# Patent

## Title
Composition for high performance glass fibers and fibers formed therewith

## Abstract

A composition for the manufacture of high strength glass fibers suitable for manufacture in a refractory lined glass melter is disclosed. The glass composition of the present invention includes 64-75 weight % SiO2, 16-24 weight % Al2O3, 8-11 weight % MgO and 0.25 to 3.0 weight % R2O where R2O is the sum of Li2O and Na2O. A composition of the present invention includes 64-75 weight % SiO2, 16-24 weight % Al2O3, 8-11 weight % MgO and 0.25 to 3.0 weight % Li2O. Another composition includes 68-69 weight percent SiO2, 20-22 weight percent Al2O3, 9-10 weight percent MgO and 1-3 weight percent Li2O. By using oxide based refractory lined furnaces the cost of production of glass fibers is substantially reduced in comparison with the cost of fibers using a platinum lined melting furnace. Fibers formed by the present invention are also disclosed. The fibers have a fiberizing temperature of less than 2650° F., a ΔT of at least 80° F. Further, the glass fibers have a strength in excess of 680 KPSI, in some instances a strength in excess of about 700 KPSI, and in others a strength in excess of about 730 KPSI. The glass fibers will desirably have a modulus greater than 12.0 MPSI, in some instances greater than about 12.18 MPSI, and in certain instances greater than about 12.7 MPSI.

## Background
TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION
The present invention is generally directed to a composition for use in manufacturing continuous high strength glass fibers and fibers formed from the composition.
BACKGROUND OF THE INVENTION
A common glass composition for making continuous high-strength glass fiber strands is “S-Glass.” The term S-Glass defines a family of glasses composed primarily of the oxides of magnesium, aluminum, and silicon with a chemical composition that produces glass fibers having a higher mechanical strength than E-Glass fibers. The chemical composition of the S-glass family produces high strength glass fiber and enables these glasses to be used in high strength applications such as ballistic armor. ASTM International defines S-Glass as family of glasses composed primarily of the oxides of magnesium, aluminum, and silicon with a certified chemical composition which conforms to an applicable material specification and which produces high mechanical strength (D578-05). The Deutsches Institut für Normung (DIN) defines S-Glass as an aluminosilicate glass without added CaO and having a partial mass of MgO where MgO is about 10% by weight (An alumino-silicate glass is defined as a glass which consists largely of aluminum trioxide and silicon dioxide and other oxides) (DIN 1259-1).
R-Glass is another family of high strength, high modulus glasses that is typically formed into fibers for use in aerospace composite applications. The R-Glass family is primarily composed of silicon oxide, aluminum oxide, magnesium oxide, and calcium oxide with a chemical composition that produces glass fibers with a higher mechanical strength than S-Glass fibers. R-Glass generally contains less silica and greater calcium oxide (CaO) than S-Glass which requires higher melting and processing temperatures during fiber forming.
Tables IA-IE set forth the compositions for a number of conventional high strength glass compositions.











TABLE I-A







RUSSIAN





Chinese
CONTINUOUS
NITTOBO
NITTOBO



High
ROVING
“T”
“T”



Strength
MAGNESIUM
Glass
Glass Fabric


Constituent
glass
ALUMINOSILICATE
Fabric “B”
(Yarn) “C”



















