CN117417125A - Preparation method of medical glass with low boron volatilization - Google Patents

Preparation method of medical glass with low boron volatilization Download PDF

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Publication number
CN117417125A
CN117417125A CN202311350620.3A CN202311350620A CN117417125A CN 117417125 A CN117417125 A CN 117417125A CN 202311350620 A CN202311350620 A CN 202311350620A CN 117417125 A CN117417125 A CN 117417125A
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China
Prior art keywords
glass
bao
cao
temperature
melting
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CN202311350620.3A
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Chinese (zh)
Inventor
彭寿
李常青
石丽芬
曹欣
崔介东
高强
仲召进
王萍萍
赵凤阳
王巍巍
柯震坤
李金威
杨勇
韩娜
张晓雨
单传丽
倪嘉
王鹏
胡文涛
周刚
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China National Building Material Group Co Ltd CNBM
China Building Materials Glass New Materials Research Institute Group Co Ltd
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China National Building Material Group Co Ltd CNBM
China Building Materials Glass New Materials Research Institute Group Co Ltd
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Priority to CN202311350620.3A priority Critical patent/CN117417125A/en
Publication of CN117417125A publication Critical patent/CN117417125A/en
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B25/00Annealing glass products
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03BMANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/235Heating the glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum

Abstract

The invention discloses medical glass with low boron volatilization and a preparation method thereof, wherein the medical glass comprises the following components in percentage by weight: 55-70wt% SiO 2 15-20wt% of Al 2 O 3 0.1 to 5wt% of B 2 O 3 3-8wt% of Na 2 O, 0.5-5.5wt% K 2 O, 0.5-6wt% CaO, 0.5-6wt% BaO, 0.1-2wt% P 2 O 5 0.1-3wt% ZrO 2 0-2% NaCl, 0-2% CeO 2 0-2% NaNO 3 And then adopting multistage gradient fusion molding. Compared with the traditional neutral borosilicate glass, the invention greatly reduces boron volatilization, has stable glass composition and thermal expansion coefficient of 4.6-5.2 multiplied by 10 –6 Water resistance at a temperature of °cThe acid resistance reaches level 1, the alkali resistance reaches level 2, the yield is high, the quality is stable, the process is simple, the cost is low, and the method is suitable for industrial production.

