# Patent

## Title
Low viscosity E-glass composition enabling the use of platinum and rhodium free bushings

## Abstract

A low viscosity E-glass composition including SiO2 in an amount ranging from 52-54 weight percent, Al2O3 in an amount ranging from 12-14 weight percent, F2 in an amount ranging from 0-1.0 weight percent, Fe2O3 in an amount ranging from 0 to 0.8 weight percent, Na2O in an amount ranging from 0-2.0 weight percent, K2O in an amount ranging from 0-2.0 weight percent, CaO in an amount ranging from 16-23 weight percent, MgO in an amount ranging from 0-3.0 weight percent, Li2O in an amount ranging from 0-3.0, TiO2 in an amount ranging from 0-1.5 weight percent, ZnO in an amount ranging from 0-4.0 weight percent, and B2O3 in an amount ranging from 8.0-10 weight percent is provided. The glass composition has a log 3 viscosity temperature between 1750 and 2150° F. and a ΔT temperature greater than 50° F.

## Background
TECHNICAL FIELD AND INDUSTRIAL APPLICABILITY OF THE INVENTION
The present invention relates generally to a glass composition, and more particularly, to glass compositions that enable the production of E-glass products utilizing metal alloy bushings that do not contain platinum or rhodium.
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, A-glass, C-glass, and ECR-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. Non-physical considerations given to commercial glass compositions include the raw material cost and environmental impact caused by manufacturing the glass.
E-glass compositions are the most common glass compositions for making continuous glass fiber strands used in textile and reinforcement applications. One advantage of E-glass is that its liquidus temperature is approximately 200° F. below its forming temperature, which is commonly defined as the temperature at which the viscosity of the glass equals 1000 poise. E-glass has a wide range of forming temperatures and a low devitrification rate. Historically, commercial E-glass compositions possessed forming temperatures between 2150° F. and 2350° F. and liquidus values from approximately 100° F. to 250° F. below the forming temperature.
Producing glass fibers from E-glass compositions is well-known in the fiberglass industry. To be defined as an E-glass according to ASTM D578, the glass composition is composed primarily of the oxides of calcium, aluminum, and silicon. E-glass for use in glass fiber products for general applications as defined by ASTM D578 contains the components in the ranges set forth in Table 1. ASTM D578 teaches that E-glass for use in glass fiber yarn products for printed circuit boards and in aerospace applications has the components and percentages set forth in Table 2.










TABLE 1







Chemical
% by weight









B2O3
 0–10



CaO
16–25



Al2O3
12–16



SiO2
52–62



MgO
0–5



TiO2
  0–1.5



Fe2O3
0.05–0.8 



F2
  0–1.0



Na2O + K2O
0–2




















TABLE 2







Chemical
% by weight









B2O3
 5–10



CaO
16–25



Al2O3
12–16



SiO2
52–56



MgO
0–5



TiO2
  0–0.8



Fe2O3
0.05–0.4 



F2
  0–1.0



Na2O + K2O
0–2










Attempts have been made to create or modify E-glass compositions to achieve certain desired properties or characteristics. Early efforts to develop E-glasses with good forming characteristics include U.S. Pat. No. 2,334,961 to Schoenlaub and U.S. Pat. No. 2,571,074 to Tiede, et al. The glass compositions taught by Schoenlaub and Tiede, et al. are set forth in Table 3.











TABLE 3








U.S. Pat.
U.S. Pat.




No. 2,334,961
No. 2,571,074




(Schoenlaub)
(Tiede, et al.)



