USRE29388E - Glass compositions and fibers made therefrom - Google Patents
Glass compositions and fibers made therefrom Download PDFInfo
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- USRE29388E USRE29388E US05/759,237 US75923777A USRE29388E US RE29388 E USRE29388 E US RE29388E US 75923777 A US75923777 A US 75923777A US RE29388 E USRE29388 E US RE29388E
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- 239000000203 mixture Substances 0.000 title claims abstract description 92
- 239000011521 glass Substances 0.000 title claims abstract description 36
- 239000000835 fiber Substances 0.000 title claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 20
- 229910011255 B2O3 Inorganic materials 0.000 claims abstract description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 8
- 229910018404 Al2 O3 Inorganic materials 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910004554 P2 O5 Inorganic materials 0.000 claims abstract 3
- 239000003513 alkali Substances 0.000 claims description 22
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000292 calcium oxide Substances 0.000 claims description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 9
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 9
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 229940044927 ceric oxide Drugs 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 229910004742 Na2 O Inorganic materials 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 239000012535 impurity Substances 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001950 potassium oxide Inorganic materials 0.000 abstract description 2
- 230000003014 reinforcing effect Effects 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910017344 Fe2 O3 Inorganic materials 0.000 description 1
- 229910011763 Li2 O Inorganic materials 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- -1 fluoride ions Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 239000002994 raw material Substances 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
-
- 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
- C03C13/00—Fibre or filament compositions
- C03C13/001—Alkali-resistant fibres
- C03C13/002—Alkali-resistant fibres containing zirconium
-
- 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
-
- 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
-
- 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
Definitions
- This invention concerns improvements in or relating to glass compositions, fiber made therefrom and cementitious materials including such fiber as reinforcement.
- compositions which are chemically durable, have a low liquidus temperature and slow devitrification and are capable of being formed into fibers by rotary spinning and attenuation of the strands so obtained. These compositions comprise, in weight percent;
- glass fibers which are especially water durable, and can be made from these compositions by rotary or centrifugal spinning.
- U.S. Pat. No. 3,861,925 discloses alkali resistant fiberizable glass compositions which are zirconia free and consist essentially of, in weight percent.
- a glass composition consists essentially, by weight of the composition, of:
- Titania from .[.1.]. .Iadd.7 .Iaddend.to 15% Titania
- R 2 O is sodium oxide, potassium oxide or a mixture of both, optionally including up to 5% by weight lithium oxide (based on the total composition), and R 1 O is MgO, CaO, BaO or SrO, or a mixture of two or more thereof.
- a preferred glass composition consists essentially, by weight of the compositions, of:
- R 2 O is selected from the group consisting of Na 2 O, K 2 O and mixtures of the two and mixtures thereof additionally containing up to 1% by weight lithium oxide (based on the total weight of the composition) and R 1 O is selected from the group consisting of MgO, CaO, BaO, SrO and mixtures of two or more thereof.
- compositions preferably comprise at least 20% by weight of ZrO.sub. 2 and TiO 2 together, and at least 23% by weight of ZrO.sub. 2, TiO 2 and rare earth oxide together.
- the composition preferably contains not more than 30%, and more preferably not more than 25% by weight, of titania and zirconia together, and not more than 7% by weight of R 1 O.
- the R 1 O and F may be deliberately added to the composition, within the ranges of content stated above. If Li 2 O is used in place of fluorine then comparable amounts of Al 2 O 3 will be added (necessarily but not desirably) by way of the raw materials commercially available at present. Al 2 O 3 should not exceed more than 2% by weight of the composition.
- rare earth (metal) oxide imparts to the glass compositions of this invention a degree of alkali resistance not, in general, exhibited by glass compositions of otherwise similar formulation. At least 0.8% rare earth oxide is present in the composition.
- the rare earth oxide used may be any of the naturally occurring ones, preferably ceric oxide, or a mixture of naturally occurring rare earth oxides.
- the term "naturally occurring rare earth oxide mixture" is well recognised in the Art used in the following examples according to its accepted meaning denoting a mixture of rare earth metal compounds (mainly the oxides) in which such metals are present in relative abundancies approximately equivalent to their naturally occurring relative abundancies.
