CN113831013A - Neutral borosilicate glass composition, neutral borosilicate glass, and preparation method and application thereof - Google Patents
Neutral borosilicate glass composition, neutral borosilicate glass, and preparation method and application thereof Download PDFInfo
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- CN113831013A CN113831013A CN202111011243.1A CN202111011243A CN113831013A CN 113831013 A CN113831013 A CN 113831013A CN 202111011243 A CN202111011243 A CN 202111011243A CN 113831013 A CN113831013 A CN 113831013A
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- 239000005388 borosilicate glass Substances 0.000 title claims abstract description 62
- 230000007935 neutral effect Effects 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 41
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 10
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000003708 ampul Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 11
- 239000005022 packaging material Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003814 drug Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000006060 molten glass Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229930182555 Penicillin Natural products 0.000 description 2
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940049954 penicillin Drugs 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007663 fining method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012907 medicinal substance Substances 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
- A61J1/00—Containers specially adapted for medical or pharmaceutical purposes
- A61J1/05—Containers specially adapted for medical or pharmaceutical purposes for collecting, storing or administering blood, plasma or medical fluids ; Infusion or perfusion containers
- A61J1/06—Ampoules or carpules
- A61J1/065—Rigid ampoules, e.g. glass ampoules
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
Abstract
The invention relates to the field of medical glass packaging materials, and discloses a neutral borosilicate glass composition, a neutral borosilicate glass, a preparation method and an application thereof, wherein the neutral borosilicate glass composition contains the following components which are respectively independently stored or are mixed and stored: SiO 22、Al2O3、B2O3、Na2O、K2O、Li2O、CeO2Chloride, ZrO2MgO, CaO, the neutral borosilicate glass prepared from the neutral borosilicate glass composition of the invention not only has high chemical stability and excellent hydrolytic resistance, but also has low crystallization tendency and lower melting and softening temperaturesEasy processing and good processing performance.
Description
Technical Field
The invention relates to the field of medical glass packaging materials, in particular to a neutral borosilicate glass composition, neutral borosilicate glass, and a preparation method and application thereof.
Background
In the medical field, glass is widely used as a packaging material, and the special material properties, such as high transparency, mechanical resistance, low permeability, high chemical stability and the like, are critical to maintaining the quality of the medicinal substance and even the efficacy thereof.
In particular, borosilicate glass for medical containers such as vial and ampoule is required to have the following properties:
(1) the components in the filled liquid medicine do not react with the components in the glass;
(2) chemical durability and hydrolysis resistance are high, and the filled liquid medicine is prevented from being polluted;
(3) a low thermal expansion coefficient, so that the glass tube is not easily damaged by thermal shock in the manufacturing process of the glass tube or the processing of penicillin, an ampoule and the like; the operation temperature is low, so that penicillin bottles, ampoules and the like can be processed at low temperature.
The glass pharmaceutical containers or primary packages are usually in direct contact with the contained pharmaceutical substance and therefore comply with strict requirements. They are intended to be able to remove the contents in a suitable manner, while minimizing losses and changes, preferably without physical or chemical changes, of the contents. The quality of the contents should not change due to direct contact with the container or primary package so as to exceed the required limit values. In any case, it is ensured that the glass material does not release a certain amount of substance which could affect the stability of the pharmaceutical substance or even be toxic to the user.
In the case of aqueous pharmaceutical substances, the most important property of a glass package is the stability of its inner surface, which comes into contact with and is attacked by the aqueous pharmaceutical substance. Thereby potentially dissolving and releasing various ions from the glass surface. For example, a change in the pH of the aqueous medium, which may be due to alkali metal ions or alkaline earth metal ions, may reduce the efficacy of the pharmaceutical substance.
Furthermore, there is concern about aluminium in the glass composition, for example in humans with specific genetic characteristics, excessive aluminium uptake in the metabolic system may lead to health damage. To avoid health risks, the glass should generally be dissolved to release as few ions as possible.
The medical glass packaging material produced in China at present mainly comprises soda-lime-silica glass and low borosilicate glass, only a small amount of neutral borosilicate glass exists, the performance stability and the water resistance of the medical glass packaging material are different from those of similar foreign products, the manufacturing and melting difficulty of the neutral borosilicate glass is high, the defects of stones, gas lines and the like easily occur in the glass tube forming process, the qualification rate of finished products is low, and the medical glass packaging material cannot be used.
