Composition for high performance glass, high performance glass fibers and articles therefrom

Information

  • Patent Grant
  • 8586491
  • Patent Number
    8,586,491
  • Date Filed
    Tuesday, January 30, 2007
    18 years ago
  • Date Issued
    Tuesday, November 19, 2013
    11 years ago
Abstract
Glass batch compositions for the formation of high-modulus, and high-strength glass fibers as well as fibers suitable for use as textile and reinforcements are disclosed. Fibers formed of the composition are especially suitable for use in high-strength, low-weight applications such as windmill blades and high strength and modulus applications where strength and stiffness are required in the composite. The glass composition is up to about 70.5 weight % SiO2, about 24.5 weight % Al2O3, about 22 weight % alkaline earth oxides and may include small amounts of alkali metal oxides and ZrO2. Additionally, glass fibers formed from the inventive composition are non-corrosive or substantially non-corrosive in nature. Due to the non-corrosive nature of the glass fibers, glass fibers made with the inventive composition may be used in applications where the glass fibers or a composite formed from the glass fibers are in contact with a corrosive substance.
Description
TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION

The present invention relates generally to a composition for continuous glass fibers, and more particularly to a glass composition for use in high-strength applications as well as high-strength glass fibers and articles that have non-corrosive properties.


BACKGROUND OF THE INVENTION

Fiberglass is manufactured from various raw materials combined in specific proportions to yield a desired chemical composition. This proportion is commonly termed a “glass batch.” The composition of the glass batch and the glass manufactured from it are typically expressed in terms of percentages of the components, which are expressed as oxides. SiO2, Al2O3, CaO, MgO, B2O, Na2O, K2O, Fe2O3, and minor amounts of other oxides are common components of a glass batch. Numerous types of glasses may be produced from varying the amounts of these oxides, or eliminating some of the oxides, in the glass batch. Examples of such glasses that may be produced include E-glass, S-glass, R-glass, and E-CR-glass. The glass composition determines the properties of the glass including properties such as the viscosity, the liquidus temperature, the durability, the density, the strength, and the Young's modulus of the glass.


To form glass fibers, typically the glass batch is melted, the molten glass is drawn into filaments through a bushing or orifice plate, and an aqueous sizing composition containing lubricants, coupling agents, and film-forming binder resins is applied to the filaments. After the sizing composition is applied, the fibers may be gathered into one or more strands and wound into a package or, alternatively, the fibers may be chopped while wet and collected. The collected chopped strands may then be dried and cured to form dry chopped fibers or they can be packaged in their wet condition as wet chopped fibers.


The most common glass composition for making continuous glass fiber strands is “E-glass.” The liquidus temperature of E-glass is approximately 2100° F. (1149° C.) or lower. One advantage of E-glass is that its liquidus temperature allows operating temperatures for producing glass fibers to be approximately 1900° F. to 2400° F. (1038° C. to 1316° C.). The ASTM D578 classification for E-glass fiber yarns used in printed circuit boards and aerospace applications defines the composition to be 52 to 56 weight % SiO2, 16 to 25 weight % CaO, 12 to 16 weight % Al2O3, 5 to 10 weight % B2O3, 0 to 5 weight % MgO, 0 to 2 weight % Na2O and K2O, 0 to 0.8 weight % TiO2, 0.05 to 0.4 weight % Fe2O3 and 0 to 1.0 weight % Fluorine. The phrase weight %, as used herein, is intended to be defined as the percent by weight of the total composition.


Boron-free fibers are sold under the trademark ADVANTEX (Owens Corning, Toledo, Ohio, USA). Boron-free fibers, such as are disclosed in U.S. Pat. No. 5,789,329 to Eastes, et al., which is incorporated herein by reference in its entirety, offer a significant improvement in operating temperatures over boron-containing E-glass. Boron-free glass fibers fall under the ASTM D578 definition for E-glass fibers for use in general-use applications. In particular, the ASTM D578 classification for E-glass fibers for use in general use applications defines the composition to be 52 to 62 weight % SiO2, 16 to 25 weight % CaO, 12 to 16 weight % Al2O3, 0 to 10 weight % B2O3, 0 to 5 weight % MgO, 0 to 2 weight % Na2O and K2O, 0 to 1.5 weight % TiO2, 0.05 to 0.8 weight % Fe2O3 and 0 to 1.0 weight % Fluorine.


S-glass is a family of glasses composed primarily of the oxides of magnesium, aluminum, and silicon with a chemical composition that produces glass fibers that have a higher mechanical strength than E-glass fibers. The composition for forming S-glass includes approximately 65 weight % SiO2, 25 weight % Al2O3, and 10 weight % MgO. S-glass has a composition that was originally designed to be used in high-strength applications such as ballistic armor.


R-glass is a family of glasses that are composed primarily of the oxides of silicon, aluminum, magnesium, and calcium with a chemical composition that produces glass fibers with a higher mechanical strength than E-glass fibers. R-glass has a composition that contains about 58 to about 60 weight % SiO2, about 23.5 to about 25.5 weight % Al2O3, about 14 to about 17 weight % CaO plus MgO, 0% B2O3, 0% F2 and less than about 2 weight % of miscellaneous components. R-glass contains more alumina and silica than E-glass and requires higher melting and processing temperatures during fiber forming. Typically, the melting and processing temperatures for R-glass are at least about 160° C. higher than those for E-glass. This increase in processing temperature requires the use of a high-cost platinum-lined melter. In addition, the close proximity of the liquidus temperature to the forming temperature in R-glass requires that the glass be fiberized at a viscosity lower than E-glass, which is customarily fiberized at or near about 1000 poise. Fiberizing R-glass at the customary 1000 poise viscosity would likely result in glass devitrification, which causes process interruptions and reduced productivity.


Tables 1A-1E set forth the compositions for a number of conventional high-strength glass compositions.













TABLE 1-A







RUSSIAN
NITTOBO
NITTOBO



Chinese
CONTINUOUS
“T”
“T”



High
ROVING
Glass
Glass



Strength
MAGNESIUM
Fabric
Fabric


Constituent
glass
ALUMINOSILICATE
“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
0.00
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
0.00
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
0.00
0.00


Cr2O3
0.00
0.011
0.003
0.003


Li2O
0.00
1.63
0.00
0.00


CeO2
0.00
0.00
0.00
0.00





















TABLE 1-B









Vetrotex






Nitto
Saint






Boseki TE
Gobain
Polotsk



Nitto
Nitto
Glass
SR Glass
STEKLOVO-



Boseki
Boseki
RST-
Stratifils
LOKNO



A&P
NT6030
220PA-
SR CG
High


Constituent
Yarn
Yarn
535CS
250 P109
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
0.00
0.00
0.00
0.00
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
0.00
0.00
0.00
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
0.00
0.00
0.00
0.00


Cr2O3
0.0010
0.00
0.00
0.001
0.023


Li2O
0.00
0.00
0.00
0.00
0.00


CeO2
0.00
0.00
0.00
0.00
0.00





















TABLE 1-C






Chinese
Chinese






High
High
Zentron

Advanced



Strength
Strength
S-2
SOLAIS
Glass



Yarn
Glass
Glass
Glass
Yarns


Constituent
(8 micron)
Roving
Roving
Sample
R Glass




















SiO2
55.22
55.49
64.74
64.81
58.46


CaO
0.73
0.29
0.14
0.55
9.39


Al2O3
24.42
24.88
24.70
24.51
24.55


B2O3
3.46
3.52
0.00
0.02
0.04


MgO
12.46
12.28
10.24
9.35
5.91


Na2O
0.104
0.06
0.17
0.16
0.079


Fluorine
0.07
0.00
0.00
0.02
0.054


TiO2
0.32
0.36
0.015
0.04
0.196


Fe2O3
0.980
0.930
0.045
0.238
0.400


K2O
0.240
0.150
0.005
0.03
0.67


ZrO2
0.00
0.00
0.00
0.00
0.00


Cr2O3
0.0050
0.00
0.00
0.007
0.005


Li2O
0.59
0.63
0.00
0.00
0.00


CeO2
1.23
1.25
0.00
0.00
0.00





















TABLE 1-D










IVG





IVG

Vertex



Advanced

Vertex
IVG
Outside



Glass

B96
Vertex
#1



Yarns
Culimeta
675
Glass
Glass


Constituent
S Glass
Roving
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
0.00
0.00
0.00


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
0.00
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
0.00
0.48
0.42
0.28
0.29


ZrO2
0.00
0.152
0.129
0.165
0.157


Cr2O3
0.0050
0.0120
0.0100
0.0120
0.0120


Li2O
0.00
0.00
0.00
0.00
0.00


CeO2
0.00
0.00
0.00
0.00
0.00


















TABLE 1-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
0.00
0.00


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
0.00


Li2O
0.00
0.00


CeO2
0.00
0.00









Glass fibers formed from compositions such as those described above are used in a variety of applications. For example, glass fibers are commonly used as reinforcements in polymer matrices to form glass fiber reinforced plastics or composites. The glass fibers may be used to form structural composites such as door liners or hoodliners for automobiles, storage drums, aircraft flooring, wind turbine blades, and pressure vessels. Alternatively, the glass fibers may be used to form non-structural articles such as automobile panels, insulator rods, and ballistic panels. In some situations, such as storage drums formed from glass fibers, wind turbine blades, and pressure vessels, the glass fibers may come into contact with a corrosive substance, such as corrosive chemicals or saltwater. It is therefore desirable to have a glass composition that can be utilized to form glass fiber composite articles that are non-corrosive in nature and which optimally possess adequate strength for the desired application. Further, the costs of forming R-glass and S-glass fibers are dramatically higher than E-glass fibers due to the cost of producing these fibers in a platinum-lined melter.