- Such mixtures are constituted by, for example, a natural rare earth ore such as bastnaesite or monoazite; the term is also used as herein to denote such an ore which has been treated to remove undesirable components such as carbonate, phosphate or fluoride ions.
- bastnaesite for example, is treated to remove such ions, the rare earth metal content remains constant, and remains proportional to the naturally occurring abundance.
- suitable naturally occurring rare earth oxide mixture can be prepared by taking an ore such as bastnaesite or monazite and pre-treating it in an appropriate manner.
- the glass compositions of this invention consist essentially of the ingredients specified above, but may be found to include also a trace amount, i.e. up to about 1%, of phosphate and/or of chlorine present as the chloride.
- a glass of the following composition was prepared and was melt drawn at 1230° C:
- the glass fibers obtained exhibited a tensile strength of 1.36 GPa (Giga Pascals - equivalent to GN/m 2 ).
- Fibers of this composition were boiled in saturated Ca(OH) 2 for 4 hours, washed successively with water, 1% hydrochloric acid (1 minute), water, and acetone, and then dried. The strength of the fiber was increased to 1.55 GPa.
- the alkali resistance of the above compositions make them eminently suitable for use as fibrous reinforcement in cementitious materials. They may be used in an amount up to 30% by weight of the total dry weight of cementitious materials, preferably in an amount of from 5 to 10% by weight.
- Example 2 of U.S. Pat. No. 2,877,124 (which Example contains the maximum proportions of TiO 2 and ZrO 2 exemplified in this patent), and to this composition an addition of 4% by weight of CeO 2 was made, 4% CeO 2 being the maximum content of rare earth oxide mentioned in U.S. Pat. No. 3,127,277, to provide the following glass composition:
- this modified composition should provide fibers of an alkali resistance equivalent to that obtained by use of the present invention. I have found, however, that such similar properties are not obtained as demonstrated below.
- Fibers were made from this composition, and were tested for alkali resistance, by the methods described in the preceding Examples.
- the fibers exemplified in Examples 1 to 5 have strengths after alkali treatment of from 1.04 to 1.55 GPa, which clearly shows that fibers produced from these compositions exhibit considerably greater strengths after alkali treatment than can fibers produced by the modification referred to above. That is, fibers made in accordance with this invention have greater alkali resistance.
- Example 2 was repeated using 4% ceric oxide; this gave fibers having a strength of 0.94 GPa before treatment with alkali, and 0.90 GPa after alkali treatment. Without any ceric oxide a similar composition gives a strength of 0.66 GPa before treatment and 0.57 after alkali treatment. Thus, the percentage decline in the strength of fibers made from Example 2 composition, with or without ceric oxide, is less than for an Example A (I) composition with ceric oxide.
- compositions of this invention may not necessarily exhibit an especially marked increase in alkali resistance over similar compositions not containing rare earth oxide, or may exhibit a tendency to devitrify during fibre drawing; accordingly, the considerations and adjustments already used in glass technology to account for these difficulties should be applied to the invention for such compositions, not exemplified above, as come within the scope of the invention.
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- Chemical & Material Sciences (AREA)
- 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
Glass compositions, having improved chemical resistance and useful in the form of fibers for reinforcing cementitious materials, consisting essentially of:
From 50 to 75 percent by weight Silica
From 10 to 25 percent by weight R2 O
from .[.1.]. .Iadd.7 .Iaddend.to 15 percent Titania
From 1 to 20 percent by weight Zirconia
From 0.8 to 20 percent by weight Rare Earth Oxide
From 0 to 20 percent by weight Boric Oxide
From 0 to 10 percent by weight R1 O
from 0 to 1 percent by weight Fluorine as (fluoride)
From 0 to 2 percent by weight Al2 O3
from 0 to 1 percent by weight P2 O5
from 0 to 1 percent by weight Chlorine (as chloride)
Where R2 O is sodium oxide, potassium oxide or a mixture of both, optionally including up to 5% by weight of lithium oxide (based on the total composition) and R1 O is MgO, CaO, BaO, or SrO, or a mixture of two or more thereof.