Chemical
% by weight
% by weight









B2O3
 9–11
 8–13



CaO
16–19
19–25



Al2O3
12–16
12–16



SiO2
52–56
52–56



MgO
3–6
—










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.
Current glass compositions, including current E-glass compositions, have a high forming viscosity that requires the use of bushings made from platinum and rhodium. Platinum-rhodium bushings are expensive and increase the manufacturing costs of the glass fibers and products or articles formed from the glass fibers.
Despite the existence of E-glass compositions, there is an existing need in the art for improved or new E-glass compositions that meet the requirements of ASTM D578, that maintain or exceed the physical properties of conventional E-glass compositions, and that possess a viscosity that is low enough to utilize a platinum and rhodium-free bushing and reduce the manufacturing costs associated with the production of E-glass fibers.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an E-glass composition that includes B2O3 in an amount from 8-10% by weight, CaO in an amount from 16-23% by weight, Al2O3 in an amount from 12-14% by weight, SiO2 in an amount from 52-54% by weight, and Fe2O3 in an amount from 0-0.8% by weight of the total composition. The composition may also include TiO2 in an amount from 0-1.5% by weight, MgO in an amount from 0-3% by weight, F2 in an amount from 0-1% by weight, Na2O in an amount from 0-2% by weight, K2O in an amount from 0-2% by weight, Li2O in an amount from 0-3% by weight, and ZnO in an amount from 0-4% by weight. The phrase % by weight, as used herein, is intended to be defined as the percent by weight of the total composition. In addition, the composition may optionally contain trace quantities of other components or impurities. The E-glass compositions may be used to form continuous glass strands for use as textiles and as reinforcements. E-glass fibers formed by the inventive compositions possess a forming viscosity that is low enough to utilize bushings fabricated from precious metal-based alloys (e.g., palladium-based alloys), stainless steels (e.g., nickel and chromium stainless steels), or Inconel® (a nickel-based alloy with chromium and iron manufactured by lnco Alloys International, Inc). The liquidus temperature of the inventive E-glass compositions is less than about 2100° F., the log 3 temperature is greater than about 20150° F., and the ΔT is greater than or equal to 50° F.
It is another object of the present invention to provide a continuous E-glass fiber formed of the composition described above and produced using a bushing that is free or substantially free of platinum and/or rhodium. The E-glass fibers have a log 3 temperature less than about 2150° F., generally from about 1750° F. to about 2150° F. and a ΔT is greater than or about 50° F., generally from about 50° F. to about 250° F. In addition, the E-glass fibers are able to be formed utilizing low cost platinum and rhodium-free bushings or metal alloy bushings. Examples of materials that may be used to form the platinum and rhodium-free bushings include precious metal-based alloys (e.g., palladium-based alloys), stainless steels (e.g., nickel and chromium stainless steels), or Inconel® (a nickel-based alloy with chromium and iron manufactured by Inco Alloys International, Inc). By utilizing a metal alloy bushing such as a palladium based alloy bushing, manufacturing costs associated with E-glass fiber production, products used in general applications (e.g., reinforcements), and yarn products for printed circuit boards may be dramatically reduced.
It is yet another object of the present invention to provide a method of forming an E-glass fiber. The fibers may be formed by obtaining the raw ingredients and mixing the components in the appropriate quantities to give the desired weight percentages of the final composition. The mixture of raw ingredients is then melted in a melter or furnace and drawn through orifices of a platinum and rhodium-free bushing. The platinum and rhodium-free bushing may be formed from a metal alloy such as a precious metal-based alloy (e.g., palladium-based alloys), stainless steels (e.g., nickel and chromium stainless steels), or Inconel® (a nickel-based alloy with chromium and iron manufactured by Inco Alloys International, Inc). In some embodiments, precious metals such as platinum and/or rhodium may be utilized in the bushing to provide additional structural or mechanical strength to the bushing and/or to provide corrosion resistance. Strands of E-glass fibers are formed by gathering the individual filaments together. The strands may be wound and further processed in a conventional manner suitable for the intended application.
It is an advantage of the present invention that the glass composition possesses a forming viscosity that is low enough to utilize low cost metal alloy bushings instead of conventional high cost platinum-rhodium bushings in the formation of the glass fibers.
It is another advantage of the present invention that the energy necessary to melt the inventive E-glass is less than the energy necessary to melt commercially available E-glass formulations.
It is yet another advantage of the present invention that fibers formed from the inventive E-glass composition may be formed at a lower cost due to the lower energy input needed to melt the glass composition.
It is a feature of the present invention that E-glasses formed from the inventive compositions have a log 3 temperature below 2150° F. and a ΔT greater than about 50° F.
It is another feature of the present invention that the forming viscosity of the inventive E-glass is less than that of E-glass formed from current E-glass compositions.
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.