Thus, there exists a need in the art for glass compositions useful in the formation of non-corrosive, high performance fibers that can be formed by a direct-melt process in a refractory-lined furnace.


SUMMARY OF THE INVENTION

The invention, in part, is a glass composition for the formation of continuous glass fibers that are suitable for use in high-strength applications. The composition of the present invention 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 glass fibers. Once formed into fibers, the glass composition provides the strength characteristics of higher-priced glass fibers such as S-glass. The composition of the present invention includes about 60.5 to about 70.5 weight % SiO2, about 10.0 to about 24.5 weight % Al2O3, about 6.0 to about 20.0 weight % RO, where RO equals the sum of MgO, CaO, SrO and BaO, and about 0.0 to about 3.0 weight % alkali metal oxides. In a preferred embodiment, the glass composition is composed of about 61 to about 68 weight % SiO2, about 15 to about 19 weight % Al2O3, about 15 to about 20 weight % RO, where RO equals the sum of MgO, CaO, SrO and BaO, and about 0 to about 3 weight % alkali metal oxides. The composition preferably does not contain more than about 4 weight % of oxides or halogens selected from the group consisting of ZnO, SO3, Fluorine, B2O3, TiO2, ZrO2 and Fe2O3. The desired properties of the glass composition of the present invention include a fiberizing temperature of less than about 2650° F. and a liquidus temperature that is preferably below the fiberizing temperature by at least about 80° F., more preferably by at least about 120° F., and most preferably by at least about 150° F. Additionally, fibers produced from the inventive composition are non-corrosive or substantially (e.g., nearly) non-corrosive in nature. The non-corrosive properties of the glass fibers formed from the inventive composition permit the glass fibers to be used in applications in which the fibers are in contact with corrosive substances.


It is an advantage of the present invention that glass fibers formed from the inventive composition can be melted in a refractory-lined melter because both its melting and fiberizing temperatures are below the upper use temperatures of conventional refractories.


It is another advantage of the present invention that glass fibers formed from the inventive composition possess corrosion-resistant properties.


It is yet another advantage of the present invention that the glass composition has a lower fiberizing temperature that allows for a higher throughput, which reduces production costs.


It is a feature of the present invention that glass fibers formed from the inventive composition have a fiberizing temperature of less than about 2650° F., a ΔT of at least about 80° F., and a coefficient of thermal expansion (CTE) of about 2.28×10−6 in/in/° F. to about 2.77×10−6 in/in/° F.


It is another feature of the present invention that glass fibers made from the inventive composition possess corrosion resistant properties that are equal to or better than E-glass and boron-free glass fibers.


The foregoing and other objects, features, and advantages of the invention will appear more fully hereinafter from a consideration of the detailed description that follows. It is to be expressly understood, however, that the drawings are for illustrative purposes and are not to be construed as defining the limits of the invention.





BRIEF DESCRIPTION OF THE DRAWINGS

The advantages of this invention will be apparent upon consideration of the following detailed disclosure of the invention, especially when taken in conjunction with the accompanying drawings wherein:



FIG. 1 is a graphical illustration of the percentage of weight loss of glass fibers and basalt after immersion in 10% nitric acid at 96° C. for 24 hours, 100 hours, and 240 hours;



FIG. 2 is a graphical illustration of the percentage of weight loss of glass fibers and basalt after immersion in 5% sulfuric acid at 96° C. for 24 hours, 100 hours, and 240 hours;



FIG. 3 is a graphical illustration of the percentage of weight loss of glass fibers and basalt after immersion in water at 96° C. for 24 hours, 100 hours, and 240 hours; and



FIG. 4 is a graphical illustration of the 3-point bending strength retention of glass fibers after one month strain corrosion in 5% sulfuric acid.





DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS OF THE INVENTION

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described herein. All references cited herein, including published or corresponding U.S. or foreign patent applications, issued U.S. or foreign patents, and any other references, are each incorporated by reference in their entireties, including all data, tables, figures, and text presented in the cited references. It is to be appreciated that in the drawings, the thickness of the lines, layers, and regions may be exaggerated for clarity.


Fiberizing properties of the glass composition of the present invention include the fiberizing temperature, the liquidus temperature, and delta-T. The fiberizing temperature is defined as the temperature that corresponds to a viscosity of about 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 usage. 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 temperature is defined as the highest temperature at which equilibrium exists between liquid glass and its primary crystalline phase. At all temperatures above the liquidus temperature, the glass is free from crystals in its primary phase. At temperatures below the liquidus temperature, crystals may form.


Another fiberizing property is delta-T (ΔT), which is defined as the difference between the fiberizing temperature and the liquidus temperature. 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, which are widely used in the manufacture of glass reinforcement fibers. Starting batch components typically include SiO2 (ground silica sand), and Al2O3 (calcined alumina), as well as chain modifiers from source materials such as MgCO3 (magnesite), CaCO3 (limestone), SrCO3 (strontianite), BaCO3 (witherite), ZrSiO4 (zircon), and Na2CO3 (natrite).


The glass batch is preferably composed of about 60.5 to about 70.5 weight percent SiO2, about 10.0 to about 24.5 weight percent Al2O3, about 6.0 to about 20.0 weight percent RO, where RO equals the sum of MgO, CaO, and SrO, and about 0.0 to about 3.0 weight percent alkali metal oxides. The phrase weight percent, as used in conjunction with the present invention, is intended to be defined as the percent by weight of the total composition. A fiber formed in accordance with the present invention will typically also include small amounts of ZnO, SO3, Fluorine, B2O3, TiO2 and Fe2O3, preferably in an amount of less than 4 weight percent. It is to be appreciated that impurities or tramp materials may be present in the glass composition without adversely affecting the glasses or the fibers. These impurities may enter the glass as raw material impurities or may be products formed by the chemical reaction of the molten glass with furnace components.


In general, glass fibers according to the present invention may be formed by obtaining the raw materials or ingredients and mixing or blending the components in a conventional manner in the appropriate quantities to give the desired weight percentages of the final composition. The mixed batch may then be melted in a refractory-lined melter, and the resulting molten glass may be passed along a forehearth and into platinum based bushings located along the bottom of the forehearth. The molten glass is pulled or attenuated through holes or orifices in the bottom or tip plate of the bushing to form individual glass filaments or fibers. Strands of glass fibers are formed by gathering the individual filaments together, such as with a gathering shoe. The strands are each formed of a plurality of individual glass filaments and may be wound on a forming tube mounted on a rotatable collet of a winding machine. The glass fibers may be further processed in a conventional manner suitable for the intended application.


A glass fiber formed in accordance with the present invention will preferably having a fiberizing temperature of less than about 2650° F., a ΔT of at least about 80° F., preferably a ΔT of at least about 120° F., and most preferably a ΔT of at least 150° F., and a coefficient of thermal expansion (CTE) of about 2.28×10−6 in/in/° F. to about 2.77×10−6 in/in/° F. Further, the glass fibers of the present invention preferably have a strength in excess of about 600 KPSI, preferably a strength in excess of about 630 KPSI, and most preferably a strength in excess of about 695 KPSI. Further, the glass fibers will desirably have a modulus greater than about 12.0 MPSI, preferably greater then about 12.18 MPSI, and most preferably greater then about 12.6 MPSI. It will be appreciated that certain details of construction are not provided in view of such details being conventional and well within the skill of the art.


The present invention also includes a composite material including glass fibers, as described above, in combination with a hardenable matrix material. The composite material is especially useful in applications where high strength, high stiffness, and low weight are desired. Such applications include aircraft, automotive, and wind energy (such as windmill blades) as well as any other application where low weight, stiffness, and high strength are desired. Suitable hardenable matrix materials include thermoset and thermoplastic resins. By way of example, suitable thermoset matrix materials include vinyl esters, polyesters, resin epoxies and combinations or copolymers thereof. Typically, windmill blades are formed by any suitable composite fabrication technique, such as vacuum-assisted resin infusion or pre-impregnated reinforcement lay-up.


Additionally, glass fibers formed from the inventive composition are non-corrosive or substantially non-corrosive in nature. Due to the non-corrosive nature of the glass fibers, glass fibers made in accordance with the present invention may be used in applications where the glass fibers or a composite formed from the glass fibers are in contact with a corrosive substance. Thus, the glass fibers may be used in applications such as chemical drums, grating, sail battens, and wind turbine blades.


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
Example 1
Glass Formation

The glasses in the examples set forth in Tables 2A-2P 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), Softening Point (° F.) and coefficient of thermal expansion (CTE) (in/in/(° F.)) were measured.


The fiberizing temperature was measured using a rotating spindle viscometer. The fiberizing viscosity is defined as 1000 Poise. The liquidus temperature 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. The CTE was measured with a dilatometer over the range of temperature from 25 to 600° C. The softening point temperature was measured using the ASTM C338 fiber-elongation method.















TABLE 2-A





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





















SiO2
62.63
62.42
61.75
63.01
63.07
63.16


CaO
8.49
8.64
8.57
4.84
4.85
4.8


Al2O3
18.50
18.54
18.82
19.99
20.03
19.76


MgO
9.47
9.64
9.65
11.26
11.28
11.33


Na2O
0.70
0.69
0.00
0.70
0.70
0.00


TiO2
0.00
0.01
0.01
0.00
0.01
0.02


Fe2O3
0.20
0.05
0.045
0.20
0.05
0.037


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2491
na
na
2514
na
na


Viscosity








(° F.)








Measured
2261
2247
na
2335
na
na


Liquidus








Temp








(° F.)








Measured
230
na
na
179
na
na


ΔT (° F.)








Measured
672
na
na
695
na
na


Strength








(KPsi)








Measured
2.556
na
na
2.530
na
na


Density








(g/cc)








Measured
12.4
12.6
na
12.6
12.7
na


Modulus








(MPsi)








Softening
na
na
na
1765
na
na


Point








(° F.)