Description
This application is a continuation-in-part of new earlier application Ser. No. 441,984 filed Feb. 13, 1974, now abandoned.
This invention concerns improvements in or relating to glass compositions, fiber made therefrom and cementitious materials including such fiber as reinforcement.
Glass compositions, containing beryllia, magnesia, strontium oxide, titania, cadmium oxide or zirconia have been known for many years (see, for example, U.K. Patent Specification Nos. 595,498 and 791,374 and U.S. Pat. No. 2,640,784). From these, refractory glass fiber and other articles may be made.
More recently, U.S. Pat. No. 2,877,124 discloses compositions which are chemically durable, have a low liquidus temperature and slow devitrification and are capable of being formed into fibers by rotary spinning and attenuation of the strands so obtained. These compositions comprise, in weight percent;
______________________________________
SiO.sub.2 50 to 65
Al.sub.2 O.sub.3 0 to 8
CaO 3 to 4
MgO 0 to 10
Na.sub.2 O, K.sub.2 O, L.sub.2 O
10 to 20
B.sub.2 O.sub.3 5 to 15
TiO.sub.2 0 to 8
ZrO.sub.3 0 to 8
BaO 0 to 8
Fe.sub.2 O.sub.3 0 to 12
MnO 0 to 12
ZnO 0 to 2
______________________________________
And preferably are essentially free from at least a majority of the six last-named components.
U.S. Pat. No. 3,127,277 discloses glasses of high modulus of elasticity, of composition, in weight percent:
______________________________________ SiO.sub.2 45-60 CaO 9-19 MgO 6-10 BeO 7-12 ZrO.sub.2 1-3 Li.sub.2 O up to 4 TiO.sub.2 2-10 CeO.sub.2 up to 4 ______________________________________
Optionally including other ingredients such as Fe2 O3 and Al2 O3.
U.S. Pat. No. 3,817,764 disloses glass compositions, in weight percent:
______________________________________ SiO.sub.2 49-57 Al.sub.2 O.sub.3 3-5 B.sub.2 O.sub.3 6-12 Na.sub.2 O 18-20 CaO 0-2 TiO.sub.2 9-12 ZrO.sub.2 0-7 Fe.sub.2 O.sub.3 0-0.5 LiO.sub.2 0-1 ______________________________________
and states that glass fibers which are especially water durable, and can be made from these compositions by rotary or centrifugal spinning.
Finally, U.S. Pat. No. 3,861,925 discloses alkali resistant fiberizable glass compositions which are zirconia free and consist essentially of, in weight percent.
______________________________________
SiO.sub.2 55-65
TiO.sub.2, La.sub.2 O.sub.2 or CeO.sub.2,
12-25
CaO 4-6
Na.sub.2 O, 12-18
K.sub.2 O 0-3
______________________________________
Despite such disclosures, however, there is still a need for glasses having improved chemical durability -- in particular improved resistance to alkali attack, for example for use in reinforcing cementitious articles.
According to the present invention, a glass composition consists essentially, by weight of the composition, of:
from 50 to 75% Silica
from 10 to 25% R2 O
from .[.1.]. .Iadd.7 .Iaddend.to 15% Titania
from 1 to 20% Zirconia
up to 20% Rare Earth Oxide
from 0 to 20% Boric Oxide
from 0 to 10% R1 O
from 0 to 1% Fluorine (as fluoride)
from 0 to 2% Al2 O3
where R2 O is sodium oxide, potassium oxide or a mixture of both, optionally including up to 5% by weight lithium oxide (based on the total composition), and R1 O is MgO, CaO, BaO or SrO, or a mixture of two or more thereof.
A preferred glass composition consists essentially, by weight of the compositions, of:
from 50 - 58% Silica
from 11 - - % R2 O
from 8 - 10% Titania
from 10 - 14% Zirconia
from 0.8 - 15% Rare Earth Oxide
from 0.5 - 4% Boric Oxide
from 0.1 - 6% R1 O
from 0 - 1% Fluorine (as fluoride)
from 0.1 - 0.4% Chlorine (as chloride)
Wherein R2 O is selected from the group consisting of Na2 O, K2 O and mixtures of the two and mixtures thereof additionally containing up to 1% by weight lithium oxide (based on the total weight of the composition) and R1 O is selected from the group consisting of MgO, CaO, BaO, SrO and mixtures of two or more thereof.