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. The terms “composition” and “formulation” may be used interchangeably herein.
The present invention relates to an E-glass composition that complies with the requirements of an “E-glass” in accordance with ASTM D578 and may be used to form continuous glass strands for use as textiles and as reinforcements. The E-glass formed by the inventive composition possesses a forming viscosity that is low enough to enable the use of low cost metal alloy bushings instead of conventional high cost platinum-rhodium bushings in the formation of the glass fibers. In particular, the forming viscosity of the inventive E-glass is less than that of E-glass formed from conventional E-glass compositions, which have forming viscosities in a range from 2150° F. to 2350° F. By utilizing a metal alloy bushing such as a palladium-based alloy bushing, manufacturing costs associated with E-glass fiber production, products used in general applications (e.g., reinforcements), and yarn products for printed circuit boards may be dramatically reduced. The energy necessary to melt the inventive E-glass is less than the energy necessary to melt commercially available E-glass formulations. Such lower energy requirements may lower the overall manufacturing costs associated with the inventive E-glass.
The forming viscosity of a glass composition is often defined by its log 3 temperature. The log 3 temperature is the temperature at which the molten glass composition has a viscosity of 1,000 poise (i.e., roughly the fiberizing viscosity), where the viscosity is determined by measuring the torque needed to rotate a cylinder immersed in the molten glass material according to ASTM C965. Lowering the fiberizing temperature may reduce the production cost of the glass fibers because it allows for a longer bushing life, increased throughput, and reduced energy usage. By lowering the log 3 viscosity, a bushing operates at a cooler temperature and does not quickly “sag”. Sag occurs in bushings held at an elevated temperature for extended periods of time. Lowering the log 3 temperature reduces the sag rate, and, as a result, the bushing life may be increased. In addition, a lower log 3 temperature permits the bushing to have a higher throughput since more glass can be melted in a given period of time. Thus, the production cost of the glass fibers may be reduced.
The liquidus temperature of the glass composition is the temperature below which the first crystal appears in the molten glass material when it is held at that temperature for 16 hours, according to ASTM C829. Additionally, the liquidus temperature is the greatest temperature at which devitrification can occur upon cooling the glass melt. At all temperatures above the liquidus temperature, the glass is completely molten and free of crystals.
The difference between the log 3 temperature and the liquidus temperature is termed “ΔT”. A larger ΔT offers a greater degree of flexibility during fiberizing and helps to avoid devitrification, which is the formation of crystals within the glass melt. Increasing the ΔT also reduces the production cost of the glass fibers by allowing for a greater bushing life and a less sensitive forming process.
The inventive composition lowers the viscosity of the molten E-glass so that a high ΔT is achieved and the glass composition can be utilized in a glass forming apparatus that contains a platinum and rhodium-free bushing, such as a palladium alloy bushing. If the ΔT is too small, the molten E-glass may crystallize within the fiberizing apparatus and cause a break in the manufacturing process. It is preferred that the log 3 temperature of the inventive E-glass composition is less than 2150° F., and even more preferably less than or equal to 2100° F. In at least one exemplary embodiment of the present invention, the log 3 temperature falls within a range from 1750° F. to 2100° F. Desirably, the liquidus temperature ranges from about 1750° F. to about 2100° F. such that the ΔT is greater than or equal to about 50° F. In some exemplary embodiments of the present invention, the ΔT ranges from 50° F. to 250° F. It is preferred that the ΔT be as large as possible for a given forming viscosity, although other factors such as raw material costs should be considered when selecting a glass composition for production.
Despite the lower viscosity of the inventive E-glass, the ΔT, tensile modulus, density, strength, and refractive index are similar to traditional boron-containing E-glass compositions. Thus, the composition of the present invention retains the ability to make a commercially acceptable E-glass fiber and fiber product produced from the E-glass fibers and is able to reduce the cost of production by utilizing a bushing that is free or substantially free of platinum and rhodium. As used herein, the phrase “substantially free” is meant to indicate that a percentage of the bushing is formed of precious metals, particularly platinum and/or rhodium. The percentage may be a very small amount, such as, for example, a trace amount (e.g., less than 5%), or it may be a larger percentage, such as up to 25% or up to 50% of the bushing. It is to be appreciated that even at a 50% inclusion of precious metals in the bushing, a large cost savings is achieved due to the extremely high cost of the precious metals. It is an advantageous feature of the inventive composition that the E-glass composition enables the use of a platinum/rhodium free bushing, unlike conventional E-glass compositions that require a platinum/rhodium bushing. Furthermore, the addition of some platinum and/or rhodium in the bushing may enable the bushing to have a longer life.
The inventive E-glass composition includes the following components in the weight percent ranges given in Table 4. Preferred weight percentages of the components are set forth in Table 5. As used herein, the terms “weight percent” and “percent by weight” are meant to denote the weight percent (or percent by weight) based on the total composition.