Disclosure of Invention
The invention aims to overcome the defects of poor hydrolysis resistance, chemical stability and processability of neutral borosilicate glass in the prior art.
In order to achieve the above object, a first aspect of the present invention provides a neutral borosilicate glass composition containing two or more kinds of boron compounds each independently or in combinationThe following components were present: SiO 22、Al2O3、B2O3、Na2O、K2O、Li2O、CeO2Chloride, ZrO2、MgO、CaO；
The SiO is based on the total mass of the glass composition2In an amount of 69 to 77 wt%, the Al2O3In an amount of 4-7 wt%, said B2O3Is 8-12 wt% of the Na2The content of O is 5-10 wt%, and K is2O content of 0.5 to 3 wt%, and Li2O content of 0-1.5 wt%, the CeO2Is 0.05 to 2 wt%, the chloride is 0 to 0.5 wt%, and the ZrO is2Is 0 to 0.5 wt%, the sum of the contents of MgO and CaO is 0 to 1.5 wt%, and Na is2O, said K2O and the Li2The sum of the contents of O, SiO and the like is 7-12wt percent2The Al2O3And said B2O3The sum of the contents of the three components is 85-93 wt%.
Preferably, the SiO is based on the total mass of the glass composition2Is 70-76 wt%, the Al2O3In an amount of 5-6 wt%, said B2O3Is 10 to 12 wt%, the Na2The content of O is 6-8 wt%, and K is2The content of O is 1 to 3 wt%, and the Li2The content of O is 0-1 wt%, and the CeO2Is 0.1 to 1 wt%, the chloride is 0 to 0.2 wt%, and the ZrO is2Is 0 to 0.5 wt%, the sum of the contents of MgO and CaO is 0 to 1 wt%, and the Na is2O, said K2O and the Li2The sum of the contents of O and SiO is 7-11.5wt percent2The Al2O3And said B2O3The sum of the contents of the three components is 85-93 wt%.
Preferably, the neutral borosilicate glass composition further contains Fe2O3And the Fe is based on the total mass of the neutral borosilicate glass composition2O3Is 0.001 to 0.06 wt.%, more preferably 0.001 to 0.04 wt.%.
Preferably, the chloride is selected from at least one of sodium chloride and magnesium chloride.
In a second aspect, the present invention provides a method of making a neutral borosilicate glass, the method comprising: the components of the neutral borosilicate glass composition of the first aspect are sequentially mixed, melted, clarified, formed, and annealed.
Preferably, the mixing conditions include at least: the stirring speed is 10-20rpm, the temperature is 1450-1500 ℃, and the time is 20-30 min.
Preferably, the melting conditions include at least: the temperature is 1500-1650 ℃, and the time is 300-480 min.
Preferably, the clarifying conditions comprise at least: the temperature is 1580-1630 ℃, and the time is 30-60 min.
Preferably, the molding conditions include at least: the temperature is 1250-1280 ℃.
Preferably, the annealing conditions at least include: the temperature is 560-595 ℃, and the time is 10-20 min.
In a third aspect, the invention provides a neutral borosilicate glass prepared by the method of the second aspect.
Preferably, the ion elution amount of the neutral borosilicate glass is 1.0ppm or less.
Preferably, the neutral borosilicate glass has a liquid phase viscosity of greater than 104.5dpa·s。
Preferably, the linear thermal expansion coefficient of the neutral borosilicate glass is less than 58 x 10 in the temperature range of 30-380 DEG C-7/. degree.C., more preferably 48X 10-7/℃-55×10-7/℃。
In a fourth aspect, the invention provides a use of the neutral borosilicate glass of the third aspect in the preparation of a medical container.
Preferably, the medical container is selected from at least one of a vial and an ampoule.