SiO2
55.08
55.81
64.58
64.64


CaO
0.33
0.38
0.44
0.40


Al2O3
25.22
23.78
24.44
24.57


B2O3
1.85

0.03
0.03


MgO
15.96
15.08
9.95
9.92


Na2O
0.12
0.063
0.08
0.09


Fluorine
0.03

0.034
0.037


TiO2
0.023
2.33
0.019
0.018


Fe2O3
1.1
0.388
0.187
0.180


K2O
0.039
0.56
0.007
0.010


ZrO2
0.007
0.15


Cr2O3

0.011
0.003
0.003


Li2O

1.63


CeO2





















TABLE I-B






Nitto
Nitto

Vetrotex Saint




Boseki
Boseki
Nitto Boseki TE
Gobain SR Glass
Polotsk



A&P
NT6030
Glass RST-
Stratifils SR CG
STEKLOVOLOKNO


Constituent
Yarn
Yarn
220PA-535CS
250 P109
High Strength Glass




















SiO2
65.51
64.60
64.20
63.90
58.64


CaO
0.44
0.58
0.63
0.26
0.61


Al2O3
24.06
24.60
25.10
24.40
25.41


B2O3




0.04


MgO
9.73
9.90
9.90
10.00
14.18


Na2O
0.04
0.06
0.020
0.039
0.05


Fluorine
0.07



0.02


TiO2
0.016
0.000
0.000
0.210
0.624


Fe2O3
0.067
0.079
0.083
0.520
0.253


K2O
0.020
0.020
0.020
0.540
0.35


ZrO2
0.079


Cr2O3
0.0010


0.001
0.023


Li2O


CeO2




















TABLE I-C







Chinese
Advanced





High
Glass



Chinese High
Strength
Yarns



Strength Yarn
Glass
Zentron S-2
SOLAIS Glass


Constituent
(8 micron)
Roving
Glass Roving
Sample



















SiO2
55.22
55.49
64.74
64.81


CaO
0.73
0.29
0.14
0.55


Al2O3
24.42
24.88
24.70
24.51


B2O3
3.46
3.52

0.02


MgO
12.46
12.28
10.24
9.35


Na2O
0.104
0.06
0.17
0.16


Fluorine
0.07


0.02


TiO2
0.32
0.36
0.015
0.04


Fe2O3
0.980
0.930
0.045
0.238


K2O
0.240
0.150
0.005
0.03


ZrO2


Cr2O3
0.0050


0.007


Li2O
0.59
0.63


CeO2
1.23
1.25





















TABLE I-D






Advanced

IVG
IVG
IVG Vertex



Glass

Vertex
Vertex
Outside



Yarns
Culimeta
B96
Glass
#1 Glass


Constituent
S Glass
Roving
675 Yarn
Roving
Roving




















SiO2
64.61
59.37
58.34
58.58
58.12


CaO
0.17
0.27
0.31
0.30
0.31


Al2O3
24.84
25.49
23.81
24.26
24.09


B2O3
0.04
0.05


MgO
10.11
13.47
14.99
15.02
15.36


Na2O
0.118
0.024
0.05
0.02
0.03


Fluorine
0.03

0.04
0.04
0.04


TiO2
0.011
0.530
1.380
0.67
0.91


Fe2O3
0.042
0.374
0.333
0.336
0.303


K2O

0.48
0.42
0.28
0.29


ZrO2

0.152
0.129
0.165
0.157


Cr2O3
0.0050
0.0120
0.0100
0.0120
0.0120


Li2O


CeO2




















TABLE I-E








IVG Vertex
RH CG250 P109




Outside #2
Glass Fiber



Constituent
Glass Roving
Strand




















SiO2
58.69
58.54



CaO
0.29
9.35



Al2O3
24.3
25.39



B2O3



MgO
15.06
6.15



Na2O
0.03
0.10



Fluorine
0.04
0.16



TiO2
0.64
0.008



Fe2O3
0.331
0.069



K2O
0.36
0.14



ZrO2
0.187
0.006



Cr2O3
0.0130



Li2O



CeO2










Typical R-Glass and S-Glass are generally produced by melting the constituents of the compositions in a platinum lined melting container. The costs of forming R-Glass and S-Glass fibers are dramatically higher than E-Glass fibers due to the cost of producing the fibers in such melters. Thus, there is a need in the art for methods of forming glass compositions useful in the formation of high performance glass fibers in a more cost-effective process.
SUMMARY OF THE INVENTION
The present invention is a glass composition for the formation of continuous glass fibers suitable for use in high strength applications. The composition may be inexpensively formed into glass fibers using low-cost, direct melting in refractory-lined furnaces due to the relatively low fiberizing temperature of the composition. Once formed into fibers, the glass composition provides the strength characteristics of S-Glass. One composition of the present invention includes 64-75 weight % SiO2, 16-24 weight % Al2O3, 8-11 weight % MgO and 0.25 to 3.0 weight % R2O where R2O is the sum of Li2O and Na2O. The composition of the present invention includes 64-75 weight % SiO2, 16-24 weight % Al2O3, 8-11 weight % MgO and 0.25 to 3.0 weight % Li2O. In certain embodiments, the glass composition is composed of 64-70 weight % SiO2, 17-22 weight % Al2O3, 9-11 weight % MgO and 1.75-3.0 weight % R2O where R2O is the sum of Li2O and Na2O. In another embodiment, the glass composition is composed of 64-70 weight % SiO2, 17-22 weight % Al2O3, 9-11 weight % MgO and 1.75-3.0 weight % LiO2. In certain embodiments, the composition does not contain more than about 5.0 weight % of oxides or compounds selected from the group consisting of CaO, P2O5, ZnO, ZrO2, SrO, BaO, SO3, F2, B2O3, TiO2 and Fe2O3.
The desired properties of the high performance composite fibers manufactured by the present invention include a fiberizing temperature of less than about 2650° F., less than about 2625° F., less than about 2600° F., or even less than about 2575° F. and a liquidus temperature that is below the fiberizing temperature, in some instances by at least 80° F., in others by at least about 120° F., and in certain other instances by at least about 150° F. The present invention also includes fibers formed from such a composition.


DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION
The fiberizing properties of the glass batch composition of the present invention include the fiberizing temperature, the liquidus, and delta-T (ΔT). The fiberizing temperature is defined as the temperature that corresponds to a viscosity of 1000 Poise. As discussed in more detail below, a lowered fiberizing temperature reduces the production cost of the fibers, allows for a longer bushing life, increases throughput permits the glass to be melted in a refractory-lined melter, and reduces energy consumption. For example, at a lower fiberizing temperature, a bushing operates at a cooler temperature and does not “sag” as quickly. Sag is a phenomenon that occurs in bushings that are held at an elevated temperature for extended periods of time. By lowering the fiberizing temperature, the sag rate of the bushing may be reduced and the bushing life can be increased. In addition, a lower fiberizing temperature allows for a higher throughput since more glass can be melted in a given period at a given energy input. As a result, production cost is reduced. In addition, a lower fiberizing temperature will also permit glass formed with the inventive composition to be melted in a refractory-lined melter since both its melting and fiberizing temperatures are below the upper use temperatures of many commercially available refractories.
The liquidus of a glass is defined as the highest temperature at which equilibrium exists between liquid glass and its primary crystalline phase. At all temperatures above the liquidus, the glass is free from crystals in its primary phase. At temperatures below the liquidus, crystals may form. Crystals in the melt will cause blockages in the bushing and weakness in the fibers.
Another fiberizing property is delta-T (ΔT), which is defined as the difference between the fiberizing temperature and the liquidus. A larger ΔT offers a greater degree of flexibility during the formation of the glass fibers and helps to inhibit devitrification of the glass (that is, the formation of crystals within the melt) during melting and fiberizing. Increasing the ΔT also reduces the production cost of the glass fibers by allowing for a greater bushing life and by providing a wider process window for forming fibers.
The glasses of the present invention are suitable for melting in traditional commercially available refractory-lined glass melters that are widely used in the manufacture of glass reinforcement fibers, in what is commonly called a direct-melt process. This is contrasted to prior art formulations, which were melted in a platinum lined melting container, since those prior art formulations typically do not have properties which are compatible with direct-melt processes. With the present invention, starting batch components typically include SiO2 (ground silica sand), and Al2O3 (calcined alumina) or pyrophyllite, as well as chain modifiers from source materials such as talc, magnesite or dolomite. The carbon included in materials such as magnesite is off gassed as oxides of carbon such as CO2.
In certain embodiments, a fiber formed in accordance with the present invention will include 64-75 weight % SiO2, 16-24 weight % Al2O3, 8-11 weight % MgO and 0.25 to 3.0 weight % R2O where R2O is the sum of Li2O and Na2O. In other embodiments, the composition will include 0.25 to 3.0 weight % Li2O rather than a combination of Li2O and Na2O. In yet other embodiments, the glass composition is composed of 64-70 weight % SiO2, 17-22 weight % Al2O3, 9-11 weight % MgO and 1.75 to 3.0 weight % R2O where R2O is the sum of Li2O and Na2O. In certain other embodiments, the composition will include 1.75 to 3.0 weight % LiO2. A fiber formed in accordance with the present invention will typically include small amounts of CaO, P2O5, ZnO, ZrO2, SrO, BaO, SO3, F2, B2O3, TiO2 and Fe2O3, in certain embodiments in a total amount of less than 5 weight percent, and in other embodiments less