CTE in/
na
na
na
2.28 × 10−6
na
na


in/(° F.)






















TABLE 2-B





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





















SiO2
62.32
63.89
63.14
61.39
61.39
65.00


CaO
11.56
11.21
11.96
11.96
8.71
13.00


Al2O3
17.25
16.39
16.39
18.14
18.89
15.00


MgO
7.98
6.62
6.62
6.62
9.62
5.00


Na2O
0.70
0.75
0.75
0.75
0.25
1.00


TiO2
0.00
0.75
0.75
0.75
0.75
1.00


Fe2O3
0.20
0.39
0.39
0.39
0.39
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2458
2493
2435
2431
2434
2509


Viscosity








(° F.)








Measured
2301
2268
2294
2353
2261
2226


Liquidus








Temp








(° F.)








Measured
157
225
141
78
173
283


ΔT (° F.)








Measured
632
636
622
615
682
612


Strength








(KPsi)








Measured
2.573
2.553
2.567
2.567
2.564
na


Density








(g/cc)








Measured
12.2
12.2
12.2
12.2
12.6
na


Modulus








(MPsi)








Softening
1729
na
na
na
na
na


Point








(° F.)








CTE in/
2.77 × 10−6
na
na
na
na
na


in/(° F.)






















TABLE 2-C





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





















SiO2
63.89
65.00
64.00
63.89
65.00
65.00


CaO
6.96
14.00
4.00
8.96
14.00
12.50


Al2O3
18.64
15.00
20.00
18.89
15.00
15.00


MgO
9.62
6.00
11.00
6.62
5.00
5.00


Na2O
0.25
0.00
1.00
0.75
0.00
1.00


TiO2
0.25
0.00
0.00
0.75
1.00
1.00


Fe2O3
0.39
0.00
0.00
0.14
0.00
0.50


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2513
2508
2548
2565
2481
2523


Viscosity








(° F.)








Measured
2337
2373
2401
2288
2403
2227


Liquidus








Temp








(° F.)








Measured
176
135
147
277
78
296


ΔT (° F.)








Measured
695
624
na
na
604
na


Strength








(KPsi)








Measured
2.480
2.554
na
na
2.546
na


Density








(g/cc)








Measured
12.3
12.0
na
na
11.9
na


Modulus








(MPsi)








Softening
na
na
na
na
na
na


Point (° F.)








CTE in/in/
na
na
na
na
na
na


(° F.)






















TABLE 2-D





Glass
Ex. 19
Ex. 20
Ex. 21
Ex. 22
Ex. 23
Ex. 24





















SiO2
64.50
65.00
65.00
65.00
65.00
65.00


Al2O3
15.00
15.00
20.00
20.00
20.00
20.00


CaO
14.00
13.50
4.00
7.50
4.00
9.00


MgO
5.00
5.00
11.00
5.00
10.50
5.00


Na2O
1.00
0.00
0.00
1.00
0.00
1.00


TiO2
0.00
1.00
0.00
1.00
0.00
0.00


Fe2O3
0.50
0.50
0.00
0.50
0.50
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2515
0.00
0.00
0.00
0.00
0.00


Viscosity








(° F.)








Measured
2258
2530
2594
2672
2602
2642


Liquidus








Temp (° F.)








Measured ΔT
257
2395
2487
2347
2481
2391


(° F.)








Measured
593
612
na
na
na
na


Strength (KPsi)








Measured
2.538
2.560
na
na
na
na


Density (g/cc)








Measured
11.82
12.00
na
na
na
na


Modulus








(MPsi)








Softening Point
na
na
na
1819
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
2.33
na
na






















TABLE 2-E





Glass
Ex. 25
Ex. 26
Ex. 27
Ex. 28
Ex. 29
Ex. 30





















SiO2
63.89
63.89
63.89
63.89
63.89
61.39


Al2O3
16.39
18.89
18.89
18.89
17.89
18.89


CaO
11.96
9.96
9.21
6.96
6.96
8.46


MgO
6.62
6.62
6.62
9.12
9.62
9.62


Na2O
0.50
0.25
0.75
0.25
0.75
0.75


TiO2
0.25
0.25
0.25
0.75
0.75
0.75


Fe2O3
0.39
0.14
0.39
0.14
0.14
0.14


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2486
2509
2522
2525
2495
2417


Viscosity








(° F.)








Measured
2287
2312
2327
2348
2267
2273


Liquidus








Temp (° F.)








Measured ΔT
199
197
195
177
228
144


(° F.)








Measured
631
na
628
670
651
648


Strength (KPsi)








Measured
2.547
na
2.526
2.540
2.544
2.574


Density (g/cc)








Measured
12.16
na
12.08
12.32
12.43
12.42


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-F





Glass
Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35
Ex. 36





















SiO2
65.00
65.00
65.00
65.00
65.00
62.85


Al2O3
15.00
15.00
15.00
15.00
15.00
19.92


CaO
14.00
14.00
6.50
7.50
8.00
4.62


MgO
5.00
5.00
11.00
11.00
11.00
11.36


Na2O
0.00
0.50
1.00
1.00
1.00
0.72


TiO2
0.50
0.00
1.00
0.00
0.00
0.02


Fe2O3
0.50
0.50
0.50
0.50
0.00
0.04


Fluorine
0.00
0.00
0.00
0.00
0.00
0.02


Measured
2446
2468
2458
2467
2461
2527


Viscosity








(° F.)








Measured
2391
2367
2396
2359
2461
2479


Liquidus








Temp (° F.)








Measured ΔT
55
101
62
108
0
48


(° F.)








Measured
623
611
na
na
640
na


Strength (KPsi)








Measured
2.523
2.542
na
na
na
na


Density (g/cc)








Measured
11.74
11.92
na
na
na
na


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-G





Glass
Ex. 37
Ex. 38
Ex. 39
Ex. 40
Ex. 41
Ex. 42





















SiO2
62.30
62.61
62.39
62.18
70.26
60.00


Al2O3
13.98
18.64
18.73
18.83
19.69
25.00


CaO
23.72
5.60
6.68
7.75
10.05
9.00


MgO
0.00
11.53
10.85
10.17
0.00
6.00


Na2O
0.00
1.63
1.35
1.08
0.00
0.00


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2373
2462
2472
2451
na
2544


Viscosity








(° F.)








Measured
2233
2254
2268
2247
2621
0


Liquidus








Temp (° F.)








Measured ΔT
140
208
204
204
na
0


(° F.)








Measured
547
na
na
na
na
na


Strength (KPsi)








Measured
2.575
2.552
na
na
na
na


Density (g/cc)








Measured
11.49
11.89
na
na
na
na


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-H





Glass
Ex. 43
Ex. 44
Ex. 45
Ex. 46
Ex. 47
Ex. 48





















SiO2
62.30
64.29
66.28
68.27
70.26
64.36


Al2O3
13.98
15.41
16.84
18.26
19.69
18.75


CaO
23.72
20.30
16.89
13.47
10.05
16.89


MgO
0.00
0.00
0.00
0.00
0.00
0.00


Na2O
0.00
0.00
0.00
0.00
0.00
0.00


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2367
2466
2615
2813
na
na


Viscosity








(° F.)








Measured
2216
2256
2421
2507
2519
2506


Liquidus








Temp (° F.)








Measured ΔT
151
210
194
306
na
na


(° F.)








Measured
na
na
na
na
na
na


Strength (KPsi)








Measured
na
na
na
na
na
na


Density (g/cc)








Measured
na
na
na
na
na
na


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-I





Glass
Ex. 49
Ex. 50
Ex. 51
Ex. 52
Ex. 53
Ex. 54





















SiO2
61.33
60.85
63.78
61.38
63.10
65.35


Al2O3
23.40
22.90
17.24
18.32
20.00
19.25


CaO
0.15
3.15
8.12
9.67
4.90
4.15


MgO
15.03
13.00
10.08
9.65
11.30
10.55


Na2O
0.03
0.03
0.70
0.90
0.70
0.70


TiO2
0.01
0.01
0.01
0.01
0.00
0.00


Fe2O3
0.05
0.05
0.05
0.05
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
na
2476
na
na
2531
2602


Viscosity








(° F.)








Measured
na
2547
na
na
2498
2450


Liquidus








Temp (° F.)








Measured ΔT
na
−71
na
na
33
152


(° F.)








Measured
na
na
na
na
676
na


Strength (KPsi)








Measured
na
2.561
na
na
2.537
na


Density (g/cc)








Measured
na
13.30
na
na
12.75
na


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-J





Glass
Ex. 55.
Ex. 56
Ex. 57
Ex. 58
Ex. 59
Ex. 60





















SiO2
62.35
62.35
62.35
63.85
63.85
63.85


Al2O3
22.25
19.25
19.25
20.75
19.25
19.25


CaO
4.15
7.15
4.15
4.15
5.65
4.15


MgO
10.55
10.55
13.55
10.55
10.55
12.05


Na2O
0.70
0.70
0.70
0.70
0.70
0.70


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2554
2504
2470
2680
2555
2531


Viscosity








(° F.)








Measured
2527
2333
2385
2498
2431
2425


Liquidus








Temp (° F.)








Measured ΔT
27
171
85
182
124
106


(° F.)








Measured
680
680
na
na
672
670


Strength (KPsi)








Measured
na
2.554
2.556
na
2.532
2.532


Density (g/cc)








Measured
na
12.12
na
na
12.10
12.31


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-K





Glass
Ex. 61
Ex. 62
Ex. 63
Ex. 64
Ex. 65
Ex. 66





















SiO2
62.35
62.35
62.35
64.23
62.73
62.73


Al2O3
20.75
20.75
19.25
19.63
21.13
19.63


CaO
5.65
4.15
5.65
4.53
4.53
6.03


MgO
10.55
12.05
12.05
10.93
10.93
10.93


Na2O
0.70
0.70
0.70
0.70
0.70
0.70


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2534
2516
2498
2560
2547
2514


Viscosity








(° F.)