The neutral borosilicate glass prepared from the neutral borosilicate glass composition has high chemical stability and excellent hydrolysis resistance, also has low crystallization tendency and lower melting and softening temperatures, is easy to process, has good processability, is suitable for industrial production, and has excellent hydrolysis resistance and high chemical resistance when being applied to preparation of medical containers, and does not release or only rarely releases ions when being contacted with aqueous or water-containing medicinal substances.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a neutral borosilicate glass composition containing the following components stored independently of each other or in a mixture of two or more of them: SiO 22、Al2O3、B2O3、Na2O、K2O、Li2O、CeO2Chloride, ZrO2、MgO、CaO；
The SiO is based on the total mass of the glass composition2In an amount of 69 to 77 wt%, the Al2O3In an amount of 4-7 wt%, said B2O3Is 8-12 wt% of the Na2The content of O is 5-10 wt%, and K is2O content of 0.5 to 3 wt%, and Li2O content of 0-1.5 wt%, the CeO2Is 0.05 to 2 wt%, the chloride is 0 to 0.5 wt%, and the ZrO is2Is 0 to 0.5 wt%, the sum of the contents of MgO and CaO is 0 to 1.5 wt%,
the Na is2O, said K2O and the Li2The sum of the contents of O, SiO and the like is 7-12wt percent2The Al2O3And said B2O3Three componentsThe sum of the contents of (A) and (B) is 85-93 wt%.
Preferably, the SiO is based on the total mass of the glass composition2Is 70-76 wt%, the Al2O3In an amount of 5-6 wt%, said B2O3Is 10 to 12 wt%, the Na2The content of O is 6-8 wt%, and K is2The content of O is 1 to 3 wt%, and the Li2The content of O is 0-1 wt%, and the CeO2Is 0.1 to 1 wt%, the chloride is 0 to 0.2 wt%, and the ZrO is2Is 0 to 0.5 wt%, the sum of the contents of MgO and CaO is 0 to 1 wt%, and the Na is2O, said K2O and the Li2The sum of the contents of O and SiO is 7-11.5wt percent2The Al2O3And said B2O3The sum of the contents of the three components is 85-93 wt%.
Preferably, the neutral borosilicate glass composition further contains Fe2O3And the Fe is based on the total mass of the neutral borosilicate glass composition2O3The content of (B) is 0.001-0.06 wt%, more preferably 0.001-0.04 wt%.
In the present invention, the Fe is2O3Is introduced in the form of impurities.
Preferably, the chloride is selected from at least one of sodium chloride and magnesium chloride.
As previously mentioned, a second aspect of the present invention provides a method of making a neutral borosilicate glass, the method comprising: the components of the neutral borosilicate glass composition of the first aspect are sequentially mixed, melted, clarified, formed, and annealed.
In the present invention, there is no particular limitation on the specific operations of mixing, melting, clarifying, forming and annealing, and known operations in the art may be used, and the specific operations exemplified hereinafter in the present invention should not be construed as limiting the present invention by those skilled in the art.
Preferably, the shaping method is selected from danner method and vero method.
Preferably, the fining method is to adjust the temperature of the molten glass obtained by melting to a viscosity of 102.5Pa.s-102.6And Pa.s, discharging bubbles in the molten glass.
Preferably, the mixing conditions include at least: the stirring speed is 10-20rpm, the temperature is 1450-1500 ℃, and the time is 20-30 min.
Preferably, the melting conditions include at least: the temperature is 1500-1650 ℃, and the time is 300-480 min.
Preferably, the clarifying conditions comprise at least: the temperature is 1580-1630 ℃, and the time is 30-60 min.
Preferably, the molding conditions include at least: the temperature is 1250-1280 ℃.
Preferably, the annealing conditions at least include: the temperature is 560-595 ℃, and the time is 10-20 min.
In a third aspect, the invention provides a neutral borosilicate glass prepared by the method of the second aspect.
Preferably, the ion elution amount of the neutral borosilicate glass is 1.0ppm or less.
Preferably, the neutral borosilicate glass has a liquid phase viscosity of greater than 104.5dpa·s。
Preferably, the linear thermal expansion coefficient of the neutral borosilicate glass is less than 58 x 10 in the temperature range of 30-380 DEG C-7/. degree.C., more preferably 48X 10-7/℃-55×10-7/℃。
According to a particularly preferred embodiment, the neutral borosilicate glass is present in the form of a neutral borosilicate glass tube.
In a fourth aspect, the invention provides a use of the neutral borosilicate glass of the third aspect in the preparation of a medical container.
Preferably, the medical container is selected from at least one of a vial and an ampoule.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
Example 1
This example illustrates the preparation of a neutral borosilicate glass composition according to the present invention according to the formulation and process parameters set forth in table 1, and as described below.