than about 4 weight percent. In addition, a fiber formed in accordance with the method and composition of the present invention will having a fiberizing temperature of less than 2650° F., and in certain embodiments less than about 2625° F., in other embodiments less than about 2600° F. and in certain embodiments less than about 2575° F. and a liquidus temperature that is below the fiberizing temperature in certain embodiments by at least 80° F., and in other embodiments by at least about 120° F., and in yet other embodiments by at least about 150° F. Further, the glass of the present invention in certain embodiments will have a pristine fiber strength in excess of 680 KPSI, and in certain other embodiments a strength in excess of about 700 KPSI, and in yet other embodiments a strength in excess of about 730 KPSI. Further, the glass fibers will desirably have a modulus greater than 12.0 MPSI, and in certain embodiments greater than about 12.18 MPSI, and in some embodiments greater than about 12.6 MPSI.
The glass batch of the present invention is melted, in some instances using a glass melting furnace made from appropriate refractory materials such as alumina, chromic oxide, silica, alumina-silica, zircon, zirconia-alumina-silica, or similar oxide-based refractory materials. Often, such glass melting furnaces include one more bubblers and/or electrical boost electrodes (One suitable glass melting furnace is disclosed in U.S. Application Number 20070105701 entitled “Method of Manufacturing High Performance Glass Fibers in a Refractory Lined Melter and Fiber Formed Thereby” herein incorporated by reference). The bubblers and/or electrical boost electrodes increase the temperature of the bulk glass and increase the molten glass circulation under the batch cover.
The melted glass is delivered to a bushing assembly from a forehearth. The bushing includes a tip plate with a plurality of nozzles, each nozzle discharges a stream of molten glass, which are mechanically drawn to form continuous filaments. Typically, the filaments are coated with a protective sizing, gathered into a single continuous strand and wound onto a rotating collet of a winder device to form a package. The filaments may also be processed into other forms including, without limitation, wet used chopped strand fibers, dry use chopped strand fibers, continuous filament mats, chopped strand mats, wet formed mats or air laid mats.
Having generally described this invention, a further understanding can be obtained by reference to certain specific examples illustrated below which are provided for purposes of illustration only and are not intended to be all inclusive or limiting unless otherwise specified.
EXAMPLES
The glasses in the examples listed in Tables IIA-IID were melted in platinum crucibles or in a continuous platinum-lined melter for determining the mechanical and physical properties of the glass and fibers produced therefrom. The units of measurement for the physical properties are: Viscosity (° F.), Liquidus temperature (° F.) and ΔT (° F.). In some examples the glasses were fiberized and Strength (KPsi), Density (g/cc), Modulus (MPsi) were measured.
The fiberizing temperature was measured using a rotating spindle viscometer. The fiberizing viscosity is defined as 1000 Poise. The liquidus was measured by placing a platinum container filled with glass in a thermal gradient furnace for 16 hours. The greatest temperature at which crystals were present was considered the liquidus temperature. The modulus was measured using the sonic technique on a single fiber of glass. The tensile strength was measured on a pristine single fiber.













TABLE IIA





Glass
Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5
Ex. 6





















SiO2
67.2
69
67
70
70
65


Al2O3
20
22
22
17
17
21


MgO
9.8
9
11
11
10
11


Li2O
3
0
0
2
3
3


Measured
2531
2761
2648
2557
2558
2461


Viscosity (° F.)


1st Measured
2313
2619
2597
2332
2302
2296


Liquidus (° F.)


