GB2136413A - Soda-alumina-borosilicate glass - Google Patents
Soda-alumina-borosilicate glass Download PDFInfo
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- GB2136413A GB2136413A GB08306858A GB8306858A GB2136413A GB 2136413 A GB2136413 A GB 2136413A GB 08306858 A GB08306858 A GB 08306858A GB 8306858 A GB8306858 A GB 8306858A GB 2136413 A GB2136413 A GB 2136413A
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- liquidus
- glass
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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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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
There is disclosed a barium-free Type I, Class B laboratory glass according to the standard specification set forth in ASTM E-80a having a linear coefficient of expansion (0 to 300 DEG C, cm/cm- DEG Cx10-<7>) of about 48 to 56 and having a chemical durability, maximum titration equivalent of: 0.02N H2SO4/10g of glass of 1.0 ml, the composition consisting essentially of the following ingredients in approximate percent by weight: <IMAGE> the glass composition having an annealing point of about 550 DEG C to 585 DEG C, a liquidus of about 1730 DEG F to 1760 DEG F and a Log n at the liquidus about 5.0 to 5.5.
Description
SPECIFICATION
Soda-alumina-borosilicate glass
The present invention relates to Type I, Class B laboratory glasses as set forth in the standard specification in ASTM E 438-80a and particularly relates to barium-free soda-alumina-borosilicate laboratory glasses especially useful for pharmaceutical glass containers including ampuls, vials and syringes.
As set forth in ASTM E 438--80a (Standard Specification for Glasses in Laboratory Apparatus),
Type I, Class B alumino-borosilicate laboratory glasses have the following chemical and physical requirements:
Chemical Requirements
Major Constituents, Approx. Weight Percent
SiO2 73
B203 10
Al203 7
BaO 2
CaO 1
Na2O 6 K20 Trace Constituents, Max.
As202 plus Sb203 0.1
PbO 0.1
MgO 0.3
ZnO 0.1
Ail other constituents, max. 1.0
Physical Requirements
Weight Percent
Linear coefficient of expansion, Oto3OO0Ccm/cm-0C x 10-7 48to 56+2 Annealing point, OC 574 + 10
Softening point, OC 783 to 799 + 10
Density, annealed, g/cm3 2.36 + 0.02
Chemical durability, titration
equivelant of: 0.02N H2SOg/10g of glass, max. ml 1.0
It is desirable to have a laboratory glass for pharmaceutical containers made from a soda-alumina borosiiicate glass composition that can be melted and fabricated into containers such as ampuls or vials with speed suitable for economical production.According to ASTM E 438--80a, a particular composition provides such a glass with an outstanding balance of chemical and physical properties
including high chemical durability and a relatively low thermal coefficient of expansion.
However, during storage of the pharmaceutical containers, it is believed that barium from BaO in the glass may leach out very slowly in very small amounts and may react with minute quantities of sulfate or phosphate ions in the drug product to form precipitates which destroy the integrity of the product.
The barium-free glass composition of the present invention may meet the relatively strict requirements of ASTM E 438--80a and may be capable of being melted and fabricated economically by known tube drawing processes such as the Danner or downdraw processes.
According to one aspect of the present invention there is provided a barium-free Type I, Class B laboratory glass according to the standard specification set forth in ASTM E 438--80a having a linear coefficient of expansion (0 to 3000C, cm/cm -- OC x 10-7) of about 48 to 56 and having a chemical durability, maximum titration equivalent of: 0.02N H2SO4/10 g of glass of 1.0 ml, the composition consisting essentially of the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 70-74 B203 9-13 Al203 5-8 Na2O 5-8
K20 0-4 CaO 0--3 MgO 0--1 the glass composition having an annealing point of about 5500C to 5850C, a liquidus of about 1 730C to 1 7600F and preferably a Log n at the liquidus about 5.0 to 5.5.
According to another aspect of the present invention there is provided a barium free sodaalumina-borosilicate glass having a composition comprising the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 70-74 B2Os 9-13 Al203 5-8 Na2O 5-8
K20 0-4 CaO 0--3 MgO 0--1 the glass composition having an annealing point of about 5500C to 5850C, a liquidus of about 1 7300F to 1 7600F and a Log n at the liquidus about 5.0 to 5.5.