The compositions preferably comprise at least 20% by weight of ZrO.sub. 2 and TiO2 together, and at least 23% by weight of ZrO.sub. 2, TiO2 and rare earth oxide together.
The composition preferably contains not more than 30%, and more preferably not more than 25% by weight, of titania and zirconia together, and not more than 7% by weight of R1 O. The R1 O and F may be deliberately added to the composition, within the ranges of content stated above. If Li2 O is used in place of fluorine then comparable amounts of Al2 O3 will be added (necessarily but not desirably) by way of the raw materials commercially available at present. Al2 O3 should not exceed more than 2% by weight of the composition.
The inclusion of a rare earth (metal) oxide imparts to the glass compositions of this invention a degree of alkali resistance not, in general, exhibited by glass compositions of otherwise similar formulation. At least 0.8% rare earth oxide is present in the composition.
The rare earth oxide used may be any of the naturally occurring ones, preferably ceric oxide, or a mixture of naturally occurring rare earth oxides. The term "naturally occurring rare earth oxide mixture" is well recognised in the Art used in the following examples according to its accepted meaning denoting a mixture of rare earth metal compounds (mainly the oxides) in which such metals are present in relative abundancies approximately equivalent to their naturally occurring relative abundancies. Such mixtures are constituted by, for example, a natural rare earth ore such as bastnaesite or monoazite; the term is also used as herein to denote such an ore which has been treated to remove undesirable components such as carbonate, phosphate or fluoride ions. When bastnaesite, for example, is treated to remove such ions, the rare earth metal content remains constant, and remains proportional to the naturally occurring abundance.
The detrimental effect of excessive amounts of certain ions, such as phosphate or fluoride, in glass making is well known to those skilled in the art, so as suitable naturally occurring rare earth oxide mixture can be prepared by taking an ore such as bastnaesite or monazite and pre-treating it in an appropriate manner.
It is already well known that the chemical properties of rare earth metals and their oxides are markedly similar; I would expect that most, if not all, of the rare earth oxides -- and particularly any mixture thereof containing cerium -- give a result closely similar to the results obtained from compositions containing cerium oxide as the sole rare earth oxide.
The glass compositions of this invention consist essentially of the ingredients specified above, but may be found to include also a trace amount, i.e. up to about 1%, of phosphate and/or of chlorine present as the chloride.
Preferred embodiments of the invention, embodying the above principles, are illustrated in the following Examples 1 to 5; comparative results for a modified prior art composition are illustrated in Example A.
A glass of the following composition was prepared and was melt drawn at 1230° C:
______________________________________ Silica 50% weight Sodium Oxide 10% Lithium Oxide 1% Boric Oxide 3% Titania 10% Zirconia 10% Cerium Oxide 15% Sodium Fluoride 1% ______________________________________
The glass fibers obtained exhibited a tensile strength of 1.36 GPa (Giga Pascals - equivalent to GN/m2).
Fibers of this composition were boiled in saturated Ca(OH)2 for 4 hours, washed successively with water, 1% hydrochloric acid (1 minute), water, and acetone, and then dried. The strength of the fiber was increased to 1.55 GPa.
Glasses of various compositions as set forth in the following table were melt drawn, and the tensile strength thereof was determined before and after alkali treatment, with the results shown.
______________________________________
Composition Examples
% by weight 2 3 4 5
______________________________________
SiO.sub.2 58 56 58 58
Li.sub.2 O -- -- -- --
Na.sub.2 O 13 12 14 13
TiO.sub.2 9 8 10 7
ZrO.sub.2 12 13 13 14
B.sub.2 O.sub.3 3 3 4 0.5
CaO -- 6 -- 4
BaO -- -- 0.1 0.6
CeO.sub.2 5 2 -- --
Naturally occurring
Rare Earth Oxide mixture*
-- -- 0.8 2.5
F -- -- -- --
Cl -- -- 0.1 0.4
Tensile Strength (GPa)
before alkali treatment
1.22 1.04 1.07 1.25
Tensile Strength (GPa)
after alkali treatment
0.87 0.63 0.73 1.19
______________________________________
*Obtained by treating a bastnaesite ore to remove carbonate and fluoride
ions.