The method for preparing the neutral borosilicate glass comprises the following steps:
the components of the glass composition shown in table 1 were weighed and mixed uniformly to obtain a mixture, the mixture was put into a 1550 ℃ melting furnace to be melted for 350 minutes to obtain a molten glass, the molten glass was clarified to 1580 ℃ and bubbles were discharged to obtain a molten glass, the obtained molten glass was formed by the danna method, the formed glass was cut into a predetermined length (1500mm), and annealing was carried out at 560 ℃ for 15 minutes to obtain a glass sample.
The remaining examples and comparative examples were carried out using the same procedure as in example 1, except that the composition of the neutral borosilicate glass composition and the process parameters for preparing the neutral borosilicate glass were different, unless otherwise specified, see in table 1.
TABLE 1
TABLE 1 (continuation)
TABLE 1 (continuation)
Test example
The performance of each of the neutral borosilicate glass samples prepared in the examples and comparative examples was tested, and the specific test results are shown in table 2.
Density: the measurement was carried out by the Archimedes method.
Coefficient of linear thermal expansion: the measurements were carried out on glass samples, which were rod-shaped glasses having dimensions of phi 5mm x 50mm, using an dilatometer at a temperature range of 20-380 ℃.
Strain point PsAnnealing point TaAnd a softening point Ts: the measurement was carried out by a glass fiber elongation method.
Operating temperature Tw: the viscosity was 10 according to the calculation formula for the viscosity of Fulecher4Temperature at dPa · s.
Hydrolysis resistance: the glass samples were crushed using alumina-made mortars and pestles, following the method of the powder test method carried out on YBB2015 version.
Acid resistance: the surface area of the glass sample was set to 50cm2The amount of 6mol/L hydrochloric acid as a dissolution liquid was set to 800ml and carried out in accordance with DIN 2116.
Quality of the foam: a sample having a length of 2cm, a width of 2cm and a thickness of 3mm was cut out from the center of the glass sample, both surfaces were polished, and 1cm was observed with a microscope2Wherein the number of bubbles having a size of 100 μm or more is 1 or less, and the number exceeding 1 is determined as X.
Transmittance: a sample having a length of 3cm, a width of 2cm and a thickness of 1mm was cut out from the center of the glass sample, and both sides were polished, and then the transmittance at 800nm was measured using a spectrophotometer. When the transmittance at 400nm is 90% or more, the determination is that the transmittance is less than 90%, and the determination is X.
Liquid phase temperature: a platinum boat of about 120 x 20 x 10mm was filled with the crushed glass sample and charged into an electric furnace with a linear temperature gradient for 24 hours. Thereafter, the crystal deposition site was identified by microscopic observation, and the temperature corresponding to the crystal deposition site was calculated from the temperature gradient map of the electric furnace, and this temperature was defined as the liquid phase temperature.
Liquid phase viscosity: the viscosity of the liquid phase of the glass was measured by means of an orthoton RSV-1600 high temperature rotational viscometer, i.e., the product of the measurement value of the rotational viscometer and a specific coefficient on the rotational viscometer coefficient table.
Ion elution amount: and (3) detecting by using an ICP (inductively coupled plasma) luminescence analysis device, wherein N.D. represents that the detection limit is lower than that of the ICP luminescence analysis device.
Water resistance: the measurement was carried out in accordance with the method of measuring the water resistance of YBB00362004-2015 glass particles at 98 ℃ and the method of measuring the water resistance of YBB00252003-2015 glass particles at 121 ℃.
Alkali resistance: the measurement was carried out in accordance with "method for measuring the erosiveness of glass to boiling mixed alkali aqueous solution" YBB 00352004-2015.