The present invention provides a preferred barium-free Type I, Class B (ASTM E 438-80a) glass
composition, the composition having the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 71-73 B203 10-12
Al203 6-7
Na2O 6-7
K2O 1-3
CaO 0.2-2 MgO 0.1-0.3 According to a highly preferred embodiment of the invention there is provided a barium-free glass composition that meets the requirements of ASTM E 438-80a and yet can be economically processed into pharmaceutical containers, the composition having the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 71.8
B203 11.5
Al2O3 6.8
Na2O 6.4
K2O 2.7
CaO 0.5
MgO 0.2
the glass composition having the following properties::
Property Approximate Units
Working Point (etc) 1135
Softening Point (OC) 782
Annealing Point (OC) 560
Strain Point (OC) 516
Expansion Coefficient (x 10-7) 54
Density (g/cc) 2.335
Chemical Durability (ml) 0.34
Viscosity, log 5 (OF) 1815
Viscosity, log 3 (OF) 2470
Liquidus (OF) 1740
Log n at Liquidus 5.4
The present invention also provides another highly preferred glass composition, although for some
purposes such as high chemical durability and high-speed production, not as outstanding as the preceding composition.This barium-free glass composition has the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 70.6 B203 11.7 At203 6.6
Na2O 6.1
K2O 2.5
CaO 2.2
MgO 0.2 the glass composition having the following properties:
Property Approximate Units
Working Point (Ct) 1118
Softening Point (OC) 779
Annealing Point (OC) 574
Strain Point (OC) 532
Expansion Coefficient (x 10-7) 55
Density (g/cc) 2.348
Chemical Durability (ml) 0.49
Viscosity, log 5 (OF) 1795
Viscosity, log 3 (OF) 2435
Liquidus (CF) 1760
Log n at Liquidus 5.2
The following example illustrates the present invention and is not intended to be limiting in any way.
EXAMPLE
Two barium-free ASTM E 438--80a soda-alumina-borosiiicate glass compositions were made from glass raw batch materials consisting of sand, borax, boric acid, burnt dolomite lime, feldspar, potassium nitrage and sodium chloride, by methods well known in the art.The raw batches were melted and fired as known in the art to produce glasses A and B with the following chemical compositions in approximate percentages by weight and with the following chemical and physical properties as set forth in Table
TABLE I
CHEMICAL AND PHYSICAL PROPERTIES
A B
ASTM E 438-80a Measured Calculated Measured Calculated Standard Glass
Chemical Composition (%)
Silica (SiO2) 71.93 71.80 70.35 70.60 70.6
Boric Oxide (B203) 11.62 11.55 12.00 11.70 11.2
Alumina (Al203) 6.69 6.75 6.40 6.60 6.6
Barium Oxide (BaO) None None None None 2.2
Calcium Oxide (CaO) 0.43 0.50 2.30 2.20 0.5
Magnesium Oxide (MgO) 0.21 0.20 0.01 0.20 0.2
Sodium Oxide (Na2O) 6.61 6.40 6.35 6.10 6.1
Potassium Oxide (K2O) 2.49 2.70 2.29 2.50 2.5 Chloride (Cl-) 0.17 0.10 0.22 0.10 0.1
O - Cl 0.04 0.05
Total 100.11 99.87
TABLE I (continued)
CHEMICAL AND PHYSICAL PROPERTIES
A B
ASTM E 438-80a Measured Calculated Measured Calculated Standard Glass
Physical Properties
Working Point (OC) 1135 1135 1118 1124 1130
Softening Point (CC) 782 788 779 788 785
Annealing Point (OC) 560 574 575
Strain Point (OC) 516 532 530
Expansion Coefficient, O-3000C(x 10-7) 54.3 54.7 55.2 55.5 55
Contraction Coefficient, A.P.-250C(x 10-7) 68.1 71.2 73
Density (g/cc) 2.3335 2.3476 2.374
Refractive Index (n,) 1.4904 1.4948 1.495
TABLE I (continued)
CHEMICAL AND PHYSICAL PROPERTIES
A B
ASTM E 438-80a Measured Calculated Measured Calculated Standard Glass
Physical Properties (Cont.) Chemical Durability,
USP XX (ml 0.02N acid) 0.34 0.49 0.36
Cooling Time (sec.) 79 79 78 77 79
Viscosity (OF): Log n = 7.6 1440 1435 1445
7.0 1505 1505 1495 1500 1500
6.0 1635 1640 1625 1635 1635
5.0 1815 1825 1795 1810 1815
4.0 2075 2075 2045 2055 2070
3.0 2470 2470 2435 2430 2460
2.5 2765 2725 2740
2.0 3165 3145 3125 3085 3120 Liquidus(CF) 1741 1758 1754
Log n at Liquidus 5.41 5.22 5.35
Primary Phase Tridymite Tridymite Tridymite
The barium-free compositions A and B of the present invention are compared to an ASTM E 438-80a standard glass (made according to that standard specification with BaO).Compositions A and B compared closely with the standard composition in physical properties such as liquidus, chemical durability, annealing point, brilliance, workabilite and flake proneness. The agreement of the properties of composition A and the standard glass in the important properties of viscosity, expansion coefficient and chemical durability is especially close.
The glasses were fabricated into pharmaceutical containers, the forming characteristics, surface durability, lack of proneness to flaking, the lack of blooming, and the ampul break force characteristics being satisfactory.
Yet, glass compositions A and B contained no barium oxide. Surprisingly, the requirement of economical fabrication into glass containers and the strict requirements of ASTM E 438-80a were satisfied.
In the Hagedorn U.S. Patent No. 3,054,686, there is disclosed modified borosilicate glasses suitable for the manufacture of small containers for packaging pharmaceutical and drug products. The
Hagedorn patent sets forth the following theoretical glass composition in percent by weight.