The alkali resistance of the above compositions make them eminently suitable for use as fibrous reinforcement in cementitious materials. They may be used in an amount up to 30% by weight of the total dry weight of cementitious materials, preferably in an amount of from 5 to 10% by weight.
I. A composition was made as disclosed in Example 2 of U.S. Pat. No. 2,877,124 (which Example contains the maximum proportions of TiO2 and ZrO2 exemplified in this patent), and to this composition an addition of 4% by weight of CeO2 was made, 4% CeO2 being the maximum content of rare earth oxide mentioned in U.S. Pat. No. 3,127,277, to provide the following glass composition:
______________________________________ SiO.sub.2 50.98 weight % B.sub.2 O.sub.3 6.04 Al.sub.2 O.sub.3 2.38 Fe.sub.2 O.sub.3 2.97 MgO 3.60 CaO 7.40 BaO 2.80 Na.sub.2 O 12.90 TiO.sub.2 2.97 ZrO.sub.2 3.40 CeO.sub.2 4.00 ______________________________________
At first instance it might appear that this modified composition should provide fibers of an alkali resistance equivalent to that obtained by use of the present invention. I have found, however, that such similar properties are not obtained as demonstrated below.
Fibers were made from this composition, and were tested for alkali resistance, by the methods described in the preceding Examples.
The following results were obtained:
Strength before alkali treatment 0.99 GPa
Strength after alkali treatment 0.64 GPa
II. A composition as in (I) above, but containing no rare earth oxide was formed into fibers, and these were tested, by the same methods, with the following results:
Stength before alkali treatment 1.24 GPa
Strength after alkali treatment 0.48 GPa
The fibers exemplified in Examples 1 to 5 have strengths after alkali treatment of from 1.04 to 1.55 GPa, which clearly shows that fibers produced from these compositions exhibit considerably greater strengths after alkali treatment than can fibers produced by the modification referred to above. That is, fibers made in accordance with this invention have greater alkali resistance.
III. As a further comparison, Example 2 was repeated using 4% ceric oxide; this gave fibers having a strength of 0.94 GPa before treatment with alkali, and 0.90 GPa after alkali treatment. Without any ceric oxide a similar composition gives a strength of 0.66 GPa before treatment and 0.57 after alkali treatment. Thus, the percentage decline in the strength of fibers made from Example 2 composition, with or without ceric oxide, is less than for an Example A (I) composition with ceric oxide.
Obviously, modifications may be made in the compositions of this invention as exemplified above. It should be noted, however, that certain compositions within the composition ranges of this invention may not necessarily exhibit an especially marked increase in alkali resistance over similar compositions not containing rare earth oxide, or may exhibit a tendency to devitrify during fibre drawing; accordingly, the considerations and adjustments already used in glass technology to account for these difficulties should be applied to the invention for such compositions, not exemplified above, as come within the scope of the invention.
Claims (21)
1. A glass composition, having improved chemical resistance to alkali attack, consisting essentially of:
from 50 to 75 percent by weight Silica
from 10 to 25 percent by weight R2 O
from .[.1.]. .Iadd.7 .Iaddend.to 15 percent by weight Titania
from 1 to 20 percent by weight Zirconia
from 0.8 to 20 percent by weight Rare Earth Oxide
from 0 to 20 percent by weight Boric Oxide
from 0 to 10 percent by weight R1 O
from 0 to 1 percent by weight Fluorine (as fluoride)
from 0 to 2 percent by weight Al2 O3
from 0 to 1 percent by weight P2 O5
from 0 to 1 percent by weight Chlorine (as chloride)
wherein R2 O is selected from the group consisting of Na2 O, K2 O, mixtures thereof, and mixtures thereof containing up to 5% by weight lithium oxide (based on the total weight of the composition) and R1 O is selected from the group consisting of MgO, CaO, BaO, and SrO, and mixtures of two or more thereof.
