to the potassium oxide is (6.1-6.9): 1, the chemical stability of the borosilicate glass composition produced meets the requirements of a neutral pharmaceutical container glass and does not increase the energy consumption too much due to the higher melting temperature.
In addition, in order to ensure the transparency of the borosilicate glass composition to be produced, a clarifying agent needs to be added during the production process, and the clarifying agent is widely in various types, wherein the clarifying agent contains CL-Ions and containing F-The most commonly used agent for ions, note that CL in the fining agent-Polarity ratio F of ions-The polarity of ions is large, the glass network is easy to damage, and meanwhile, a great deal of research and experiments of the inventor prove that the upper crystallization limit temperature of the glass containing the CL element is 21 ℃ higher than that of the glass containing the F element under the condition that the same amount of clarifying agent is added into the medium borosilicate glass with the same basic components; thus, in this example, the fining agent is selected to be a fluorochemical fining agent.
Further, the specific form of the fluorine compound is not limited as long as it can perform a refining function, and the fluorine-containing compound is preferably calcium fluoride in this embodiment, considering the requirements of the glass production process and the subsequent processing process.
Furthermore, when the content of the F element in the prepared molten glass is low, the clarification effect on the glass is not obvious, and when the content of the F element is too high, the clarification effect on the glass is not further promoted, and only the material is wasted; therefore, repeated research and tests of the inventor show that in the preparation process, when the weight percentage of fluorine element in the added clarifying agent is 0.06-0.09 wt%, the clarifying effect is not obvious, and raw materials are not wasted.
In order to make the temperature difference (Δ Tw-x) between the glass crystallization upper limit temperature (Tx) and the production molding start temperature (Tw) greater than 120 ℃ and reduce the possibility of glass crystallization, in the present embodiment, the ratio of the total weight of alumina and zirconia to the weight of silica needs to be controlled to be 1: (10.85-13.11); the weight ratio of the total weight of calcium oxide and barium oxide to boron oxide is 1: (2.76-6.52).
The component proportion of the glass determines the crystallization performance of the glass, and in the preparation process of the neutral borosilicate glass, the tightness degree of oxide network connection plays an important role in glass crystallization, namely, the tighter the oxide network connection (the less the non-bridge oxygen content), the less easy the glass liquid is adjusted to be in regular arrangement in the cooling, molding and curing process, namely, the less easy the glass crystallization is generated; conversely, the more the oxide network breaks (i.e., the more non-bridging oxygen content), the more likely the glass will devitrify during the cool-down forming solidification process.
The silicon dioxide is a core substance for forming a glass network, the aluminum oxide is a glass intermediate, and non-bridge oxygen is reduced when the silicon dioxide enters the network so as to enable the structure to be compact; zr4+In the glass structure in a cubic structure [ ZrO8]Is present because of the higher field strength, the surrounding free oxygen O2-The glass is required to be arranged according to the coordination number, so that the content of free oxygen in the glass is reduced, and the glass structure is more compact; thus, in the above-described ingredients for preparing borosilicate glass compositions, the amount of alumina and zirconia combined increases (i.e., SiO2/(Al2O3+ZrO2) The weight ratio is reduced), the structure of the prepared borosilicate glass composition is more and more compact, and glass crystallization is less and less likely to occur (namely, the glass crystallization upper limit temperature is lower and lower); thus, passing through the hairThe best-known people repeatedly research and test to obtain: when SiO is present2/(Al2O3+ZrO2) When the weight ratio is more than 13.11, the glass crystallization performance of the borosilicate glass composition with the components can not meet the requirement; when SiO is present2/(Al2O3+ZrO2) At a weight ratio of less than 10.85, i.e. (Al)2O3+ZrO2) The melting temperature of the glass is significantly increased by increasing the content more, so that, in this embodiment, the ratio of the total weight of alumina and zirconia to the weight of silica is controlled to be 1: (10.85-13.11), the compact structure of the prepared borosilicate glass control composition can be ensured, the possibility of glass crystallization is further reduced, and the product yield is improved.