Measured
2441
2444
2400
2443
2482
2385


Liquidus








Temp (° F.)








Measured ΔT
93
72
98
117
65
129


(° F.)








Measured
na
na
na
na
na
670


Strength (KPsi)








Measured
na
2.545
2.556
na
na
2.546


Density (g/cc)








Measured
na
na
na
na
na
12.21


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-L





Glass
Ex. 67
Ex. 68
Ex. 69
Ex. 70
Ex. 71
Ex. 72





















SiO2
62.73
62.10
63.10
63.10
63.10
62.85


Al2O3
19.63
20.00
19.00
20.00
20.00
19.75


CaO
4.53
4.90
4.90
3.90
4.90
4.65


MgO
12.43
11.30
11.30
11.30
10.30
11.05


Na2O
0.70
0.70
0.70
0.70
0.70
0.70


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
1.00
1.00
1.00
1.00
1.00


Measured
2504
2492
2508
2522
2531
2509


Viscosity








(° F.)








Measured
2369
2433
2352
2470
2406
2425


Liquidus








Temp (° F.)








Measured ΔT
135
59
156
52
125
84


(° F.)








Measured
676
na
na
na
na
na


Strength (KPsi)








Measured
2.547
na
na
na
na
na


Density (g/cc)








Measured
12.42
na
na
na
na
na


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-M





Glass
Ex. 73
Ex. 74
Ex. 75
Ex. 76
Ex. 77
Ex. 78





















SiO2
62.56
63.55
62.56
60.57
60.57
61.00


Al2O3
17.87
18.87
18.87
18.87
19.86
19.00


CaO
8.94
6.95
6.95
7.94
8.94
8.00


MgO
9.93
9.93
10.92
11.92
9.93
12.00


Na2O
0.70
0.70
0.70
0.70
0.70
0.00


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2504
2563
2506
2430
2472
2448


Viscosity








(° F.)








Measured
2273
2353
2330
2306
2343
2358


Liquidus








Temp (° F.)








Measured ΔT
231
210
176
124
129
90


(° F.)








Measured
na
na
na
na
na
na


Strength (KPsi)








Measured
2.553
2.532
2.550
2.583
2.573
2.582


Density (g/cc)








Measured
12.44
12.29
12.70
12.84
12.64
12.84


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na






















TABLE 2-N





Glass
Ex. 79
Ex. 80
Ex. 81
Ex. 82
Ex. 83
Ex. 84





















SiO2
62.16
62.12
62.07
63.00
63.12
64.32


Al2O3
19.12
19.22
19.23
18.00
18.84
18.54


CaO
8.03
7.94
8.01
9.00
4.82
4.52


MgO
9.69
9.64
9.76
10.00
12.52
12.22


Na2O
1.00
0.97
0.99
0.00
0.70
0.40


TiO2
0.00
0.02
0.01
0.00
0.00
0.00


Fe2O3
0.00
0.05
0.04
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2512.75
2491
na
2518
2490
2534


Viscosity (° F.)








Measured
2268
na
na
2322
2442
2428


Liquidus Temp (° F.)








Measured
244.75
na
na
196
48
106


ΔT (° F.)








Measured
na
664
na
na
na
na


Strength (KPsi)








Measured
2.549
na
na
2.560
2.546
2.533


Density (g/cc)








Measured
na
12.62
na
12.64
12.77
na


Modulus (MPsi)








Softening
na
960
na
na
na
na


Point (° F.)








CTE in/in/(° F.)
2.32
na
na
na
na
na






















TABLE 2-O





Glass
Ex. 85
Ex. 86
Ex. 87
Ex. 88
Ex. 89
Ex. 90





















SiO2
62.82
62.82
62.82
62.82
62.16
62.96


Al2O3
20.04
18.54
18.54
18.54
19.12
18.92


CaO
4.52
6.02
4.52
4.52
8.03
7.83


MgO
12.22
12.22
13.72
12.22
9.69
9.49


Na2O
0.40
0.40
0.40
1.90
1.00
0.80


TiO2
0.00
0.00
0.00
0.00
0.00
0.00


Fe2O3
0.00
0.00
0.00
0.00
0.00
0.00


Fluorine
0.00
0.00
0.00
0.00
0.00
0.00


Measured
2534
2506
2489
2492
2514
2532


Viscosity








(° F.)








Measured
2478
2363.5
2446
2364.5
2262
2285


Liquidus








Temp (° F.)








Measured ΔT
56
142.5
43
127.5
252
247


(° F.)








Measured
na
na
na
na
na
na


Strength (KPsi)








Measured
2.548
2.555
2.557
2.538
2.556
2.552


Density (g/cc)








Measured
na
na
na
na
12.62
na


Modulus








(MPsi)








Softening Point
na
na
na
na
na
na


(° F.)








CTE in/in/(° F.)
na
na
na
na
na
na





















TABLE 2-P






Glass
Ex. 91
Ex. 92
Ex. 93
Ex. 94





















SiO2
61.96
61.96
61.96
61.96



Al2O3
19.92
18.92
18.92
18.92



CaO
7.83
8.83
7.83
7.83



MgO
9.49
9.49
10.49
9.49



Na2O
0.80
0.80
0.80
1.80



TiO2
0.00
0.00
0.00
0.00



Fe2O3
0.00
0.00
0.00
0.00



Fluorine
0.00
0.00
0.00
0.00



Measured
2524
2489
2488
2504



Viscosity







(° F.)







Measured
2337
2274.5
2333
2267.5



Liquidus







Temp (° F.)







Measured ΔT
187
214.5
155
236.5



(° F.)







Measured
na
na
na
na



Strength (KPsi)







Measured
2.561
2.568
2.567
2.557



Density (g/cc)







Measured
na
na
na
na



Modulus







(MPsi)







Softening Point
na
na
na
na



(° F.)







CTE in/in/(° F.)
na
na
na
na









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.


Example 2
Corrosion Resistance of Glass Fibers Formed from the Inventive Composition in 10% HNO3

Samples from rovings of glass fibers formed in accordance with the inventive composition and a sample from a roving of boron-free fibers were desized by heating the fibers in a furnace at 625° C. for 30 minutes. The bare fibers were then permitted to cool in a dessicator. Once the fibers were cool, the samples were taken from the dessicator and each of the bare fiber samples were weighed (W1) and recorded. A sample of basalt was also obtained, weighed (W1), and recorded. The samples (i.e., inventive bare fibers, boron-free bare fibers, and basalt) were individually placed in flasks to which 150 ml of 10% HNO3 was added. The flasks were placed in a bath at 96° C. for 24 hours, 100 hours, and 240 hours. At the end of their respective time period, the samples of inventive fibers, boron-free fibers, and basalt were removed from the flasks and filtered through filter paper. The paper filters were placed in cleaned crucibles and heated in a furnace at 625° C. for 30 minutes. The samples were then placed in a dessicator to cool. After the samples were cool, the final weight (W2) of each of the samples was recorded. The percent weight loss of the fibers and basalt was calculated using the formula 100·((W1−W2)/W1).


The results of the percent weight loss of the glass fibers formed from the inventive composition compared to the percent weight loss of the boron-free fibers and basalt are graphically illustrated in FIG. 1. Percent weight loss is a measure of the corrosion resistance of a particular substance, such as glass fibers. In particular, the lower the percent weight loss for a glass fiber in a corrosive substance, the higher the corrosion resistance for that glass fiber. As shown in FIG. 1, fibers formed from the inventive composition had a percent weight loss that was equal to or better than the boron-free fibers. Thus, the inventive glass fibers demonstrated a corrosion resistance in nitric acid that was equal to or better than the boron-free fibers. It can be concluded that the glass fibers formed from the inventive composition would form commercially acceptable products with respect to corrosion resistance compared to current products formed from boron-free glass fibers. It is also clearly shown in FIG. 1 that the inventive fibers had a lower percent weight loss than the basalt and therefore had superior corrosion resistance compared to the basalt.


Example 3
Corrosion Resistance of Glass Fibers Formed from the Inventive Composition in 5% H2SO4

Samples from rovings of glass fibers formed in accordance with the inventive composition, a sample from a roving of boron-free fibers, a sample from a roving of E-glass fibers, and a sample from a roving of E-CR glass were desized by heating the fibers in a furnace at 625° C. for 30 minutes. The bare fibers were then permitted to cool in a dessicator. Once the fibers were cool, the samples were taken from the dessicators and each of the bare fiber samples were weighed (W1) and recorded. A sample of basalt was also obtained, weighed (W1), and recorded. The samples (i.e., inventive bare fibers, boron-free bare fibers, E-glass bare fibers, E-CR bare fibers, and basalt) were individually placed in flasks and 150 ml of 5% H2SO4 was added. The flasks were then placed in a bath at 96° C. for 24 hours, 100 hours, and 240 hours. At the end of their respective time period, the samples of inventive fibers, boron-free fibers, E-glass fibers, E-CR glass fibers, and basalt were removed from the flasks and filtered through filter paper. The paper filters were placed in cleaned crucibles and heated in a furnace at 625° C. for 30 minutes. The samples were then placed in a dessicator to cool. After the samples were cooled, the weight (W2) of each of the samples was recorded. The percent weight loss of the fibers and basalt was calculated using the formula 100·((W1−W2)/W1).