TABLE 4







% by weight



















B2O3
 8–10



CaO
16–23



Al2O3
12–14



SiO2
52–54



MgO
0–3



TiO2
  0–1.5



Fe2O3
  0–0.8



F2
0–1



Na2O
0–2



K2O
0–2



Li2O
0–3



ZnO
0–4



Na2O + K2O
0–2



Log 3
<2150



Temperature



(° F.)



Liquidus
≦2100



Temperature



(° F.)



ΔT
≧50



















TABLE 5







% by weight



















B2O3
 8–10



CaO
18–23



Al2O3
12–14



SiO2
52–53



MgO
0–3



TiO2
0–1



Fe2O3
  0–0.5



F2
0–1



Na2O
0–2



K2O
0–1



Li2O
0–2



ZnO
0–2



Na2O + K2O
0–2



Log 3
≦2100



Temperature



(° F.)



Liquidus
≦2000



Temperature



(° F.)



ΔT
≧100










It is to be appreciated that impurities or tramp materials may be present in the E-glass compositions 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, 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. For example, the components may be obtained from suitable ingredients or raw materials such as sand for SiO2, limestone for CaO, and dolomite for MgO. The composition may optionally contain trace quantities of other components or impurities. The mixed batch is then melted in a furnace or melter, and the resulting molten glass is passed along a forehearth and into non-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 E-glass filaments or fibers. Strands of E-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 E-glass filaments and may be wound on a forming tube mounted on a rotatable collet of a winding machine. The fibers may be further processed in a conventional manner suitable for the intended application.
The fibers formed from the inventive E-glass compositions may be formed using a lower energy cost due to the lower energy input needed to melt the glass composition and its lower melting temperatures. By lowering the melting temperature of the glass composition to a temperature that is less than conventional E-glass compositions, less energy is utilized to raise the temperature of the melter to a temperature that is sufficient to melt the glass composition. Additionally, the lower melting temperatures of the E-glass compositions may enable the use of cheaper refractories to melt the glass, which would further lower the overall cost of the glass fibers.
The ability to melt and deliver a glass at lower temperatures may also enable the production of glasses with a ΔT that is less than the ΔT of conventional E-glass compositions. In other words, the ability to fiberize glasses with a smaller forming window may be possible at lower forming temperatures due to a greater ability to control the glass temperature delivered to the bushing. Traditional E-glasses require ΔT values greater than 100° F., whereas the inventive E-glass compositions may be formed at ΔT values as low as 50° F. because of improved temperature control at lower temperatures.
The temperatures of the molten E-glass at the furnace, forehearth, and bushing are selected to appropriately adjust the viscosity of the glass. The operating temperatures may be maintained using standard manufacturing equipment such as PLC-based controls. Preferably, the temperature at the front end of the melter is automatically controlled to reduce or eliminate devitrification. Additionally, the control of the glass temperature often improves at lower temperatures. Therefore, glasses that possess lower ΔT temperatures may be manufactured provided that the forming temperature is significantly less than traditional E-glass compositions (e.g., at least 100° F. less than traditional E-glass formulations).
In general, the platinum and rhodium free bushing or bushing that is substantially free of platinum and rhodium utilized in the formation of E-glass fibers from the inventive composition should be structured to provide long life and resist sagging, which is dependent upon the pressure of the glass on the tip plate and the temperature. The bushing may be formed of metal alloys such as precious metal-based alloys (e.g., palladium-based alloys, ruthenium-based alloys, osmium-based alloys, iridium-based alloys, rhodium-based alloys, and/or platinum-based alloys), stainless steels (e.g., nickel and chromium stainless steels), Inconel® (a nickel-based alloy with chromium and iron manufactured by Inco Alloys International, Inc), RA-353 (a high temperature alloy manufactured by Rolled Alloys), and/or Haynes® 214 (a high temperature alloy manufactured by Haynes International, Inc). It is to be appreciated that although the inventive E-glass composition enables the elimination of expensive, precious metals such as platinum and rhodium in the bushing, it may be advantageous in some exemplary embodiments to use precious metals for key structural components, mechanical reinforcements, and corrosion resistance, such as T-gussets and tips.
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
E-glass compositions according to the present invention were made by obtaining reagent grade raw materials in proportioned amounts according to the weight percentages set forth in Tables 6-13 to make 600 g of glass. The raw materials were melted in a platinum crucible in an electrically heated furnace at a temperature of 2650° F. for three hours. During the three hours of heating, the melt was stirred twice. The forming viscosity (i.e., log 3 temperature), liquidus temperature, and ΔT were measured for each of the E-glass compositions. The liquidus temperature was measured by placing glass cullet in a platinum boat and heating the boat in a thermal gradient furnace for 16 hours. The liquidus temperature was the highest temperature at which crystals formed. The viscosity was measured using a calibrated rotating spindle technique known to those of skill in the art utilizing a platinum bushing and a platinum spindle.

