Ingredient Percent
SiO2 67-71 Al2O3 2.5-6.0 B203 2.0-5.0
CaO + MgO 6.0-10.0 BaO 0--2.0 Na20 10.5-14.5 K20 0.1-2.0
Li2O 0-1.0 Cl 0--0.2 SO3 0-0.2 In the above Hagedorn formulation, the amounts of CaO + MgO and the amount of Na2O are too
high to provide the outstanding glass compositions of the present invention. The outstanding
combination of properties obtained by the glass composition of the present invention (that meet the
ASTM E 438--80a specification) is not disclosed in the Hagedorn U.S. Patent No. 3,054,686 glasses.
As previously stated, the thermal expansion coefficient is an important property. It is critical in meeting the ASTM E 438--80a specification. The thermal expansion coefficient of the Hagedorn glasses is much higher than the coefficient of the glasses of the present invention, being in the range of 71 85.
Also in another important property, the chemical durability of the Hagedorn glasses, being in the range of 1.7-5.0 ml, is not as good as the glasses of the present invention and does not meet the Type
I requirements of ASTM E 438-80a.
Claims (7)
1. A barium-free Type I, Class B glass according to the standard specification set forth in ASTM E 438-80a having a linear coefficient of expansion (0 to 300 C, cm/cm 0 C x 10-7) of about 48 to 56 and having a chemical durability, maximum titration equivalent of: 0.02N H2SO1 0 g of glass of 1.0 ml, the composition comprising the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 70--74
B203 9-13 Al203 5-8
Na20 5-8
K20 0-4 CaO 0--3
MgO 0--1 the glass composition having an annealing point of about 550 c to 585 C, a liquidus of about 1 730CF to 1 760CF and a Log n at the liquidus about 5.0 to 5.5.
2. A glass composition as claimed in claim 1, having the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 71-73 B203 10-12
Al2O3 6-7 Na2O 6-7
K20 1-
3
CaO 0.2-2 MgO 0.1-0.3 3.A glass composition as claimed in claim 1, having the following ingredients in approximate percent by weight:
Ingredient Percent
SiO2 71.8
B203 11.5 Al2O3 6.8
Na20 6.
4
K20 2.7
CaO 0.
5
MgO 0.2
the glass composition having the following properties:
Property Approximate Units
Working Point ( C) 1135
Softening Point ( C) 782
Annealing Point ( C) 560
Strain Point ( C) 516
Expansion Coefficient (x 10-7) 54
Density (g/cc) 2.335
Chemical Durability (ml) 0.34
Viscosity, log5 (CF) 1815
Viscosity, log 3 (CF) 2470
Liquidus (CF) 1740
Log n at Liquidus 5.4
4.A glass composition as claimed in claim 1, having the following ingredients in approximate
percent by weight:
Ingredient Percent
SiO2 70.6 B203 i 1.2 Al2O3 6.6 Na2O 6.1
K20 2.5
CaO 2.7
MgO 0.2 the glass composition having the following properties:
Property Approximate Units
Working Point ( C) 1118
Softening Point ( C) 779
Annealing Point ( C) 574
Strain Point ( C) 532
Expansion Coefficient (x 10-7) 55
Density (g/cc) 2.348
Chemical Durability (ml) 0.49
Viscosity, log 5 ( F) 1795
Viscosity, log 3 ( F) 2435
Liquidus ( F) 1760
Log n at Liquidus 5.2
5. A barium-free soda-alumina-borosilicate glass having a composition comprising the following
ingredients in approximate percent by weight:
Ingredient Percent
SiO2 70-74 B203 9-13 Al2O3 5-8 Na2O 5-8
K20 0-4 CaO 0--3
MgO 0--1 the glass composition having an annealing point of about 550 C to 585 CC, a liquidus of about 1 730CF to 1 760CF and a Log n at the liquidus about 5.0 to 5.5.
6. A glass composition substantially as hereinbefore described in the foregoing Example.
7. A container whenever made from a glass composition as claimed in any one of the preceding claims.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08306858A GB2136413B (en) | 1983-03-12 | 1983-03-12 | Soda-alumina-borosilicate glass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08306858A GB2136413B (en) | 1983-03-12 | 1983-03-12 | Soda-alumina-borosilicate glass |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8306858D0 GB8306858D0 (en) | 1983-04-20 |
| GB2136413A true GB2136413A (en) | 1984-09-19 |
| GB2136413B GB2136413B (en) | 1986-11-12 |
Family
ID=10539456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08306858A Expired GB2136413B (en) | 1983-03-12 | 1983-03-12 | Soda-alumina-borosilicate glass |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2136413B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314704A1 (en) * | 2001-10-16 | 2003-05-28 | Schott Glas | Thermally temperable alkali-boro-silica glass, its production and its use |
-
1983
- 1983-03-12 GB GB08306858A patent/GB2136413B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1314704A1 (en) * | 2001-10-16 | 2003-05-28 | Schott Glas | Thermally temperable alkali-boro-silica glass, its production and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2136413B (en) | 1986-11-12 |
| GB8306858D0 (en) | 1983-04-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19990312 |