The percentage of weight loss of the glass fibers and basalt is illustrated in FIG. 2. As discussed above with respect to Example 2, a glass fiber's resistance to corrosion is reflected by the percentage of weight lost. In other words, the more weight that is lost from the glass fibers over time while in the acidic solution, the less the fiber is resistant to corrosion. As depicted in FIG. 2, the inventive glass fibers demonstrated a corrosion resistance in sulfuric acid that was equal to or better than boron-free glass fibers and E-CR glass fibers. It can be concluded that the glass fibers formed from the inventive composition would form commercially acceptable products with respect to corrosion resistance compared to current products formed from boron-free glass fibers and E-CR glass fibers. In addition, fibers formed from the inventive composition were clearly superior in their resistance to corrosion compared to E-glass fibers. This superior corrosion resistance of the inventive glass fibers over E-glass fibers would enable products formed from fibers made with the inventive composition to have a longer life span.


Example 4
Corrosion Resistance of Glass Fibers Formed from the Inventive Composition in H2O

Samples from rovings of glass fibers formed in accordance with the inventive composition and a sample from a roving of boron-free fibers were desized by heating in a furnace at 625° C. for 30 minutes. The bare fibers were then permitted to cool in a dessicator. Once the fibers were cool, the samples were taken from the dessicator and each of the bare fiber samples were weighed (W1) and recorded. A sample of basalt was also obtained, weighed (W1), and recorded. The samples (i.e., inventive bare fibers, boron-free bare fibers, and basalt) were individually placed in flasks to which 150 ml of H2O was added. The flasks were then placed in a bath at 96° C. for 24 hours, 100 hours, and 240 hours. At the end of their respective time period, the samples of inventive fibers, boron-free fibers, and basalt were removed from the flasks and filtered through filter paper. The paper filters were placed in cleaned crucibles and heated in a furnace at 625° C. for 30 minutes. The samples were then placed in a dessicator to cool. After the samples were cooled, the weight (W2) of each of the samples was recorded. The percent weight loss was calculated using the formula 100·((W1−W2)/W1).


The results of the percent weight loss of the glass fibers formed from the inventive composition compared to the weight loss of the boron-free fibers and basalt are graphically illustrated in FIG. 3. As depicted in FIG. 3, the inventive composition demonstrated less weight loss than the boron-free fibers. Thus, the inventive fibers had an improved corrosion resistance in water compared to the boron-free fibers. In addition, the inventive glass fibers demonstrated a corrosion resistance in water that was equal to or better than the basalt.


Example 5
Corrosion Resistance of Inventive Glass Fibers Compared to Boron-Free Glass Fibers in Various Corrosive Media

Glass fibers were made by conventional glass forming techniques utilizing the inventive composition. In particular, molten glass containing the components of the inventive composition in the desired amounts is pulled or attenuated through holes or orifices in the bottom of a bushing to form individual glass filaments. The average filament diameter was determined to be 17 μm and the bundle tex was 1200 tex. Strands of glass fibers were formed by gathering the individual filaments together.


Five samples composed of approximately 30 yards of the inventive fiber strands were used for testing. In addition, five samples of approximately 30 yards of boron-free fiber strands (average filament diameter 17 μm with a bundle tex of 1200 tex) were obtained. One 30 yard sample of the inventive fiber strands and one 30 yard sample of the boron-free fiber strands were heated in accordance with the parameters set forth in ASTM D2584 to determine the percent of sizing on the glass fibers.


The remaining eight samples were placed in eight individual glass jars. Two jars (one with an inventive glass fiber strand sample and one with a boron-free glass strand sample) were filled with deionized water. Two jars (one with an inventive glass fiber strand sample, one with a boron-free glass strand sample) were filled with 5% salt water. Two jars (one with an inventive glass fiber strand sample and one with a boron-free glass strand sample) were filled with 1N sulfuric acid. Two jars (one with an inventive glass fiber strand sample and one with a boron-free glass strand sample) were filled with 1N nitric acid. Lids were placed on each of the jars and the jars were stored at 25° C. for 500 hours.


After 500 hours had elapsed, all eight samples were triple rinsed with 150° F. (65.5° C.) deionized water, dried, and weighed. The weight of each of the samples was recorded. The samples were then heated in accordance with ASTM D2584 to burn off any remaining sizing. The percent weight loss of the fibers was calculated using the formula 100·(W1−W2/W1), where W1 was the initial weight of the sample and W2 was the weight after treatment with the corrosive substance. The final percent glass loss was determined by subtracting the size LOI from the percent weight loss determined from the final weight burn-off. The results of the experiment are set forth in Table 3.















TABLE 3










Weight








After






















Five

Final









hours
%
Weight
%
Number

%



Glass
Initial
@ 250
Weight
Burn-
Weight
of
Size
Glass



Type
Weight
° F.
Loss
Off
Loss
Hours
LOI
Loss





Deionized
Boron-
32.3055
32.195
0.34
32.079
0.70
504
0.61
0.09


water
Free










Deionized
Inventive
32.3297
32.235
0.29
32.137
0.60
504
0.57
0.03


water











5%
Boron-
32.3280
32.257
0.22
32.108
0.68
504
0.61
0.07


Saltwater
Free










5%
Inventive
32.4303
32.381
0.15
32.237
0.60
504
0.57
0.03


Saltwater











5%
Boron-
32.2758
32.114
0.50
32.014
0.81
504
0.61
0.20


Sulfuric
Free










Acid











5%
Inventive
32.3811
32.262
0.37
32.161
0.68
504
0.57
0.11


Sulfuric











Acid











IN Nitric
Boron-
32.2955
32.150
0.45
32.041
0.79
504
0.61
0.18


Acid
Free










IN Nitric
Inventive
32.4569
32.346
0.34
32.236
0.68
504
0.57
0.11


Acid









As shown in Table 3, the inventive fibers had glass loss percents that were significantly less than the percent of glass lost the boron-free glass fibers. The amount of glass that is eroded by the corrosive substance is another method of determining a fiber's resistance to corrosion. For example, the more glass that is eroded by the corrosive substance during a particular time period, the less the fiber is resistant to corrosion. From the results set forth in Table 3, it can be concluded that the fibers formed from the inventive composition had superior corrosion resistance compared to boron-free fibers. It can also be concluded that the inventive glass fibers would form commercial products that have corrosive properties at least equal to, and even superior to, current products formed from boron-free glass fibers.


Example 6
Three Point Bending Strength Retention Test

Laminates formed from E-glass fibers, boron-free fibers, and inventive fibers were formed by dry winding the glass fibers and utilizing a conventional vacuum-assisted resin infusion process. The laminates thus formed were cured for 24 hours at 35° C., followed by a post-cure for 4 hours at 90° C. Samples having a thickness of 2.09 mm and a width of 13.44 mm were obtained. Samples of the laminates from the E-glass fibers, boron-free fibers, and inventive fibers were tested for their bending strength retention prior to aging. The results were recorded. Samples from each of the laminates were immersed in 5% H2SO4 under constant strain at room temperature for one month. In particular, the samples were tested with a four point bending test at two imposed strain levels (1.03% strain (load 1) and a 1.40% strain (load 2)) for one month. It was observed that the E-glass laminate samples broke after 48 hours. After one month, neither the boron-free laminate samples nor the inventive fiber laminate samples were broken.


To evaluate the bending strength retention, a three point bending test was utilized. In this test, the aged samples were placed on a testing apparatus in which the sample is horizontally stabilized by two supports separated a distance from each other and a force is applied vertically (i.e., downwardly) to the center of the samples. The force is applied until the sample breaks. The results of the three-point bending test are illustrated in FIG. 4. It can be seen that the inventive fiber laminate samples have a higher initial strength and higher strengths after aging compared to both the boron-free glass laminate samples and the E-glass laminate samples. Thus, it can be concluded that fibers formed from the inventive composition possess superior strength compared to both E-glass fibers and boron-free fibers, thus enabling a longer life span of composite products formed from fibers made with the inventive composition.


Example 6
ISO Classification of Inventive Fibers

Inventive fibers, boron-free fibers, and E-glass fibers were tested for resistance to hydrolysis according to the standards set forth in ISO 720. Hydrolysis is one form of corrosion. According to ISO 720, utilizing HCl at 0.02N, classification HGA 1 is 0.10 ml, HGA 2 is 0.85 ml, and HGA 3 is 1.50 ml. The results are set forth in Table 4.













TABLE 4






Example 1
Example 2
Average




(ml 0.02 N
(ml 0.02 N
(ml 0.02 N
ISO 720



HCl)
HCl)
HCl)
Classification







Inventive
0.08
0.08
0.08
HGA 1


Glass Fibers






Boron-Free
0.14
0.14
0.14
HGA 2


Glass Fibers






E-Glass fibers
0.14
0.14
0.14
HGA 2









As shown in Table 4, based on the average weight loss, the inventive glass fibers were placed in the classification HGA 1, whereas the boron-free fibers and the E-glass fibers were classified as HGA 2. A classification of HGA 1 indicates a better resistance to hydrolysis (i.e., corrosion) than a classification of HGA 2. Thus, composite products formed from the inventive glass fibers would be expected to have a better hydrolysis resistance than products formed from boron-free glass fibers or E-glass fibers.