2nd Measured
2302
2620
2614
2346
2308
2318


Liquidus (° F.)


ΔT (° F.)
218
142
51
225
256
165


Measured
2.459
2.452
2.481
2.450
2.441
2.482


Density (g/cc)






















TABLE II-B





Glass
Ex. 7
Ex. 8
Ex. 9
Ex. 10
Ex. 11
Ex. 12





















SiO2
70
69
70
65
66
65


Al2O3
18
17
21
22
22
22


MgO
9
11
9
11
9
10


Li2O
3
3
0
2
3
3


Measured
2544
2496
2752
2525
2523
2486


Viscosity


(° F.)


1st Measured
2311
2234
2597
2468
2391
2361


Liquidus (° F.)


2nd Measured
2324
2343
2603
2462
2394
2382


Liquidus (° F.)


ΔT (° F.)
233
262
155
57
132
125


Measured
2.434
2.455
2.443
2.486
2.460
2.474


Density (g/cc)






















TABLE II-C





Glass
Ex. 13
Ex. 14
Ex. 15
Ex. 16
Ex. 17
Ex. 18





















SiO2
70
67.32
67.57
68.27
68.02
67.76


Al2O3
19
20.49
20.49
20.10
20.10
20.10


MgO
11
10.00
10.00
9.69
9.69
9.69


Li2O
0
2.00
1.75
1.75
2.00
2.25


Measured Viscosity
2679
2563
2584
2598
2578
2547


(° F.)


1st Measured Liquidus
2596
2456
2486
2446
2431
2399


(° F.)


2nd Measured
2582
2447
2469
2469
2437
2406


Liquidus (° F.)


ΔT (° F.)
83
111.5
106.5
140.5
144
144.5


Measured
2.453

2.461

2.452


Density (g/cc)









The composition of the present invention may also include chain modifiers such as Na2O, CaO and B2O3. Such compositions are shown in Table II-D (below).













TABLE II-D





Glass
Ex. 19
Ex. 21
Ex. 22
Ex. 22
Ex. 23
Ex. 24





















SiO2
75
66
65
65
66
74


Al2O3
15
20
20
24
19
15


MgO
8
9
8
8
9
8


Li2O
1
1
2
0
0
0


Na2O
1
2
1
1
2
3


CaO

2
4


B2O3



2
4


Measured
2765
2607
2469
2669

2809


Viscosity


(° F.)


1st Measured
2422
2729

2614
2630
2680


Liquidus (° F.)


ΔT (° F.)
343
−122

55

129









The fibers of the present invention have superior modulus and strength characteristics. The fibers of Example 1 have a Measured Modulus of 12.71 MPsi and a Measured Strength of 688 KPsi. The fibers of Example 3 have a Measured Modulus of 12.96 MPsi and a Measured Strength of 737 KPsi. The fibers of Example 17 have a Measured Modulus of 12.75 MPsi and a Measured Strength of 734 KPsi.
As is understood in the art, the above exemplary inventive compositions do not always total 100% of the listed components due to statistical conventions (such as, rounding and averaging) and the fact that some compositions may include impurities that are not listed. Of course, the actual amounts of all components, including any impurities, in a composition always total 100%. Furthermore, it should be understood that where small quantities of components are specified in the compositions, for example, quantities on the order of about 0.05 weight percent or less, those components may be present in the form of trace impurities present in the raw materials, rather than intentionally added.
Additionally, components may be added to the batch composition, for example, to facilitate processing, that are later eliminated, thereby forming a glass composition that is essentially free of such components. Thus, for instance, minute quantities of components such as fluorine and sulfate may be present as trace impurities in the raw materials providing the silica, calcia, alumina, and magnesia components in commercial practice of the invention or they may be processing aids that are essentially removed during manufacture.
As apparent from the above examples, glass fiber compositions of the invention have advantageous properties, such as low fiberizing temperatures and wide differences between the liquidus temperatures and the fiberizing temperatures (high ΔT values). Other advantages and obvious modifications of the invention will be apparent to the artisan from the above description and further through practice of the invention). The high-performance glass of the present invention melts and refines at relatively low temperatures, has a workable viscosity over a wide range of relatively low temperatures, and a low liquidus temperature range.
The invention of this application has been described above both generically and with regard to specific embodiments. Although the invention has been set forth in what is believed to be the preferred embodiments, a wide variety of alternatives known to those of skill in the art can be selected within the generic disclosure. Other advantages and obvious modifications of the invention will be apparent to the artisan from the above description and further through practice of the invention. The invention is not otherwise limited, except for the recitation of the claims set forth below.