In addition, boron oxide is a glass former and intermediate that can generally form boron oxygen trigones (BO) under different conditions3) Or tetrahedron (BO)4) Under the condition of high-temperature melting, boron oxide generally has difficulty in forming boron-oxygen tetrahedrons and can only exist in boron-oxygen triangles; at low temperatures, however, under certain conditions B3+The ions have the tendency of capturing free oxygen to form boron-oxygen tetrahedron, so that the glass structure tends to be compact; ca2+The ions have an 'accumulation effect' on the glass structure, Ca2+When the ion content is high, crystallization is easy to occur; at the same time, Ba2+Also has the functions of polarizing bridge oxygen and weakening silicon-oxygen bonds; in the borosilicate glass composition of the above composition, the contents of calcium oxide and barium oxide decrease as the content of boron oxide increases (i.e., B2O3(CaO + BaO) weight ratio is increased), the structure of the prepared borosilicate glass composition tends to be compact, and the composition is difficult to crystallize (namely, the crystallization upper limit temperature is lower); the inventor repeatedly studies and tests to obtain that: when B is present2O3When the weight ratio of CaO + BaO is less than 2.76, the crystallization performance of the borosilicate glass composition with the components can not meet the requirement; when B is present2O3If the weight ratio of CaO + BaO is greater than 6.52, the boron oxide content is too high, which leads to a decrease in the stability of the borosilicate glass composition to be produced, and in particular, a significant decrease in the acid resistance; due to the fact thatHere, in this example, the weight ratio of the total weight of calcium oxide and barium oxide to boron oxide was controlled to be 1: (2.76-6.52), the structure of the prepared borosilicate glass composition can be ensured to be more compact, and the chemical performance of the prepared borosilicate glass composition can be ensured, particularly the acid resistance meets the requirement of neutral medicinal container glass.
Based on the borosilicate glass composition, the invention also provides a preparation method of the borosilicate glass, which comprises the following steps:
step S10, mixing a plurality of compositions, wherein the compositions comprise the borosilicate glass composition of any one of claims 1 to 8, and stirring the mixture uniformly to obtain a mixed ingredient;
step S20, melting the mixed ingredients for 5-7 hours at 1580-1670 ℃ to obtain glass liquid;
heating the smelting furnace to 1580-1670 ℃, then continuously putting the mixed ingredients into the smelting furnace, keeping the temperature between 1580-1670 ℃, continuously heating and melting for 5-7 hours to obtain molten liquid, and clarifying and homogenizing the molten liquid to obtain glass liquid.
And S30, forming the molten glass, annealing at 600-615 ℃ for 0.4-0.6 h, and cooling to room temperature to obtain the borosilicate glass.
The method for forming the molten glass is not limited in the present invention, and specifically, in an embodiment, the molten glass is poured into a glass mold, then an annealing furnace is heated to 600 to 615 ℃, the glass mold filled with the molten glass is placed in the annealing furnace, the temperature is maintained between 600 and 615 ℃, after heating for 0.4 to 0.6h, the heating is stopped, and the annealing furnace is cooled to room temperature (the room temperature is 23 to 28 ℃), so as to obtain borosilicate glass; in another embodiment, the molten glass is wound around a rotary pipe, and while blowing air from the front end portion of the rotary pipe, the glass is drawn in a tubular shape from the front end portion, and the drawn tubular object is cut into a predetermined length; and then heating the annealing furnace to 600-615 ℃, placing the cut tubular object with the preset length in the annealing furnace, keeping the temperature at 600-615 ℃, stopping heating after heating for 0.4-0.6 h, and cooling the annealing furnace to room temperature (the room temperature is 23-28 ℃) to obtain the borosilicate glass.
Wherein, in the process of preparing the borosilicate glass, the conventional procedures of melting, clarifying, homogenizing and forming in the technical field of glass are involved, and the details are not repeated. The borosilicate glass prepared by the method has stable structure and good chemical resistance, and meets the requirements of neutral medicinal container glass.
The invention also provides a medicinal glass, which comprises a borosilicate glass composition, and the specific preparation method of the borosilicate glass composition refers to the embodiment. Since the borosilicate glass composition employs all technical solutions of all the above embodiments, at least all the beneficial effects brought by the technical solutions of the above embodiments are achieved, and no further description is given here.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
(1) Weighing raw materials: 70.71kg of silicon dioxide, 5.30kg of aluminum oxide, 1.00kg of ferric oxide, 0.60kg of calcium oxide, 7.06kg of sodium oxide, 1.05kg of potassium oxide, 1.00kg of barium oxide, 0.10kg of zirconium dioxide, 10.40kg of boron oxide, 2.70kg of titanium dioxide and 0.10kg of calcium fluoride (the content of fluorine element in the calcium fluoride is 0.08 kg); uniformly mixing to obtain mixed ingredients;
wherein the weight ratio of the total weight of the aluminum oxide and the zirconium dioxide to the silicon dioxide is 1: 13.09, the weight ratio of the total weight of calcium oxide and barium oxide to boron oxide was 1:6.5, the total weight of sodium oxide and potassium oxide was 8.11kg, the total weight of silica and alumina was 76.01kg, and the weight ratio of sodium oxide to potassium oxide was 6.72: 1.