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 high performance glass fiber produced from a composition comprising: SiO2 in an amount from about 60.5 to about 70.5 weight percent of the total composition;Al2O3 in an amount from about 10 to about 24.5 weight percent of the total composition;RO in an amount from about 10 to about 24.0 weight percent of the total composition, said RO being the sum of MgO, SrO, CaO, and BaO, wherein the amount of CaO present in said RO comprises at least 4 weight percent of the total composition and the amount of MgO comprises at least 5 weight percent of the total composition;less than 1 weight percent TiO2; andalkali metal oxides in an amount from about 0 to about 3 weight percent of the total composition,wherein said glass fiber is resistant to corrosion and said composition has a ΔT of at least about 80° F.
  • 2. The high performance fiber of claim 1, further comprising: less than 4 weight percent of the total composition of at least one compound selected from the group consisting of ZnO, SO3, Fluorine, B2O3 and Fe2O3.
  • 3. The high performance fiber of claim 1, wherein said glass has a fiberizing temperature less than about 2650° F. and a ΔT for the glass is at least about 120° F.
  • 4. The high performance fiber of claim 1, wherein said glass has a strength greater than about 600 KPsi.
  • 5. The high performance glass fiber of claim 1, wherein said glass fiber has a modulus greater than about 12.0 MPsi.
  • 6. The high performance glass fiber of claim 1, wherein said glass fiber has a coefficient of thermal expansion (CTE) between about 2.28×10−6 in/in/° F. and about 2.77×106 in/in/° F.
  • 7. The high performance glass fiber of claim 1, wherein said glass fiber has a resistance to corrosion that is at least equal to a corrosion resistance of boron-free glass fibers and E-glass fibers.
  • 8. The high performance glass fiber of claim 1, wherein said glass fiber has a classification of HGA 1 according to the standards set forth in ISO 720.
  • 9. A fiberglass reinforced article comprising: glass fibers formed from a composition including: SiO2 in an amount from about 60.5 to about 70.5 weight percent of the total composition;Al2O3 in an amount from about 10 to about 24.5 weight percent of the total composition;RO in an amount from about 10 to about 24.0 weight percent of the total composition, said RO being the sum of MgO, SrO, CaO, and BaO, wherein the amount of CaO comprises at least 4 weight percent of the total composition and the amount of MgO comprises at least 5 weight percent of the total composition;Na2O in an amount from about 0.25 to about 2 weight percent; andalkali metal oxides in an amount from about 0 to about 3 weight percent of the total composition, wherein said composition has a ΔT of at least about 80° F., and
  • 10. The fiberglass reinforced article of claim 9, wherein said glass fibers further include less than 4 weight percent of the total composition of at least one compound selected from the group consisting of ZnO, SO3, Fluorine, B2O3, TiO2 and Fe2O3.
  • 11. The fiberglass reinforced article of claim 9, wherein said glass fibers have a resistance to corrosion that is at least equal to a corrosion resistance of boron-free glass fibers and E-glass fibers.
  • 12. The fiberglass reinforced article of claim 9, wherein said glass fibers have a classification of HGA 1 according to the standards set forth in ISO 720.
  • 13. The fiberglass reinforced article of claim 9, wherein said glass fibers have a fiberizing temperature less than about 2650° F. and a ΔT for the glass is at least about 120° F.
  • 14. The fiberglass reinforced article of claim 9, wherein said glass fibers have a strength greater than about 600 KPsi and a modulus greater than about 12.0 MPsi.
  • 15. The fiberglass reinforced article of claim 9, wherein said glass fibers have a coefficient of thermal expansion (CTE) between about 2.28×10−6 in/in/° F. and about 2.77×10−6 in/in/° F.
  • 16. A method of forming a high performance glass fiber comprising: providing a molten glass composition including: SiO2 in an amount from about 60.5 to about 70.5 weight percent of the total composition;Al2O3 in an amount from about 10 to about 24.5 weight percent of the total composition;RO in an amount from about 10 to about 24.0 weight percent of the total composition, said RO being the sum of MgO, SrO, CaO, and BaO, wherein the amount of CaO comprises at least 4 weight percent of the total composition and the amount of MgO comprises at least 5 weight percent of the total composition;less than 1 weight percent TiO2; andalkali metal oxides in an amount from about 0 to about 3 weight percent of the total composition; anddrawing said molten glass composition through a bushing to form a high performance glass fiber, said high performance glass fiber having a resistance to corrosion.
  • 17. The method of forming a high performance glass fiber according to claim 16, wherein said molten glass composition further include less than 4 weight percent of the total composition of at least one compound selected from the group consisting of ZnO, SO3, Fluorine, B2O3, and Fe2O3.
  • 18. The method of forming a high performance glass fiber according to claim 16, wherein said high performance glass fiber has a classification of HGA 1 according to the standards set forth in ISO 720.
  • 19. The method of forming a high performance glass fiber according to claim 16, wherein said high performance glass fiber has a corrosion resistance that is at least equal to a corrosion resistance of boron-free glass fibers and E-glass fibers.
  • 20. The method of forming a high performance glass fiber according to claim 16, wherein said reinforced article is a blade for a wind turbine.
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent application Ser. No. 11/267,739 entitled “Composition For High Performance Glass, High Performance Glass Fibers, and Articles Therefrom” filed Nov. 4, 2005, the content of which is incorporated by reference in its entirety.