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Density (g/cm)3) | 2.332 | 2.335 | 2.336 | 2.336 | 2.336 |
| Coefficient of linear thermal expansion (× 10)-7/℃) | 53 | 50 | 51 | 52 | 52 |
| Ps(℃) | 510 | 514 | 513 | 515 | 514 |
| Ta(℃) | 562 | 565 | 562 | 565 | 555 |
| Ts(℃) | 770 | 775 | 776 | 774 | 775 |
| Tw(℃) | 1175 | 1170 | 1178 | 1175 | 1170 |
| Liquid phase viscosity Log (dPa. s) | 5.1 | 4.8 | 5.5 | 5.4 | 5.1 |
| Liquid phase temperature (. degree. C.) | 1105 | 1100 | 1102 | 1103 | 1100 |
| Resistance to hydrolysis (ml) | 0.025 | 0.025 | 0.025 | 0.023 | 0.024 |
| Water resistance at 98 ℃ | HGB grade 1 | HGB grade 1 | HGB grade 1 | HGB grade 1 | HGB grade 1 |
| Water resistance at 121 DEG C | Level 1 | Level 1 | Level 1 | Level 1 | Level 1 |
| Alkali resistance | Stage 2 | Stage 2 | Stage 2 | Stage 2 | Stage 2 |
| Acid resistance (mg/dm2) | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Amount of ion elution (ppm) | N.D. | N.D. | N.D. | N.D. | N.D. |
| Quality of the foam | |||||
| Transmittance of light |
Table 2 (continuation)
| Example 6 | Example 7 | Example 8 | |
| Density (g/cm)3) | 2.334 | 2.334 | 2.335 |
| Coefficient of linear thermal expansion (× 10)-7/℃) | 54 | 50 | 54.5 |
| Ps(℃) | 510 | 515 | 508 |
| Ta(℃) | 560 | 566 | 559 |
| Ts(℃) | 768 | 776 | 767 |
| Tw(℃) | 1173 | 1173 | 1172 |
| Liquid phase viscosity Log (dPa. s) | 5.1 | 4.9 | 5.0 |
| Liquid phase temperature (. degree. C.) | 1096 | 1095 | 1098 |
| Resistance to hydrolysis (ml) | 0.026 | 0.025 | 0.026 |
| Water resistance at 98 ℃ | HGB grade 1 | HGB grade 1 | HGB grade 1 |
| Water resistance at 121 DEG C | Level 1 | Level 1 | Level 1 |
| Alkali resistance | Stage 2 | Stage 2 | Stage 2 |
| Acid resistance (mg/dm)2) | 0.5 | 0.5 | 0.5 |
| Amount of ion elution (ppm) | N.D. | N.D. | N.D. |
| Quality of the foam | |||
| Transmittance of light |
Table 2 (continuation)
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Density (g/cm)3) | 2.339 | 2.336 | 2.336 | 2.336 | 2.336 |
| Coefficient of linear thermal expansion (× 10)-7/℃) | 54 | 53 | 58 | 53 | 54 |
| Ps(℃) | 535 | 552 | 552 | 553 | 552 |
| Ta(℃) | 572 | 592 | 592 | 593 | 592 |
| Ts(℃) | 785 | 802 | 802 | 798 | 802 |
| Tw(℃) | 1198 | 1208 | 1208 | 1188 | 1208 |
| Liquid phase viscosity Log (dPa. s) | 5.6 | 5.8 | 5.4 | 5.6 | 5.6 |
| Liquid phase temperature (. degree. C.) | 1128 | 1135 | 1134 | 1123 | 1133 |
| Resistance to hydrolysis (ml) | 0.032 | 0.030 | 0.042 | 0.032 | 0.045 |
| Water resistance at 98 ℃ | HGB grade 1 | HGB grade 1 | HGB grade 1 | HGB grade 1 | HGB grade 1 |
| Water resistance at 121 DEG C | Stage 2 | Level 1 | Level 1 | Stage 2 | Level 1 |
| Alkali resistance | Stage 2 | Stage 2 | Stage 2 | Stage 2 | Stage 2 |
| Acid resistance (mg/dm)2) | 0.5 | 0.5 | 0.5 | 0.6 | 0.5 |
| Amount of ion elution (ppm) | N.D. | N.D. | N.D. | N.D. | N.D. |
| Quality of the foam | × | × | |||
| Transmittance of light | × |
As can be seen from the results in Table 2, the operating temperature T of the neutral borosilicate glass produced according to the present inventionW(viscosity: 10)4dPa.S) of not higher than 1180 deg.C, reduced difficulty in melting, softening point of less than 780 deg.C, annealing point of less than 565 deg.C, strain point of more than 515 deg.C, and thermal expansion coefficient (20-300 deg.C) of glass of 50 × 10-7/℃-53×10-7Between/° c; the product is transparent and bright, and the glass density is less than 2.4g/cm3And meets the requirements of light weight and environmental protection of medicine packaging. In addition, the water resistance of the glass reaches HGB1 grade, and the alkali resistance reaches 2 grade. Thus, it is demonstrated that neutral borosilicate glass prepared from the glass composition of the present invention has good hydrolysis resistance, chemical durability, bubble quality and transmittance, and excellent processability.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A neutral borosilicate glass composition characterized by containing the following components stored independently of each other or in a mixture of two or more of them: SiO 22、Al2O3、B2O3、Na2O、K2O、Li2O、CeO2Chloride, ZrO2、MgO、CaO；
The SiO is based on the total mass of the glass composition2In an amount of 69 to 77 wt%, the Al2O3In an amount of 4-7 wt%, said B2O3Is 8-12 wt% of the Na2The content of O is 5-10 wt%, and K is2O content of 0.5 to 3 wt%, and Li2O content of 0-1.5 wt%, the CeO2Is 0.05 to 2 wt%, the chloride is 0 to 0.5 wt%, and the ZrO is2Is 0 to 0.5 wt%, the sum of the contents of MgO and CaO is 0 to 1.5 wt%,
the Na is2O, said K2O and the Li2The sum of the contents of O, SiO and the like is 7-12wt percent2The Al2O3And said B2O3The sum of the contents of the three components is 85-93 wt%.