(2) Heating the furnace to 1610 ℃, then continuously putting the mixed ingredients into the furnace, keeping the temperature at 1610 ℃, continuously heating for 6h to obtain molten liquid, and clarifying and homogenizing the molten liquid to obtain molten glass.
(3) Pouring molten glass into a glass mold, heating an annealing furnace to 610 ℃, placing the glass mold filled with the molten glass into the annealing furnace, keeping the temperature between 610 ℃, stopping heating after heating for 0.5h, cooling the annealing furnace to room temperature (the room temperature is 23.8 ℃) to obtain the borosilicate glass.
The preparation methods and procedures of examples 2 to 31 were the same as those of example 1 except that the weight of each compound was different, and the weight of each compound of examples 2 to 31 is shown in tables 1 to 4.
TABLE 1 examples 2 to 10
TABLE 2 examples 11 to 19
TABLE 3 examples 20 to 28
TABLE 4 examples 29 to 31
| Example 29 | Example 30 | Example 31 | |
| SiO2 | 70.37 | 70.37 | 70.37 |
| Al2O3 | 5.70 | 5.7 | 5.7 |
| Fe2O3 | 1.00 | 1.00 | 1.00 |
| CaO | 0.70 | 0.70 | 0.70 |
| MgO | 0.00 | 0.00 | 0.00 |
| NaO2 | 6.96 | 7.06 | 7.06 |
| K2O | 1.15 | 1.05 | 1.05 |
| BaO | 1.30 | 1.30 | 1.30 |
| ZrO2 | 0.01 | 0.01 | 0.01 |
| B2O3 | 9.60 | 9.60 | 9.60 |
| TiO2 | 3.13 | 3.12 | 3.15 |
| F | 0.08 | 0.09 | 0.06 |
| Cl | 0.00 | 0.00 | 0.00 |
| SiO2/(Al2O3+ZrO2) | 12.32 | 12.32 | 12.32 |
| B2O3/(CaO+BaO) | 4.80 | 4.80 | 4.80 |
| SiO2+Al2O3 | 76.07 | 76.07 | 76.07 |
| NaO2+K2O | 8.11 | 8.11 | 8.11 |
| NaO2/K2O | 6.05 | 6.72 | 6.72 |
Comparative example
In addition, the preparation method and procedure of comparative examples 1 to 5 are the same as those of example 1, except that the weight of each compound is different, and the weight of each compound of comparative examples 1 to 5 is shown in table 5.
TABLE 5 comparative examples 1 to 5
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| SiO2 | 70.81 | 70.00 | 70.37 | 70.71 | 70.71 |
| Al2O3 | 5.20 | 6.50 | 5.70 | 5.30 | 5.30 |
| Fe2O3 | 1.00 | 0.80 | 1.00 | 1.00 | 1.00 |
| CaO | 0.60 | 0.60 | 0.98 | 0.60 | 0.60 |
| MgO | 0.00 | 0.00 | 0.00 | 0.00 | 0.00 |
| NaO2 | 7.06 | 7.06 | 7.06 | 7.06 | 7.06 |
| K2O | 1.05 | 1.05 | 1.05 | 1.05 | 1.05 |
| BaO | 1.00 | 1.00 | 1.90 | 1.00 | 1.00 |
| ZrO2 | 0.00 | 0.12 | 0.01 | 0.10 | 0.10 |
| B2O3 | 10.40 | 9.70 | 7.90 | 10.80 | 10.40 |
| TiO2 | 2.80 | 3.09 | 3.95 | 2.30 | 2.70 |
| F | 0.08 | 0.08 | 0.08 | 0.08 | 0.00 |
| Cl | 0.00 | 0.00 | 0.00 | 0.00 | 0.08 |
| SiO2/(Al2O3+ZrO2) | 13.62 | 10.57 | 12.32 | 13.09 | 13.09 |
| B2O3/(CaO+BaO) | 6.50 | 6.06 | 2.74 | 6.75 | 6.50 |
| SiO2+Al2O3 | 8.11 | 8.11 | 8.11 | 8.11 | 8.11 |
| NaO2+K2O | 6.72 | 6.72 | 6.72 | 6.72 | 6.72 |
| NaO2/K2O | 5.31 | 4.72 | 5.48 | 5.25 | 5.29 |
Performance testing
In the present invention, the coefficient of thermal expansion of borosilicate glass is measured according to ASTM E228-1985, test method for measuring linear thermal expansion of solid materials by means of a transparent quartz dilatometer.