TABLE 6






Ex. 1
Ex. 2
Ex. 3
Ex. 4
Ex. 5
Ex. 6
Ex. 7
Ex. 8
Ex. 9
Ex. 10



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)

























SiO2
52
52
52
52
52
52
52
52
52
52


Al2O3
12
12
12
12
12
12
12
12
12
12


F2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
2
2
2
2
2
2
2
2
2
2


K2O
0
0
0
0
0
0
0
0
0
0


CaO
20
18
22
22
19.52
18.75
16.75
16
17.5
21.25


MgO
0
0
3
0.25
0.75
3
3
3
0
0


Li2O
0
3
0
3
2.25
3
0
2.25
3
0


TiO2
1.5
1.5
0
0
0.31
0.75
0.75
0
0
0


ZnO
3
3
0
0.25
2.25
0
3
2.25
3
2.25


B2O3
9
8
8.5
8
8.4
8
10
10
10
10


Log 3
2070
1864
2049
1837
1895
1845
2076
1902
1847
2055


Viscosity


Temp


(° F.)


Liquidus
1825
1824
2016
1988
1898
1902
1938
1903
1805
1902


Temp (° F.)


ΔT (° F.)
245
40
33
−151
−3
−57
138
−1
42
153

























TABLE 7






Ex. 11
Ex. 12
Ex. 13
Ex. 14
Ex. 15
Ex. 16
Ex. 17
Ex. 18
Ex. 19



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
52
52
52
52
52
52
52
52


Al2O3
12
12
12
12
12
12
12
12
12


F2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
2
2
2
2
2
2
2
2
2


K2O
0
0
0
0
0
0
0
0
0


CaO
22
19
16.5
22
19
16
18.51
22
20.75


MgO
0
3
3
0
1.5
3
2.25
0.25
3


Li2O
1.5
0
3
1
0
3
2.25
3
1.75


TiO2
0
1.5
0
1.5
0
1.5
0.3
0
0


ZnO
0
0
3
1
3
1
0.75
0.25
0


B2O3
10
10
8
8
10
9
9.4
8
8


Log 3
1925
2058
1858
1976
2064
1853
1892
1837
1919


Viscosity


Temp


(° F.)


Liquidus
1973
1964
1889
1934
1832
1887
1858
1955
1949


Temp (° F.)