US Referenced Citations (142)
Number Name Date Kind
3044888 Provance Jul 1962 A
3189471 Thomas Jun 1965 A
3220915 Shannon Nov 1965 A
3360386 Kelley et al. Dec 1967 A
3402055 Harris et al. Sep 1968 A
3408213 Provance et al. Oct 1968 A
3484259 Lewis et al. Dec 1969 A
3498805 STalego Mar 1970 A
3524738 Grubb et al. Aug 1970 A
3535096 Bour et al. Oct 1970 A
3709705 Hagedorn Jan 1973 A
3804646 Dumbaugh, Jr. Apr 1974 A
3833388 Ohlberg Sep 1974 A
3861926 Irlam et al. Jan 1975 A
3876481 Erickson et al. Apr 1975 A
3887386 Majumdar Jun 1975 A
3892581 Burgman et al. Jul 1975 A
3902881 Pirooz Sep 1975 A
3904423 Guthrie Sep 1975 A
3945838 Erickson et al. Mar 1976 A
4002482 Coenen Jan 1977 A
4012131 Krohn Mar 1977 A
4046948 Zlochower Sep 1977 A
4063001 Zlochower Dec 1977 A
4090882 Rauschenfels May 1978 A
4199364 Neely Apr 1980 A
4325724 Froberg Apr 1982 A
4366251 Rapp Dec 1982 A
4375527 Zahner Mar 1983 A
4386164 Moser May 1983 A
4491951 Dunn Jan 1985 A
4569471 Ingemansson Feb 1986 A
4582748 Eastes Apr 1986 A
4764487 Lewis Aug 1988 A
4824806 Yokoi et al. Apr 1989 A
4857485 Brennan et al. Aug 1989 A
4882302 Horiuchi et al. Nov 1989 A
4892846 Rogers et al. Jan 1990 A
4935291 Gunnink Jun 1990 A
4976587 Johnston et al. Dec 1990 A
5212121 Omata May 1993 A
5248637 Taneda et al. Sep 1993 A
5302444 Jackson et al. Apr 1994 A
5332699 Olds et al. Jul 1994 A
5474425 Lawlor Dec 1995 A
5569629 TenEyck et al. Oct 1996 A
5576252 Rapp et al. Nov 1996 A
5585312 TenEyck et al. Dec 1996 A
5691255 Jensen et al. Nov 1997 A
5719092 Arrington Feb 1998 A
5789329 Eastes et al. Aug 1998 A
5819614 Jander Oct 1998 A
5843853 Heitmann Dec 1998 A
5851932 Dickson et al. Dec 1998 A
5935886 Jensen et al. Aug 1999 A
5948535 Chiurlo et al. Sep 1999 A
5962354 Fyles et al. Oct 1999 A
5997977 Zou et al. Dec 1999 A
6063470 Zou et al. May 2000 A
6069100 Naumann et al. May 2000 A
6089021 Senanayake Jul 2000 A
6101847 Shamp Aug 2000 A
6136735 Gallo et al. Oct 2000 A
6156683 Grove-Rasmussen et al. Dec 2000 A
6169047 Nishizawa et al. Jan 2001 B1
6214429 Zou et al. Apr 2001 B1
6237369 LeBlanc et al. May 2001 B1
6248678 Pinckney Jun 2001 B1
6300264 Ohara Oct 2001 B1
6306786 Koyama et al. Oct 2001 B1
6314760 Chenoweth Nov 2001 B1
6329310 Peuchert et al. Dec 2001 B1
6358873 Stewart Mar 2002 B1
6376403 Koyama et al. Apr 2002 B1
6399527 Kishimoto et al. Jun 2002 B1
6403676 Jia et al. Jun 2002 B1
6422041 Simpson et al. Jul 2002 B1
6451720 Kishimoto Sep 2002 B1
6457943 Olsen et al. Oct 2002 B1
6458436 Hansen et al. Oct 2002 B1
6496706 Jou et al. Dec 2002 B1
6540508 Simpson et al. Apr 2003 B1
6579599 Blum et al. Jun 2003 B1
6686304 Wallenberger Feb 2004 B1
6794322 Sircar Sep 2004 B2
6809050 McGinnis et al. Oct 2004 B1
6818575 Wallenberger Nov 2004 B2
6867158 Peuchert Mar 2005 B2
6933045 Tamura Aug 2005 B2
6933252 Pierce Aug 2005 B2
6998361 Lewis Feb 2006 B2
7022634 Hamilton et al. Apr 2006 B2
7189671 Lewis Mar 2007 B1
7259118 Jubb et al. Aug 2007 B2
7285510 Sakaguchi et al. Oct 2007 B2
7449419 Li Nov 2008 B2
7509819 Baker et al. Mar 2009 B2
7781355 Berthereau et al. Aug 2010 B2
7799713 Hofmann et al. Sep 2010 B2
7811954 Berthereau et al. Oct 2010 B2
7823417 Hofmann et al. Nov 2010 B2
20010011058 Tamura Aug 2001 A1
20020000101 Chenoweth Jan 2002 A1
20020045528 Kusuno et al. Apr 2002 A1
20030018855 McWilliams et al. Jan 2003 A1
20030077178 Stearns Apr 2003 A1
20030100431 Koyo et al. May 2003 A1
20030166446 Lewis Sep 2003 A1
20030188554 Baker et al. Oct 2003 A1
20030207748 Wallenberger Nov 2003 A1
20030224922 Wallenberger Dec 2003 A1
20040092379 Lewis May 2004 A1
20040220038 Wolff Nov 2004 A1
20050009683 Hamilton et al. Jan 2005 A1
20050014624 Jubb et al. Jan 2005 A1
20050031703 Beier et al. Feb 2005 A1
20050084440 Chacon et al. Apr 2005 A1
20050085369 Jensen Apr 2005 A1
20050090377 Shelestak et al. Apr 2005 A1
20050107238 Li May 2005 A1
20050130825 Kravchenko et al. Jun 2005 A1
20050232828 Merry Oct 2005 A1
20050234216 Klein et al. Oct 2005 A1
20060001005 Kishimoto et al. Jan 2006 A1
20060003884 Nishizawa et al. Jan 2006 A1
20060257240 Naskali et al. Nov 2006 A1
20070087139 Creux et al. Apr 2007 A1
20070105701 Hoffmann et al. May 2007 A1
20070107220 Bakhuis et al. May 2007 A1
20080009403 Hofmann et al. Jan 2008 A1
20080053152 Kurachi et al. Mar 2008 A1
20080141721 Adams et al. Jun 2008 A1
20090286440 Lecomte et al. Nov 2009 A1
20100069220 McGinnis Mar 2010 A1
20100093511 Berthereau et al. Apr 2010 A1
20100160139 McGinnis Jun 2010 A1
20100160140 McGinnis Jun 2010 A1
20100162772 McGinnis Jul 2010 A1
20100184345 Lalande et al. Jul 2010 A1
20110000263 Hofmann Jan 2011 A1
20110003678 Hofmann Jan 2011 A1
20110039681 Lecomte et al. Feb 2011 A1
Foreign Referenced Citations (76)
Number Date Country
2528923 Dec 2004 CA
1113893 Dec 1995 CN
1243501 Feb 2000 CN
1392870 Jan 2003 CN
1678654 Oct 2005 CN
101580344 Nov 2009 CN
1015979140 Dec 2009 CN
101691278 Apr 2010 CN
101838110 Sep 2010 CN
101549958 Jan 2011 CN
1496520 Aug 1969 DE
500325 Aug 1992 EP
931774 Jul 1999 EP
1357393 Apr 1964 FR
1435073 Apr 1966 FR
1534135 Dec 1968 FR
1589410 Mar 1970 FR
2223328 Oct 1974 FR
2692248 Dec 1993 FR
2856055 Dec 2004 FR
2879591 Jun 2006 FR
2916438 Nov 2008 FR
428 720 May 1935 GB
1006524 Oct 1965 GB
1147718 Apr 1969 GB
1209244 Oct 1970 GB
1531287 Nov 1978 GB
45-011228 May 1970 JP
51-055308 May 1976 JP
58 064243 Apr 1983 JP
58064243 Apr 1983 JP
58-088138 May 1983 JP
1-189985 Jul 1989 JP
1-239039 Sep 1989 JP
3-112650 May 1991 JP
4-050144 Feb 1992 JP
6-211543 Aug 1994 JP
6-219780 Aug 1994 JP
6-305773 Nov 1994 JP
7-010598 Jan 1995 JP
8-231240 Sep 1996 JP
2582361 Feb 1997 JP
11-021147 Jan 1999 JP
11-21147 Jan 1999 JP
2000-247677 Sep 2000 JP
2000-247683 Sep 2000 JP
2001-206733 Jul 2001 JP
2001-316961 Nov 2001 JP
2002-003237 Jan 2002 JP
2002-060252 Feb 2002 JP
2002-069941 Mar 2002 JP
2002-081022 Mar 2002 JP
2002-154843 May 2002 JP
2002-293574 Oct 2002 JP
2003-137590 May 2003 JP
2003-160350 Jun 2003 JP
2003-171143 Jun 2003 JP
2003-183031 Jul 2003 JP
2003-239847 Aug 2003 JP
2003-321247 Nov 2003 JP
2004-091307 Mar 2004 JP
9931021 Jun 1999 WO
0015526 Mar 2000 WO
0220419 Mar 2002 WO
0242233 May 2002 WO
2004020506 Mar 2004 WO
WO 2004094794 Nov 2004 WO
2005092808 Oct 2005 WO
2005093227 Oct 2005 WO
2006064164 Jun 2006 WO
WO 2007055964 May 2007 WO
WO 2007055968 May 2007 WO
2008073585 Jun 2008 WO
2010075258 Jul 2010 WO
2010075262 Jul 2010 WO
2010075267 Jul 2010 WO
Non-Patent Literature Citations (163)
Entry
Machine Translation of JP 2002-154843, May 28, 2002.
PCT Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, or the Declaration, Application PCT/US06/42437 dated Apr. 30, 2007.
PCT Notification of Transmittal of the International Search Report and the Written Opinion of the International Searching Authority, or the Declaration, Application PCT/US06/42406 dated May 8, 2007.
European Search Report 06 82 7125 dated Dec. 10, 2008.
Thomson Scientific, London, GB; AN 1983 50368K Database WPI Week 198321.
Conference paper by G. Fredell, “Fiber metal laminates for improved structural integrity,” 1992.
Article by P. Joosee, Literature search of mechanical properties of fiber-reinforced plastics for wind turbine rotors, Dec. 1988.
U.S. Office Action, U.S. Appl. No. 11/267,739 dated Dec. 18, 2008.
U.S. Office Action, U.S. Appl. No. 11/267,739 dated Sep. 24, 2008.
PCT Notification Concerning Transmittal of International Preliminary Report on Patentability, Application PCT/US06/042406 dated May 15, 2008.
US Office Action, U.S. Appl. No. 11/267,702 dated Sep. 24, 2008.
US Office Action, U.S. Appl. No. 11/267,702 dated Dec. 23, 2008.
Office action from U.S. Appl. No. 09/703,234 dated Apr. 15, 2002.
Office action from U.S. Appl. No. 09/703,234 dated Sep. 6, 2002.
Advisory action from U.S. Appl. No. 09/703,234 dated Nov. 19, 2002.
Office action from U.S. Appl. No. 09/703,234 dated Feb. 4, 2003.
Office action from U.S. Appl. No. 09/703,234 dated Jul. 11, 2003.
Advisory action from U.S. Appl. No. 09/703,234 dated Oct. 24, 2003.
Office action from U.S. Appl. No. 09/703,234 dated Dec. 16, 2003.
Notice of Allowance from U.S. Appl. No. 09/703,234 dated Jul. 6, 2004.
Office action from U.S. Appl. No. 10/560,068 dated Aug. 1, 2008.
Office action from U.S. Appl. No. 10/560,068 dated Dec. 15, 2008.
Advisory Action from U.S. Appl. No. 10/560,068 dated Feb. 25, 2009.
Office action from U.S. Appl. No. 10/560,068 dated May 7, 2009.
Office action from U.S. Appl. No. 10/560,068 dated Nov. 5, 2009.
Advisory Action from U.S. Appl. No. 10/560,068 dated Mar. 16, 2010.
Panel Decision of Pre-Appeal Brief from U.S. Appl. No. 10/560,068 dated Apr. 29, 2010.
Examiner's Answer from U.S. Appl. No. 10/560,068 dated Aug. 3, 2010.
Notice of Allowance from U.S. Appl. No. 11/267,702 dated Jul. 29, 2009.
Office action from U.S. Appl. No. 11/267,702 dated Dec. 3, 2009.
Notice of Allowance from U.S. Appl. No. 11/267,702 dated Jun. 16, 2010.
Notice of Allowance from U.S. Appl. No. 11/267,739 dated Jul. 13, 2009.
Office action from U.S. Appl. No. 11/267,739 dated Dec. 3, 2009.
Notice of Allowance from U.S. Appl. No. 11/267,739 dated Apr. 7, 2010.
Office action from U.S. Appl. No. 11/722,039 dated Oct. 28, 2009.
Office action from U.S. Appl. No. 11/722,039 dated Jun. 22, 2010.
Interview Summary from U.S. Appl. No. 11/722,039 dated Sep. 21, 2010.
Office action from U.S. Appl. No. 11/722,039 dated Oct. 19, 2010.
Office action from U.S. Appl. No. 11/722,039 dated Jun. 7, 2011.
Office action from U.S. Appl. No. 12/341,985 dated Nov. 17, 2010.
Office action from U.S. Appl. No. 12/341,985 dated Apr. 21, 2011.
Notice of Allowance from U.S. Appl. No. 12/341,985 dated Oct. 12, 2011.
Office action from U.S. Appl. No. 12/344,130 dated Nov. 17, 2010.
Office action from U.S. Appl. No. 12/344,130 dated Apr. 20, 2011.
Notice of Allowance from U.S. Appl. No. 12/344,130 dated Oct. 11, 2011.