The 121 ℃ water resistance of borosilicate glass was determined according to YBB00252003-2015 "determination and classification of water resistance of glass particles at 121 ℃ C., it being noted that according to this standard, when the test result is not more than 0.10g/ml, the 121 ℃ water resistance of the test glass is first order.
The acid resistance of borosilicate glasses is determined according to YBB00342004-2015 "determination of boiling hydrochloric acid resistance", it being noted that according to this criterion, the acid resistance of the test glass is first order when the test result is less than or equal to 0.70mg/dm 2.
The alkali resistance of borosilicate glasses was determined according to YBB00352004-2015 method for measuring the boiling resistance of mixed alkali aqueous solutions, it being noted that according to this standard, when the test result is > 75 to < 175mg/dm2, the alkali resistance of the test glass is of two stages.
High temperature viscosity Curve of borosilicate glass the high temperature viscosity curve of the glass was tested according to ASTM C-965 using a rotational high temperature viscometer of Orton RSV model 1600, with a viscosity of 104The temperature corresponding to dpa · s is the operating point temperature (Tw).
Devitrification ceiling temperature of borosilicate glass the devitrification ceiling temperature of the glass was tested according to ASTM C-829 using an Orton GTF-1612SLW-G gradient furnace.
The test results of examples 1 to 31 are shown in tables 6 to 9, and the test results of comparative examples 1 to 5 are shown in table 10.
TABLE 6 test results of examples 1 to 10
TABLE 7 test results of examples 10 to 18
TABLE 8 test results for examples 19 to 27
TABLE 9 examples 28 to 31
TABLE 10 test results of comparative examples 1 to 5
As can be seen from tables 6-10, the weight percentage of the aluminum oxide in the comparative example 1 is 5.2 wt%, and the ratio of the total weight of the aluminum oxide and the zirconium dioxide to the weight of the silicon dioxide is 1:13.62, which are not in the scope of the invention, so that the temperature difference delta Tw-x between the forming starting temperature and the crystallization temperature in the comparative example 1 is 85 ℃ and less than 120 ℃, and the requirement of industrial production on the crystallization performance of the glass is not met; the weight percentage of the alumina in the comparative example 2 is 6.5 wt%, the ratio of the total weight of the alumina and the zirconium dioxide to the weight of the silicon dioxide is 1:10.57, which are not in the scope of the invention, the working point temperature of the comparative example 2 is 1181 ℃, is more than 1169 ℃, the melting temperature is higher, and the production energy consumption is increased too much; comparative example 3 the weight percent of boron oxide was 7.9 wt%, the total weight of calcium oxide and barium oxide and the weight of boron oxideThe ratio is 1:2.74, the temperature difference delta Tw-x between the forming starting temperature and the crystallization temperature of the comparative example 3 is 118 ℃ and is less than 120 ℃, and the requirement of industrial production on the crystallization performance of the glass is not met; the weight percent of boron oxide in comparative example 4 was 10.8 wt%, the ratio of the total weight of calcium oxide and barium oxide to the weight of boron oxide was 1:6.75, both out of the range of the present invention, and the acid resistance test result of comparative example 4 was 0.74mg/dm2Does not meet the requirement of first-grade acid resistance; the difference between the comparative example 5 and the example 1 is that calcium chloride is added as the clarifying agent in the comparative example 5, the temperature difference delta Tw-x between the forming starting temperature and the crystallization temperature in the comparative example 5 is 101 ℃ and is less than 120 ℃, and the requirement of industrial production on the crystallization performance of the glass is not met.