ΔT (° F.)
−48
94
−31
42
232
−34
34
−118
−30

























TABLE 8






Ex. 20
Ex. 21
Ex. 22
Ex. 23
Ex. 24
Ex. 25
Ex. 26
Ex. 27
Ex. 28



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
52
52
52
52
52
52
52
52


Al2O3
12
12
12
12
12
12
12
12
12


F2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
2
2
2
2
2
2
2
2
2


K2O
0
0
0
0
0
0
0
0
0


CaO
22
17.5
18
20
22
20.14
19
18
22


MgO
0.5
3
0
0
0.75
2.25
3
3
0.5


Li2O
0
3
3
3
0
0.75
0
0
0


TiO2
0
0
1.5
1.5
0.75
3.1
1.5
1.5
0


ZnO
3
0
3
0
0
1.63
0
3
3


B2O3
8
10
8
9
10
8.4
10
8
8


Log 3
2043
1841
1865
1844
2046
1989
2059
2071
2064


Viscosity


Temp


(° F.)


Liquidus
1961
1876
1845
1912
1901
1898
1981
1952
1957


Temp (° F.)


ΔT (° F.)
82
−35
20
−68
145
91
78
119
107

























TABLE 9






Ex. 29
Ex. 30
Ex. 31
Ex. 32
Ex. 33
Ex. 34
Ex. 35
Ex. 36
Ex. 37



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
52
52
52
52
54
52
54
54


Al2O3
12
12
12
12
12
12
12
14
14


F2
0.2
0.2
0.2
0
1
1
1
0
1


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
2
2
2
0
0
1
0
1
1


K2O
0
0
0
0
0
0
0
0
0


CaO
16
17.5
17.5
20
20
20
19.2
16
16


MgO
1.5
0
0
2
0
0
2
0
2


Li2O
1.5
3
3
0
0
1
2
0
1


TiO2
1.5
0
1.5
1.5
0
1.5
1.5
1.5
0


ZnO
3
3
1.5
4.2
4.7
1.2
0
3.2
0.7


B2O3
10
10
10
8
10
8
10
10
10


Log 3
1961
1847
1852
2099
2093
2094
2016
2229
2132


Viscosity


Temp


(° F.)


Liquidus
1777
1783
1762
2001
2064
>1966
>2000
1972
1943


Temp (° F.)


ΔT (° F.)
184
64
90
98
29
—
—
257
189

























TABLE 10






Ex. 38
Ex. 39
Ex. 40
Ex. 41
Ex. 42
Ex. 43
Ex. 44
Ex. 45
Ex. 46



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
54
52
54
54
52
54
52
52


Al2O3
14
12
12
14
14
14
13.2
12
14


F2
1
0
1
0
0
0
1
0
0


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
1
0
1
0
0
0
0
1
0


K2O
0
0
0
0
0
0
0
0
0


CaO
20
20
17.2
16
18.2
20
16
20
20


MgO
2
2
0
2
2
0
2
0
2


Li2O
0
2
1
2
0
2
2
1
0


TiO2
1.5
1.5
1.5
1.5
1.5
1.5
1.5
1.5
0


ZnO
0.2
0.2
6
2.2
0
0.2
0
2.2
1.7


B2O3
8
8
8
8
10
10
10
10
10


Log 3
2111
1981
2019
2037
2187
1983
2009
2000
2130


Viscosity


Temp


(° F.)


Liquidus
1947
1916
1837
1906
>2000
1791
1855
1817
1874


Temp (° F.)


ΔT (° F.)
164
65
182
131
—
192
154
183
256

























TABLE 11






Ex. 47
Ex. 48
Ex. 49
Ex. 50
Ex. 51
Ex. 52
Ex. 53
Ex. 54
Ex. 55



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
52
54
54
54
52
54
52
54


Al2O3
12
14
14
14
12
14
14
14
14


F2
1
0
0
0
0
0
1
0
1


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
0
0
0
0
0
1
0
0
1


K2O
0
0
0
0
0
0
0
0
0


CaO
16.7
17.7
16.2
16
16
16
16
16
18.7


MgO
0
0
0
0
2
2
0
0
2


Li2O
2
0
0
2
2
1
2
2
1


TiO2
0
0
1.5
0
0
0
0
1.5
0


ZnO
6
6
6
5.7
3.7
5.7
2.7
4.2
0


B2O3
10
10
8
8
10
8
10
10
8


Log 3
1949
2163
2229
2059
2002
2065
2040
2010
2067


Viscosity


Temp


(° F.)