2. The neutral borosilicate glass composition according to claim 1, wherein the SiO is present in the glass composition based on the total mass of the glass composition2Is 70-76 wt%, the Al2O3In an amount of 5-6 wt%, said B2O3Is 10 to 12 wt%, the Na2The content of O is 6-8 wt%, and K is2The content of O is 1 to 3 wt%, and the Li2The content of O is 0-1 wt%, and the CeO2Is 0.1 to 1 wt%, the chloride is 0 to 0.2 wt%, and the ZrO is2Is 0 to 0.5 wt%, the sum of the contents of MgO and CaO is 0 to 1 wt%, and the Na is2O, theK2O and the Li2The sum of the contents of O and SiO is 7-11.5wt percent2The Al2O3And said B2O3The sum of the contents of the three components is 85-93 wt%.
3. The neutral borosilicate glass composition according to claim 1 or 2, wherein the neutral borosilicate glass composition further comprises Fe2O3And the Fe is based on the total mass of the neutral borosilicate glass composition2O3The content of (B) is 0.001-0.06 wt%, preferably 0.001-0.04 wt%.
4. The neutral borosilicate glass composition according to any one of claims 1 to 3, wherein the chloride is selected from at least one of sodium chloride and magnesium chloride.
5. A method of making a neutral borosilicate glass, the method comprising: the neutral borosilicate glass composition according to any of claims 1 to 4, wherein the components are mixed, melted, clarified, shaped, and annealed in that order.
6. The method according to claim 5, characterized in that the conditions of mixing comprise at least: the stirring speed is 10-20rpm, the temperature is 1450-;
preferably, the conditions of the melting comprise at least: the temperature is 1500-;
preferably, the clarifying conditions comprise at least: the temperature is 1580-;
preferably, the molding conditions include at least: the temperature is 1250-1280 ℃;
preferably, the annealing conditions include at least: the temperature is 560-595 ℃, and the time is 10-20 min.
7. Neutral borosilicate glass produced by the method of claim 5 or 6.
8. The neutral borosilicate glass according to claim 7, wherein an ion elution amount of the neutral borosilicate glass is 1.0ppm or less;
preferably, the neutral borosilicate glass has a liquid phase viscosity of greater than 104.5dpa·s。
9. The neutral borosilicate glass according to claim 7 or 8, wherein the linear thermal expansion coefficient of the neutral borosilicate glass is less than 58 x 10 in the temperature range of 30 to 380 ℃-7/. degree.C., preferably 48X 10-7/℃-55×10-7/℃。
10. Use of the neutral borosilicate glass according to any one of claims 7 to 9 for the production of medical containers;
preferably, the medical container is selected from at least one of a vial and an ampoule.
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| CN115093116A (en) * | 2022-07-07 | 2022-09-23 | 湖南洪康新材料科技有限公司 | Neutral medicinal borosilicate glass and preparation method thereof |
| CN115180824A (en) * | 2022-07-05 | 2022-10-14 | 河北光兴半导体技术有限公司 | Fireproof glass composition, fireproof glass and preparation method thereof |
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