Description

Preparation method of medical glass with low boron volatilization
Technical Field
The invention relates to the technical field of medical glass, in particular to a preparation method of medical glass with low boron volatilization.
Background
Chinese is highly concerned about drug administration. The 5 th 2020 injection is formally incorporated into a consistency evaluation, and the quality and performance of packaging materials and containers used for the injection must not be lower than those of a reference preparation so as to ensure that the quality of medicines is consistent with that of the reference preparation. Meanwhile, the requirements for vaccines and key medicines are greatly increased, and the productivity of the medium borosilicate glass tube is insufficient, so that the whole glass medicine packaging material industry chain is greatly impacted. In addition, with the development of the pharmaceutical industry and the enrichment of pharmaceutical products, more meta-acid or meta-alkali medicines appear, and the problem of flaking caused by incompatibility of the medicines and glass is increased, so that the research and development of the pharmaceutical glass with higher chemical stability and thermal stability are required, the safety of medicines is ensured, and the life health of people is ensured.
Medical glass has many excellent properties such as transparency, smoothness, barrier properties, chemical stability, temperature resistance, light shielding properties, compatibility, and recyclability. The packaging container is an irreplaceable packaging container for a plurality of medical products and biological agents, and is widely applied to the packaging of medicines such as vaccines, high-end infusion solutions, antibiotics, common powder, freeze-drying, blood, biological agents and the like.
The basic composition of the medical glass is borosilicate glass, the borosilicate glass has good chemical stability, when the borosilicate glass is filled with chemical reagents and medicines, the leaching amount of alkali ions in the borosilicate glass is small, the pH value change can not be caused in the process of long-term contact with the medicine liquid, and the borosilicate glass does not have the phenomena of precipitate precipitation or glass chip falling. The medical glass has the following advantages: (1) The expansion coefficient is low, the extreme cold and heat resistance is high, and the method is suitable for freeze-drying products. And (2) the product is not easy to crack in the processing process and has strong impact resistance. (3) good chemical stability and high acid, alkali and water resistance level.
However, borate glass is high in boron content and is meltedB in (B) 2 O 3 The glass is extremely volatile, the general volatile amount is 10 to 15 percent, a large amount of raw materials can be consumed, refractory materials are extremely easily eroded, the service life of the melting furnace is shortened, the actual composition and the design composition of the glass are greatly different, and B in the glass is not easy to control 2 O 3 The content of the glass, thereby affecting the physicochemical properties of the glass. In addition, B 2 O 3 The volatilization of the glass liquid in the kiln can cause layering phenomenon, and the glass liquid can also cause stripes in the glass liquid on the glass liquid surface, so that the glass is molten unevenly, and the defects of bubbles, stripes and the like are easy to occur in the tube drawing forming process, so that the control of medical glass tubes and bottle making is difficult, and the yield and the product quality are reduced.
Disclosure of Invention
The invention aims to solve the problem that boron volatilizes in the medical glass preparation process to cause defects easily, and provides a medical glass preparation method with low boron volatilization.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the preparation method of the medical glass with low boron volatilization is characterized by comprising the following steps of:
s1, preparing a batch: taking 55-70wt% of SiO according to the weight percentage 2 15-20wt% of Al 2 O 3 0-7wt% of B 2 O 3 0-5wt% of Li 2 O, 1-8wt% Na 2 O, 0.5-5.5wt% K 2 O, 0.5-6wt% CaO, 0.5-6wt% BaO, 0.1-3wt% ZrO 2 0.1-2wt% TiO 2 0-2.5% NaCl and 0-2% CeO 2 0-2.5% NaNO 3 As a raw material, wherein SiO 2 +Al 2 O 3 The value is 73-87%, li 2 O+Na 2 O+K 2 The O value is 5-12.5%, naCl+CeO 2 +NaNO 3 The value is 0.05-3%.
S2, glass melting: and (3) mixing the batch materials prepared in the step (S1), putting the mixture into a crucible, forming clear glass liquid by adopting a multistage gradient melting process, uniformly stirring the glass liquid, cooling and forming, and annealing at 550 ℃ to obtain the medical glass.
In the invention, the multistage gradient melting system in the S2 is as follows: (1) heating section: the temperature is raised to 1050-1150 ℃ from room temperature, and the temperature rise time is 1.5-2.5h; (2) melting section: continuously heating to 1550-1640 ℃ for 2-3h; (3) heat preservation section: preserving heat at 1550-1640deg.C for 1-4h; (4) annealing section: transferring to 550 ℃ for annealing, and keeping the temperature for 0.5-2.5h.
In the present invention, siO 2 Is the main component of glass, siO 2 Is one of the main determinants of glass melting process performance and physicochemical properties. If SiO 2 The content of the glass tube is too small, the chemical stability of the medical glass tube is reduced, and the potential safety hazard of medication caused by glass flaking during medicament containing is increased. On the other hand, if SiO 2 The medicine glass SiO has the advantages of obviously increased melting temperature and processing temperature, difficult clarification of glass, increased manufacturing difficulty and production cost 2 The content is 55-70wt%.
In the present invention, al 2 O 3 The method is favorable for enhancing the compactness of a glass network structure, improving the chemical stability of the glass, and increasing the melting and clarifying difficulty of the glass due to excessive content of the medical glass Al 2 O 3 15-20wt%.
In the invention, B 2 O 3 Can reduce brittleness of glass, improve chemical stability of glass, and simultaneously B 2 O 3 Is also a good auxiliary melting agent, can greatly reduce the glass melting temperature, and is also beneficial to the vitrification process, and the medical glass B 2 O 3 0-7wt%.
In the present invention, na 2 O、K 2 O can reduce the viscosity of the glass, properly increase the alkali metal content can promote the melting process of the glass, reduce the melting temperature, but excessive content can reduce the chemical stability of the glass. The medical glass Na 2 O content of 1-8wt%, K 2 The content of O is 0.5-5.5wt%.