2. A glass composition according to claim 1, including not more than 30%, by weight of the titania and zirconia together.
3. A glass composition according to claim 1, comprising at least 20% by weight of ZrO2 and TiO2 together.
4. A glass composition according to claim 1, comprising at least 23% by weight of ZrO2, TiO2 and rare earth oxide together.
5. A glass composition according to claim 1, including not more than 7% by weight of the R1 O.
6. A glass composition according to claim 1, wherein any of R1 O, fluorine Al2 O3, P2 O5 or chlorine's present in impurity amounts.
7. A glass composition according to claim 1, containing not more than 15% by weight of zirconia.
8. Glass fiber having a composition as defined in claim 1.
9. Cementitious material, including as reinforcement therein up to 30% by weight of glass fiber as defined in claim 6.
10. A glass composition consisting of:
______________________________________ Silica 50% by weight Sodium Oxide 10% Lithium Oxide 1% Boric Oxide 3% Titania 10% Zirconia 10% Cerium Oxide 15% Sodium Fluoride 1% ______________________________________
11. A glass composition according to claim 10, in the form of fibers.
12. A glass composition consisting of:
______________________________________ Silica 58% by weight Sodium Oxide 13% Titania 9% Zirconia 12% Boric Oxide 3% Ceric Oxide 5% ______________________________________
13. A glass composition according to claim 12, in the form of fibers.
14. A glass composition consisting of:
______________________________________ Silica 56% by weight Sodium Oxide 12% Titania 8% Zirconia 13% Boric Oxide 3% Calcium Oxide 6% Ceric Oxide 2% ______________________________________
15. A glass composition according to claim 14, in the form of fibers.
16. A glass composition consisting essentially of:
______________________________________ Silica 58% by weight Sodium Oxide 14% Titania 10% Zirconia 13% Boric Oxide 4% Barium Oxide 0.1% Mixture of naturally accuring rare earth oxides 0.8% Cl 0.1% ______________________________________
17. A glass composition according to claim 16, in the form of fibers.
18. A glass composition consisting essentially of:
______________________________________ Silica 58% by weight Sodium Oxide 13% Titania 7% Zirconia 14% Boric Oxide 0.5% Calcium Oxide 4% Barium Oxide 0.6% Mixture of naturally accurring rare earth oxides 2.5% Cl 0.4% ______________________________________
19. A glass composition according to claim 18, in the form of fibres.
20. A glass composition, having improved chemical resistance to alkali attack, consisting essentially of:
______________________________________
from 50-58 percent by weight
Silica
" 11-14 " " " R.sub.2 O
" 8-10 " " " Titania
" 10-14 " " " Zirconia
" 0.8-15 " " " Rare Earth Oxide
" 0.5-4 " " " Boric Oxide
" 0.1-6 " " " R.sup.1 O
" 0-1 " " " Fluorine (as fluoride)
" 0.1-0.4 " " " Chlorine (as chloride)
______________________________________
wherein .[.R20.]. .Iadd.R2 O .Iaddend.is elected from the group consisting of Na2 O, K2 O, mixtures of the two, and mixtures thereof additionally containing up to 1% by weight lithium oxide (based on the total weight of the composition) and R1 O is selected from the group consisting of MgO, CaO, BaO, SrO and mixtures of two or more thereof.