The weight percentages of the components in the embodiments 1-31 are all within the scope of the invention, and the following are obtained through detection: the expansion coefficient of the prepared borosilicate glass is 4.87 multiplied by 10-6/K-1～5.47×10-6/K-1Meets the requirement of the glass of the neutral medicinal container; the water resistance of the particles at 98 ℃ is first grade, the water resistance of the particles at 121 ℃ is first grade, the acid resistance is first grade, the alkali resistance is second grade, and the chemical resistance stability of the glass is good; viscosity 104The working point temperature (Tw) at dpa s is lower than 1169 ℃, and the glass has good melting property and subsequent processability; the temperature difference delta Tw-x between the crystallization upper limit temperature (Tx) of the borosilicate glass and the production molding starting temperature (Tw) is more than 120 ℃, and the requirement of industrial production on the crystallization performance of the glass is met.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. A borosilicate glass composition, characterized in that said borosilicate glass composition comprises the following components in percent by weight:
69.6-71.4 wt% of silicon dioxide, 5.3-6.4 wt% of aluminum oxide, 8-10.4 wt% of boron oxide, 5.6-7.9 wt% of sodium oxide, 0.6-3.4 wt% of potassium oxide, 0.6-0.9 wt% of calcium oxide, 1.1-1.9 wt% of barium oxide, 0.6-1.4 wt% of ferric oxide, 2.5-4.8 wt% of titanium dioxide and 0.05-0.12 wt% of clarifying agent.
2. The borosilicate glass composition of claim 1, further comprising zirconium dioxide in a weight percent amount of not greater than 0.1 wt.%.
3. The borosilicate glass composition according to claim 1, wherein in said borosilicate glass composition,
the sum of the weight percentages of the silicon dioxide and the aluminum oxide is 75.1-76.5 wt%; and/or the presence of a gas in the gas,
the sum of the weight percentages of the sodium oxide and the potassium oxide is 8-8.4 wt%.
4. The borosilicate glass composition according to claim 3, wherein in said borosilicate glass composition,
the weight ratio of the sodium oxide to the potassium oxide is (6.1-6.9): 1.
5. the borosilicate glass composition of claim 1, wherein said fining agent comprises a fluorine-containing compound.
6. The borosilicate glass composition according to claim 5, wherein the fluorine-containing compound comprises 0.06 to 0.09 wt% of fluorine in the borosilicate glass composition.
7. The borosilicate glass composition of claim 5, wherein said fluorine-containing compound comprises calcium fluoride.
8. The borosilicate glass composition according to claim 1, wherein in said borosilicate glass composition,
the ratio of the total weight of the aluminum oxide and the zirconium dioxide to the weight of the silicon dioxide is 1: (10.85-13.11); and/or the presence of a gas in the gas,
the weight ratio of the total weight of the calcium oxide and the barium oxide to the boron oxide is 1: (2.76-6.52).
9. A method for preparing borosilicate glass is characterized by comprising the following steps:
mixing a plurality of compositions, the compositions comprising the borosilicate glass composition of any of claims 1 to 8, and stirring the mixture to homogeneity to obtain a mixed batch;
melting the mixed ingredients for 5-7 h at 1580-1670 ℃ to obtain glass liquid;
and forming the molten glass, annealing at 600-615 ℃ for 0.4-0.6 h, and cooling to room temperature to obtain the borosilicate glass.
10. A pharmaceutical glass comprising the borosilicate glass composition according to any one of claims 1 to 8.
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| US20110070444A1 (en) * | 2008-06-18 | 2011-03-24 | Nippon Sheet Glass Company, Limited | Scale-like glass and coated scale-like glass |
| JP2012206861A (en) * | 2011-03-29 | 2012-10-25 | Nippon Electric Glass Co Ltd | Method for manufacturing glass substrate |
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| CN112321152A (en) * | 2020-09-23 | 2021-02-05 | 湖南旗滨医药材料科技有限公司 | Borosilicate glass and preparation method thereof |
| CN113213755A (en) * | 2021-05-20 | 2021-08-06 | 河北光兴半导体技术有限公司 | Neutral borosilicate glass composition, neutral borosilicate glass product, and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110070444A1 (en) * | 2008-06-18 | 2011-03-24 | Nippon Sheet Glass Company, Limited | Scale-like glass and coated scale-like glass |
| JP2012206861A (en) * | 2011-03-29 | 2012-10-25 | Nippon Electric Glass Co Ltd | Method for manufacturing glass substrate |
| CN105621883A (en) * | 2016-02-02 | 2016-06-01 | 彩虹（合肥）液晶玻璃有限公司 | Liquid crystal substrate glass and preparation method thereof |
| CN112321152A (en) * | 2020-09-23 | 2021-02-05 | 湖南旗滨医药材料科技有限公司 | Borosilicate glass and preparation method thereof |
| CN113213755A (en) * | 2021-05-20 | 2021-08-06 | 河北光兴半导体技术有限公司 | Neutral borosilicate glass composition, neutral borosilicate glass product, and preparation method and application thereof |
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