In the invention, caO and BaO can regulate and reduce high-temperature viscosity and improve glass melting performance, and can not reduce glass strain point, but excessive content can reduce glass chemical stability. The medical glass contains 0.5-6wt% of CaO and 0.5-6wt% of BaO.
In the present invention, zrO 2 Can improve the chemical stability of glass, especially alkali resistance. ZrO (ZrO) 2 Too little content can not play the role of improving the chemical stability of the glass; excessive glass viscosity can be increased, melting temperature can be increased, and melting difficulty can be increased. The medical glass ZrO 2 The content of (C) is 0.1-3wt%.
In the invention, P 2 O 5 The introduction of (2) can reduce the melting temperature and forming temperature of the glass and increase the thermal expansion coefficient, but excessive introduction can crystallize the glass and reduce the chemical stability. The medical glass P 2 O 5 The content of (C) is 0.1-2wt%.
In the invention, the medical glass preferably comprises the following components in percentage by weight: 57-68wt% SiO 2 17-20wt% of Al 2 O 3 0-5wt% of B 2 O 3 0-3wt% of Li 2 O, 3-8wt% Na 2 O, 0.5-4wt% K 2 O, 0.5-4wt% CaO, 0.5-4wt% BaO, 0.1-2wt% ZrO 2 0-2% NaCl, 0-1.5% CeO 2 0-2% NaNO 3 Wherein SiO is 2 +Al 2 O 3 Has a value of 75-85%, li 2 O+Na 2 O+K 2 The O value is 6-12%, naCl+CeO 2 +NaNO 3 The value is 0.05-2%.
The medical glass is characterized in that the medical glass with low boron volatilization has a thermal expansion coefficient (20-300 ℃): 4.6 to 5.2X10 -6 The water resistance and the acid resistance reach 1 level, the alkali resistance reaches 2 level, and the operation temperature T w < 1240 ℃, melting temperature T m <1710℃。
In the present invention, the metal oxide is formed by limiting (Na 2 O+K 2 O+CaO+BaO)/Al 2 O 3 0.6-1.05, B 2 O 3 /(ZrO 2 +P 2 O 5 ) The value is 0.03-3.5, (CaO+BaO)/(Na) 2 O+K 2 O) is 0.1-1.25, and the proportion of alkali metal, alkaline earth metal and network external oxide glass is adjusted to effectively inhibit boron volatilization and simultaneously introduce P 2 O 5 The glass melting temperature and forming temperature are reduced, the thermal expansion coefficient is improved, the temperature of a heating section is reduced as much as possible by adopting a multistage gradient melting process, the time of the heating section is shortened, the boron volatilization reaction amount and the reaction time are reduced, the melting section and the heat preservation section are prolonged, the influence of the increase of the glass viscosity and the increase of the melting temperature caused by composition is reduced, the glass liquid is fully melted, and the glass melting uniformity is ensured.
Compared with the traditional medical glass, the glass has the advantages that the boron content is greatly reduced, the tube drawing forming and bottle making are more stable, the product quality and the yield are improved, the thermal expansion coefficient and the melting temperature are ensured to meet the use and preparation requirements, the water resistance and the acid resistance are up to 2 levels, and the alkali resistance is up to 1 level. The multistage melting process further reduces the volatilization of boron, can ensure that the molten glass is sufficiently melted and uniformly melted, has simple operation process and low cost, and is suitable for industrial production.
Drawings
FIG. 1 shows the thermal expansion curves of medical glasses according to examples 1, 4 and 8 of the present invention;
FIG. 2 shows the high temperature viscosity curves of the medical glasses according to examples 1, 4 and 8 of the present invention.
Description of the embodiments
For a better understanding of the present invention, the following examples are further illustrated, but the present invention is not limited to the following examples.
The medical glass with low boron volatilization comprises the following components in percentage by weight: 55-70wt% SiO 2 15-20wt% of Al 2 O 3 0-7wt% of B 2 O 3 0-5wt% of Li 2 O, 1-8wt% Na 2 O, 0.5-5.5wt% K 2 O, 0.5-6wt% CaO, 0.5-6wt% BaO, 0.1-2wt% P 2 O 5 0.1-3wt% ZrO 2 0-2% NaCl, 0-2% CeO 2 0-2% NaNO 3 Wherein SiO is 2 +Al 2 O 3 Has a value of 75-85% (Na) 2 O+K 2 O+CaO+BaO)/Al 2 O 3 0.6-1.05, B 2 O 3 /(ZrO 2 +P 2 O 5 ) The value is 0.03-3.5, (CaO+BaO)/(Na) 2 O +K 2 O) is 0.1-1.25, naCl+CeO 2 +NaNO 3 The value is 0.5-2%. The prepared batch is mixed according to the components and then put into a crucible, a multi-stage gradient melting process is adopted to form clear glass liquid, the glass liquid is stirred uniformly, cooled and molded, and then the glass liquid is annealed at 550 ℃ to obtain medical glass, and the components and performances of the obtained glass samples in examples 1-14 and comparative examples 1-4 are shown in tables 1, 2 and 3.
The boron volatilization rate is calculated according to the change of the boron content before and after glass melting, and the unit is percent.
The thermal expansion coefficient of glass at 20-300 ℃ is measured by using an dilatometer and is measured according to GB/T7962.16-2010 and the unit is multiplied by 10 -6 /℃。
Glass height Wen Nianwen curve was measured using a rotary high temperature viscometer, see astm c-965, 10 of which 1 The corresponding temperature at the Pa.s viscosity is the melting temperature T m ,10 2.8 The corresponding temperature at the Pa.s viscosity is the operating temperature T w The unit is DEG C
The water resistance was measured according to YBB00252003 and was classified as 1, 2 and 3.
Acid resistance is measured according to YBB00342004 and is classified into 1, 2 and 3 grades.
Alkali resistance is measured according to YBB00352004 and is classified into 1, 2 and 3 grades.
Table 1 Components and Properties of examples 1 to 7
Table 2 examples 8 to 14 Components and Properties
Table 3 comparative examples 1 to 4 components and properties
Examples 1 to 14 and comparative examples 1 to 4, the boron volatilization rate was reduced from 10% to 8% to 5%, and it can be seen that the boron volatilization was effectively suppressed by adjusting the ratio of alkali metal, alkaline earth metal and network external oxide glass composition, while P was introduced for controlling the thermal expansion coefficient of the glass and the glass melting temperature 2 O 5 The glass viscosity is effectively reduced, and the melting temperature and the forming temperature are reduced. As is evident from the examples and comparative examples, the examples have lower boron content, resulting in lower boron volatility to 8% -5%.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention in any way; any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.