Liquidus
1820
2021
>2030
1879
1861
1913
1817
1792
1900


Temp (° F.)


ΔT (° F.)
129
142
—
180
141
152
223
218
167

























TABLE 12






Ex. 56
Ex. 57
Ex. 58
Ex. 59
Ex. 60
Ex. 61
Ex. 62
Ex. 63
Ex. 64



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
54
54
53
54
52
54
54
54


Al2O3
12
12
12
13
12
12
12
12
14


F2
0
0.2
1
0.50
0
0
1
0
1


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
1
0
0
0.49
0
1
1
1
1


K2O
0
0
0
0
0
0
0
0
0


CaO
16
20
20
18
17.7
20
16
19.7
16


MgO
2
0
2
1
2
0
2
2
0


Li2O
0
2
0
0.74
0
1
0
1
0


TiO2
1.5
1.5
0
0.76
0
0
1.5
0
0


ZnO
5.2
0
2.7
3.16
6
5.7
4.2
0
5.7


B2O3
10
10
8
9
8
8
8
10
8


Log 3
2105
1973
2134
2072
2162
2011
2151
2026
2205


Viscosity


Temp


(° F.)


Liquidus
1962
1866
2114
1890
2109
1840
>1970
1902
>1970


Temp (° F.)


ΔT (° F.)
143
107
20
182
53
171
—
124
—

























TABLE 13






Ex. 65
Ex. 66
Ex. 67
Ex. 68
Ex. 69
Ex. 70
Ex. 71
Ex. 72
Ex. 73



(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by
(% by


Chemical
wt.)
wt.)
wt)
wt.)
wt.)
wt.)
wt.)
wt.)
wt.)
























SiO2
52
54
52
54
54
54
53
52
52


Al2O3
12
12
14
12
14
14
13
14
14


F2
1
0
1
0
0
1
0.50
1
1


Fe2O3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3
0.3


Na2O
0
0
0
1
1
0
0.49
0
1


K2O
0
0
0
0
0
0
0
0
0


CaO
16
20
16
16
20
20
18
20
20


MgO
2
0
2
0
0
0
1
0
0


Li2O
2
2
0
0
0
2
0.74
2
0.2


TiO2
1.5
0
1.5
1.5
0
0
0.76
0
1.5


ZnO
5.2
3.7
3.2
5.2
2.7
0
3.15
2.7
0


B2O3
8
8
10
10
8
8.7
9
8
10


Log 3
1962
1991
2158
2169
2170
1996
2077
1974
2099


Viscosity


Temp


(° F.)


Liquidus
1822
1871
>1991
>1984
1985
1787
1882
1856
1848


Temp (° F.)


ΔT (° F.)
140
120
—
—
185
209
195
118
251









The data obtained from the inventive E-glass compositions set forth in Example 1 through Example 73 was calculated to obtain the average viscosity, liquidus temperature, and ΔT. The results demonstrated that the inventive E-glass compositions had an average viscosity less than 2150° F., an average liquidus temperature less than 2100° F., and an average ΔT greater than 50° F. As shown in Tables 6-13, the liquidus temperature and the ΔT of the inventive compositions were comparative to conventional E-glass according to ASTM D578. The viscosity of the inventive compositions were lower than conventional boron containing E-glass compositions, which, as discussed above, is between 2150° F. to 2350° F. The lower forming viscosity of the inventive E-glass compositions permits the use of lower cost, non platinum/rhodium based bushings.
One preferred embodiment of the inventive E-glass composition (i.e., Example 26 of Table 8) is set forth below in Table 14, together with the comparative physical and mechanical properties of a traditional boron-containing E-glass according to ASTM D578. As shown in Table 14, the physical and mechanical properties of the inventive E-glass composition were similar to those corresponding properties of the traditional boron-containing E-glass composition. Comparing the data obtained from Examples 1-73 in Tables 6-13 and the data set forth in Table 14, it can be concluded that the inventive E-glass compositions maintain or exceed the physical properties of conventional E-glass compositions. In addition, the compositions of the present invention retain the ability to make a commercially acceptable E-glass fiber and reduce the cost of production of the fibers by utilizing a platinum and rhodium-free bushing (or a bushing that is substantially free of platinum and/or rhodium) due to their lower viscosities (i.e., compared to conventional E-glass compositions).