## Claims

1. A composition for high strength glass fibers comprising:
64-75 weight percent SiO2;
16-24 weight percent Al2O3;
8-11 weight percent MgO;
0.25-3 weight percent Li2O; and
no more than 1.0 weight percent of CaO impurities, wherein said glass fibers produced from said composition have a fiberizing temperature of less than about 2650° F. and a strength of greater than about 700 KPsi.

2. The composition of claim 1, wherein the composition further comprises less than 5 weight percent total of one or more compounds selected from the group consisting of P2O5, ZnO, ZrO2, SrO, BaO, SO3, F2, B2O3, TiO2 and Fe2O3.

3. The composition of claim 1, wherein glass fibers produced from said composition have a ΔT of at least 80° F.

4. The composition of claim 1, wherein:
said Al2O3 is present in said composition in an amount from about 17 to about 22 weight percent;
said MgO is present in said composition in an amount from about 9 to about 11 weight percent; and
said Li2O is present in said composition in an amount from about 1.75 to 3.0 weight percent.

5. The composition of claim 1, wherein the components of said composition are meltable in a refractory-lined melter.

6. A high strength glass fiber formed from a composition comprising:
64-75 weight percent SiO2;
16-24 weight percent Al2O3;
8-11 weight percent MgO;
0.25-3 weight percent Li2O, and
no more than 1.0 weight percent of CaO impurities, wherein said glass fiber has a fiberizing temperature of less than about 2650° F. and a strength of greater than about 700 KPsi.

7. The high strength glass fiber of claim 6, wherein the fiber has a modulus greater than about 12.0 MPsi.

8. The high strength glass fiber of claim 6, wherein said fiber has a pristine fiber tensile strength greater than about 730 KPsi.

9. The high strength glass fiber of claim 6, wherein said fiber has a fiberizing temperature less than about 2600° F.

10. The high strength glass fiber of claim 9, wherein said fiber has a liquidus temperature that is at least 80° F. below said fiberizing temperature.

11. The high strength glass fiber of claim 6, wherein said fiber has a ΔT of at least 80° F.

12. The high strength glass fiber of claim 6, wherein said fiber has a liquidus temperature that at least 80° F. below the fiberizing temperature.

13. The composition of claim 6, wherein Li2O is present in said composition in an amount from about 1.75 to 3.0 weight percent.

14. A glass fiber formed composition comprising:
64-75 weight percent SiO2;
16-24 weight percent Al2O3;
8-11 weight percent MgO;
0.25-3 weight percent Li2O; and
no more than 1.0 weight percent of CaO impurities, wherein said glass fibers produced from said composition have a fiberizing temperature of less than about 2650° F., a modulus of greater than 12 MPsi, and a strength of greater than about 700 KPsi.

15. The high strength glass fiber of claim 14, wherein said fiber has a liquidus temperature that is at least 80° F. below the fiberizing temperature.

16. The high strength glass fiber of claim 14, wherein said fiber has a fiberizing temperature less than about 2600° F.

17. The glass fiber of claim 16, wherein said fiber has a liquidus temperature that is at least 80° F. below said fiberizing temperature.

18. The glass fiber of claim 14, wherein said fiber has a pristine fiber tensile strength greater than about 730 KPsi.

19. The glass fiber of claim 14, wherein said fiber has a ΔT of at least 80° F.

20. The glass fiber of claim 14, wherein:
said Al2O3 is present in said composition in an amount from about 17 to about 22 weight percent;
said MgO is present in said composition in an amount from about 9 to about 11 weight percent; and
said Li2O is present in said composition in an amount from about 1.75 to 3.0 weight percent.