Claims (3)

1. The preparation method of the medical glass with low boron volatilization is characterized by comprising the following steps of:
s1, preparing a batch according to the following weight percentage, and taking 55-70wt% of SiO 2 15-20wt% of Al 2 O 3 0-7wt% of B 2 O 3 1-8wt% of Na 2 O, 0.5-5.5wt% K 2 O, 0.5-6wt% CaO, 0.5-6wt% BaO, 0.1-2wt% P 2 O 5 0.1-3wt% ZrO 2 0-2.5% NaCl and 0-2% CeO 2 0-2.5% NaNO 3
Wherein SiO is 2 +Al 2 O 3 The value is 75-85%,
(Na 2 O+K 2 O+CaO+BaO)/Al 2 O 3 is in the range of 0.6 to 1.05,
B 2 O 3 /(ZrO 2 +P 2 O 5 ) The value is 0.03-3.5,
(CaO+BaO)/(Na 2 O +K 2 o) is 0.1-1.25,
NaCl+CeO 2 + NaNO 3 the value is 0.5-2%;
s2, glass melting: mixing the batch materials prepared in the step S1, putting the mixture into a crucible, forming clear glass liquid by adopting a multistage gradient melting process, uniformly stirring the glass liquid, cooling and forming, and annealing at 550 ℃ to obtain medical glass;
the multistage gradient melting system is as follows: (1) heating section: the temperature is raised to 1050-1150 ℃ from room temperature, and the temperature rise time is 1.5-2.5h; (2) melting section: continuously heating to 1550-1640 ℃ for 2-3h; (3) heat preservation section: preserving heat at 1550-1640deg.C for 1-4h; (4) annealing section: transferring to 550 ℃ for annealing, and keeping the temperature for 0.5-2.5h.
2. The method for preparing the medical glass with low boron volatilization according to claim 1, which is characterized by comprising the following components in percentage by weight: 57-68wt% SiO 2 17-20wt% of Al 2 O 3 0-5wt% of B 2 O 3 0-3wt% of Li 2 O, 3-8wt% Na 2 O, 0.5-4wt% K 2 O, 0.5-4wt% CaO, 0.5-4wt% BaO, 0.1-1.5wt% P 2 O 5 ZrO 0.1-2.5wt% 2 0-2% NaCl, 0-1.5% CeO 2 0-2% NaNO 3 As a raw material, the water-soluble polymer is prepared,
wherein SiO is 2 +Al 2 O 3 75-83 percent,
(Na 2 O+K 2 O+CaO+BaO)/Al 2 O 3 is in the range of 0.65 to 1.0,
B 2 O 3 /(ZrO 2 +P 2 O 5 ) Is in the range of 0.05 to 3.25,
(CaO+BaO)/(Na 2 O +K 2 o) is 0.15-1.2,
NaCl+CeO 2 +NaNO 3 0.5-1.75%.
3. The method for preparing medical glass with low boron volatilization according to claim 1 or 2, wherein the medical glass has a thermal expansion coefficient of 4.6-5.2×10 at 20-300 DEG C -6 The water resistance and the acid resistance reach 1 level, the alkali resistance reaches 2 level, and the operation temperature T w < 1240 ℃, melting temperature T m <1710℃。
CN202311350620.3A 2023-10-18 2023-10-18 Preparation method of medical glass with low boron volatilization Pending CN117417125A (en)

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Application Number Priority Date Filing Date Title
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