21. A glass composition according to claim 20, in the form of fibers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/759,237 USRE29388E (en) | 1973-02-14 | 1977-01-13 | Glass compositions and fibers made therefrom |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| UK7151/73 | 1973-02-14 | ||
| GB715173A GB1459385A (en) | 1973-02-14 | 1973-02-14 | Glass fibres |
| US44198474A | 1974-02-13 | 1974-02-13 | |
| US05/647,988 US3969121A (en) | 1973-02-14 | 1976-01-09 | Glass compositions and fibers made therefrom |
| US05/759,237 USRE29388E (en) | 1973-02-14 | 1977-01-13 | Glass compositions and fibers made therefrom |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US44198474A Continuation-In-Part | 1973-02-14 | 1974-02-13 | |
| US05/647,988 Reissue US3969121A (en) | 1973-02-14 | 1976-01-09 | Glass compositions and fibers made therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE29388E true USRE29388E (en) | 1977-09-06 |
Family
ID=27447578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/759,237 Expired - Lifetime USRE29388E (en) | 1973-02-14 | 1977-01-13 | Glass compositions and fibers made therefrom |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE29388E (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4330628A (en) | 1979-03-15 | 1982-05-18 | Pilkington Brothers Limited | Alkali-resistant glass fibres |
| US4345037A (en) | 1980-02-27 | 1982-08-17 | Pilkington Brothers Limited | Alkali resistant glass fibres for cement reinforcement |
| US4537862A (en) | 1982-06-28 | 1985-08-27 | Owens-Illinois, Inc. | Lead-free and cadmium-free glass frit compositions for glazing, enameling and decorating |
| EP0500325A1 (en) * | 1991-02-19 | 1992-08-26 | Nippon Electric Glass Company., Ltd. | Chemically resistant glass fiber composition |
| US5382552A (en) * | 1993-09-14 | 1995-01-17 | Miles Inc. | Rare earth-containing alkali silicate frits and their use for the preparation of porcelain enamel coatings with improved cleanability |
| US5932347A (en) | 1996-10-31 | 1999-08-03 | Owens Corning Fiberglas Technology, Inc. | Mineral fiber compositions |
| US5962355A (en) | 1996-04-24 | 1999-10-05 | Owens Corning Fiberglas Technology, Inc. | Glass compositions having high KI values and fibers therefrom |
| US6034014A (en) | 1997-08-04 | 2000-03-07 | Owens Corning Fiberglas Technology, Inc. | Glass fiber composition |
| US6077798A (en) | 1996-08-02 | 2000-06-20 | Owens Corning Fiberglas Technology, Inc. | Biosoluble, high temperature mineral wools |
| US9643881B2 (en) | 2012-10-25 | 2017-05-09 | Nippon Electric Glass Co., Ltd. | Glass composition for glass fiber, glass fiber, and method for producing glass fiber |
| US11078107B2 (en) * | 2017-09-06 | 2021-08-03 | Samsung Electronics Co., Ltd. | Exterior material of home appliance, home appliance including the exterior material, and manufacturing method thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4330628A (en) | 1979-03-15 | 1982-05-18 | Pilkington Brothers Limited | Alkali-resistant glass fibres |
| US4345037A (en) | 1980-02-27 | 1982-08-17 | Pilkington Brothers Limited | Alkali resistant glass fibres for cement reinforcement |
| US4537862A (en) | 1982-06-28 | 1985-08-27 | Owens-Illinois, Inc. | Lead-free and cadmium-free glass frit compositions for glazing, enameling and decorating |
| EP0500325A1 (en) * | 1991-02-19 | 1992-08-26 | Nippon Electric Glass Company., Ltd. | Chemically resistant glass fiber composition |
| US5382552A (en) * | 1993-09-14 | 1995-01-17 | Miles Inc. | Rare earth-containing alkali silicate frits and their use for the preparation of porcelain enamel coatings with improved cleanability |
| US5962355A (en) | 1996-04-24 | 1999-10-05 | Owens Corning Fiberglas Technology, Inc. | Glass compositions having high KI values and fibers therefrom |
| US6077798A (en) | 1996-08-02 | 2000-06-20 | Owens Corning Fiberglas Technology, Inc. | Biosoluble, high temperature mineral wools |
| US5932347A (en) | 1996-10-31 | 1999-08-03 | Owens Corning Fiberglas Technology, Inc. | Mineral fiber compositions |
| US6034014A (en) | 1997-08-04 | 2000-03-07 | Owens Corning Fiberglas Technology, Inc. | Glass fiber composition |
| US9643881B2 (en) | 2012-10-25 | 2017-05-09 | Nippon Electric Glass Co., Ltd. | Glass composition for glass fiber, glass fiber, and method for producing glass fiber |
| US11078107B2 (en) * | 2017-09-06 | 2021-08-03 | Samsung Electronics Co., Ltd. | Exterior material of home appliance, home appliance including the exterior material, and manufacturing method thereof |
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