Office action from U.S. Appl. No. 12/403,955 dated Dec. 9, 2011.
Office action from U.S. Appl. No. 12/847,206 dated Feb. 22, 2011.
Office action from U.S. Appl. No. 12/847,206 dated Oct. 14, 2011.
Office action from U.S. Appl. No. 12/880,289 dated Jul. 20, 2011.
Notice of Allowance from U.S. Appl. No. 12/880,289 dated Dec. 22, 2011.
International Search Report from PCT/FR04/01431 dated Jun. 11, 2003.
International Search Report from PCT/FR05/51090 date Dec. 2, 2004.
International Search Report and Written Opinion from PCT/US09/68949 dated May 7, 2010.
International Search Report and Written Opinion from PCT/US09/68955 dated May 7, 2010.
International Search Report and Written Opinion from PCT/US09/68965 dated May 7, 2010.
Office action from Australian Application No. 2006312015 dated May 5, 2011.
Office action from Australian Application No. 2006312106 dated May 5, 2011.
Office action from Chinese Application No. 200580043075.7 dated Dec. 7, 2011.
Office action from Chinese Application No. 200680041104.0 dated Aug. 4, 2010.
Office action from Chinese Application No. 200680041104.0 dated Mar. 22, 2011.
Office action from Chinese Application No. 200680041104.0 dated Jul. 14, 2011.
Office action from European Application No. 01987549.1 dated Aug. 5, 2011.
Office action from European Application No. 05825565.4 dated Dec. 14, 2007.
Office action from European Application No. 05825565.4 dated Nov. 19, 2010.
Office action from European Application No. 05825565.4 dated May 9, 2011.
Office action from European Application No. 05825565.4 dated Mar. 31, 2011.
Communication from EP application No. 06827125.3 dated Jun. 4, 2009 which includes the EP OA from Feb. 13, 2009 and the Search Report dated Dec. 10, 2008.
Office action from Indian Application No. 2108/KOLNP/2007 dated Jun. 28, 2011.
Office action from Japanese Application No. 2007-546144 dated Sep. 13, 2011.
Office action from Korean Application No. 2003-7005873 dated Jun. 26, 2007.
Office action from Korean Application No. 2003-7005873 dated Nov. 29, 2007.
Office action from Mexican Application No. 07/006989 dated Oct. 24, 2011.
Communication regarding Mexican Application No. 08/05816 dated Mar. 15, 2011.
Office action from Mexican Application No. 08/005819 dated Mar. 16, 2011.
Office action from Mexican Application No. 08/005819 dated Jun. 3, 2011.
Office action from Russian Application No. 2008117091 dated Apr. 19, 2010.
Office action from Russian Application No. 2008117091 dated Dec. 13, 2010.
Office action from Russian Application No. 2008117092 dated Oct. 12, 2011.
Aslanova, “Steklyannye volokna”, Glass Fibers, Moscow, Khimiya, 1979, I, 256 pp. pp. 33, 34, Fig. 3.2).
Chernyak et alo. “Nepreryvnoe steklyannoe volokno” Continuous Glass Fiber, Moscow, Khimiya, 1965.
Popov, et al., “Proizvodstvo i primenenie plavlenolitykh ogneuporov”, Manufacture and Application of Molten Cast Refractory Materials, Moscow, Metallurgiya, 1985, IV, p. 212-213.
Office action from U.S. Appl. No. 11/722,039 dated Mar. 1, 2010.
Office action from Brazilian Application No. PI01149733 dated Mar. 10, 2009.
Office action from Canadian Application No. 2,528,923 dated Dec. 9, 2010 along with English translation of relevant portions of action.
Office action from Canadian Application No. 2,528,923 dated Jul. 12, 2011.
Office action from Chinese Application No. 200480015986.4 dated Jul. 6, 2007.
Office action from Chinese Application No. 200580043075.7 dated Feb. 5, 2010.
Office action from Chinese Application No. 200680041114.4 dated Feb. 29, 2012.
Office action from European Application No. 04767297.7 dated Sep. 8, 2006.
Search Report from French Registration No. 635569 (FR 0306981) dated Feb. 13, 2004.
Search Report from French Registration No. 658923 (FR 0413443) dated Aug. 16, 2005.
Office action from Indian Application No. 00501/KOLNP/2003 dated Jul. 7, 2006.
Office action from Indian Application No. 00501/KOLNP/2003 dated May 14, 2007.
Office action from Indian Application No. 2546/KOLNP/2005 dated Jun. 15, 2007.
Office action from Japanese Application No. 2002-544374 dated Sep. 28, 2007.
Office action from Japanese Application No. 2002-544374 dated Jul. 27, 2009.
Office action from Japanese Application No. 2002-544374 dated Jul. 12, 2010.
Office action from Japanese Application No. 2006-516274 dated Jun. 22, 2010.
Office action from Japanese Application No. 2006-516274 dated Feb. 22, 2011.
Office action from Korean Application No. 10-2005-7023679 dated Mar. 3, 2011.
Office action from Mexican Application No. PA/a/2002/000814 dated Feb. 22, 2006.
Office action from Mexican Application No. PA/a/2002/00814 dated Sep. 9, 2005.
Office action from Mexican Application No. PA/a/2002/00814 dated Jun. 23, 2005.
Office action from Mexican Application No. PA/a/2002/00814 dated Sep. 26, 2002.
Office action from Mexican Application No. 05/013323 dated Feb. 27, 2006.
Office action from Mexican Application No. 05/013323 dated May 29, 2009.
Office action from Mexican Application No. 07/06989 dated Aug. 22, 2007.
Office action from Russian Application No. 2007126843 dated Sep. 24, 2009.
Office action from Russian Application No. 2007126843 dated Dec. 11, 2009.
Office action from Canadian Application No. 2,426,637 dated Aug. 28, 2008.
Office action from Russian Application No. 2006100296/03 dated Jun. 8, 2008.
Office action from Russian Application No. 2006100296/03 dated Nov. 26, 2008.
Office action from U.S. Appl. No. 12/403,955 dated Apr. 24, 2012.
Office action from Taiwanese Application No. 094144552 dated May 7, 2012.
Notice of Allowance from U.S. Appl. No. 12/344,130 dated Jun. 7, 2012.
Notice of Allowance from U.S. Appl. No. 12/341,985 dated Jun. 11, 2012.
Office action from Russian Application No. 2008117093/03 dated Apr. 26, 2012.
Office action from Korean Application No. 2008-7010726 dated Nov. 14, 2012.
Office action from Korean Application No. 2008-7010727 dated Nov. 14, 2012.
Office action from Mexican Application No. 07/06989 dated Jun. 26, 2012.
Office action from Japanese Application No. 2008-540053 dated Jul. 30, 2012.
Office action from Japanese Application No. 2008-540052 dated Jul. 30, 2012.
Office action from Korean Application No. 10-2007-7016026 dated Aug. 9, 2012.
Office action from U.S. Appl. No. 12/643,411 dated Aug. 17, 2012.
Office action from U.S. Appl. No. 11/722,039 dated Aug. 24, 2012.
Lund, “Tensile strength of glass fibers”, dated Feb. 18, 2010.
Office action from Chinese Application No. 200680041104.0 dated Sep. 13, 2012.
Notice of Allowance from U.S. Appl. No. 12/880,289 dated Aug. 31, 2012.
Office action from Japanese Application No. 2009-533917 dated Sep. 24, 2012.
Notice of Allowance from U.S. Appl. No. 12/341,985 dated Oct. 11, 2012.
Appeal Decision from U.S. Appl. No. 10/560,068 dated Aug. 15, 2012.
Office action from Canadian Application No. 2,626,733 dated Oct. 9, 2012.
Office action from European Application No. 09796243.5 dated Oct. 2, 2012.
Office action from Chinese Application No. 20680041104.0 dated Jun. 13, 2012.
Office action from Canadian Application No. 2,591,026 dated May 15, 2012 along with English translation of relevant portions of action.
English Translation of JP Patent No. 2002-154843. Foreign patent along with English abstract previously submitted.
Office action from U.S. Appl. No. 12/643,411 dated Jan. 28, 2013.
Office action from Chinese Application No. 200680041104.0 dated Jan. 14, 2013.
Office action from Mexican Application No. 11/06712 dated Feb. 1, 2013 along with English translation of relevant portions of action.
Office action from Chinese Application No. 200680041114.4 dated Oct. 24, 2012.
Office action from European Application No. 09796559.4 dated Dec. 19, 2012.
Office action from Indian Application No. 1733/KOLNP/2008 dated Dec. 6, 2012.
Office action and Search Report from Taiwanese Application No. 95139183 dated Nov. 5, 2012 along with English translation of relevant portions of action.
Office action and Search Report from Taiwanese Application No. 95139185 dated Oct. 24, 2012 along with English translation of relevant portions of action.
Office action from Chinese Application No. 200680041114.4 dated Mar. 25, 2013.
Office action from Korean Application No. 10-2007-7016026 dated Feb. 25, 2012.
Notice of Allowance from U.S. Appl. No. 12/847,206 dated Apr. 8, 2013.
Refusal Decision from Russian Application No. 2008117092/03 dated Mar. 15, 2013.
Office action from Brazilian Application No. PI0411336-5 dated Apr. 5, 2013.
Office action from Canadian Application No. 2,591,026 dated Mar. 25, 2013.
Office action from Chinese Application No. 200980156454.5 dated Apr. 11, 2013.
Office action from Chinese Application No. 200980156910.6 dated Apr. 16, 2013.
Office action from U.S. Appl. No. 12/989,225 dated Nov. 19, 2012.
Notice of Allowance from U.S. Appl. No. 12/989,225 dated Mar. 11, 2013.
Office action from Saudi Arabian Application No. 109300629 dated Jun. 5, 2013 along with English translation of relevant portions of action.
Office action from Indian Application No. 1732/KOLNP/2008 dated Mar. 15, 2013.
Office action from Chinese Application No. 200580043075.7 dated May 2, 2013.
Notice of Allowance from U.S. Appl. No. 12/847,206 dated Jul. 5, 2013.
Examiner's Answer from U.S. Appl. No. 11/722,039 dated Jul. 26, 2013.
Office action from Chinese Application No. 200680041114.4 dated Jul. 1, 2013.
Office action from Mexican Application No. 07/006989 dated Jun. 19, 2013.
Office action from Canadian Application No. 2,626,732 dated Jun. 13, 2013.
Office action from Canadian Application No. 2,626,733 dated Jun. 27, 2013.
Related Publications (1)
Number Date Country
20130217822 A1 Aug 2013 US
Continuation in Parts (1)
Number Date Country
Parent 11267739 Nov 2005 US
Child 11699719 US