TABLE 14






Inventive E-glass
Traditional Boron-



Composition
Containing E-glass


Properties
(Example 26)
Composition

















Log 3 Viscosity Temp (° F.)
2046
2200


Liquidus Temperature (° F.)
1901
2000


ΔT
145
200


Density (g/cc)
2.61
2.58


Sonic Modulus (MPSI)
11.1
11.2


Strength (KPSI)
464
500









In Table 14, the strength is the measurement of the pristine fiber strength as the fiber was broken in tension. The sonic modulus was calculated by measuring the speed of sound in the E-glass fiber. It can be seen in Table 14 that the properties of the inventive E-glass composition are similar to the properties of a traditional boron containing E-glass. From a consumer standpoint, density and sonic modulus are important characteristics of a glass fiber. In the comparative example set forth in Table 14, the sonic modulus and strength of the inventive E-glass composition are virtually identical. Thus, the inventive E-glass composition is commercially acceptable and is provided at a lower cost due to the ability to utilize a bushing that is free of platinum and/or rhodium or one that contains significantly less platinum and/or rhodium than conventional bushings.
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. The invention is not otherwise limited, except for the recitation of the claims set forth below.

## Claims

1. A composition for preparing E-glass fibers comprising:
B2O3 in an amount from 8-10% by weight of the total composition,
CaO in an amount from 16-23% by weight of the total composition,
Al2O3 in an amount from 12-14% by weight of the total composition,
SiO2 in an amount from 52-54% by weight of the total composition,
Fe2O3 in an amount from 0-0.8% by weight of the total composition,
TiO2 in an amount from 0-1.5% by weight of the total composition,
MgO in an amount from 0-3% by weight of the total composition,
F2 in an amount from 0-1% by weight of the total composition,
Na2O in an amount from 0-2% by weight of the total composition,
K2O in an amount from 0-2% by weight of the total composition,
Li2O in an amount from 0-3% by weight of the total composition, and
ZnO in an amount from 0-4% by weight of the total composition
wherein said composition has a log 3 temperature less than or equal to 2100° F.

2. The composition of claim 1, wherein said composition has a liquidus temperature less than about 2100° F.

3. The composition of claim 1, wherein said composition has a ΔT greater than or equal to 50° F.

4. The composition of claim 1, wherein said glass fibers formed from said composition are formed in a metal alloy bushing that is substantially free of platinum and rhodium.

5. The composition of claim 4, wherein said metal alloy bushing is free of platinum and rhodium.

6. The composition of claim 4, wherein said metal alloy bushing contains less than 5% of said bushing of at least one member selected from the group consisting of palladium-based alloys, ruthenium-based alloys, osmium-based alloys, iridium-based alloys, rhodium-based alloys, platinum-based alloys, nickel and chromium stainless steels and nickel-based alloys containing chromium and iron.

7. The composition of claim 1, wherein
said B2O3 is present in said composition in an amount from 8-10% by weight of the total composition,
said CaO is present in said composition in an amount from 18-23% by weight of the total composition,
said Al2O3 is present in said composition in an amount from 12-14% by weight of the total composition,
said SiO2 is present in said composition in an amount from 52-53% by weight of the total composition,
said Fe2O3 is present in said composition in an amount from 0-0.5% by weight of the total composition,
said TiO2 is present in said composition in an amount from 0-1% by weight of the total composition,
said MgO is present in said composition in an amount from 0-3% by weight of the total composition,
said F2 is present in said composition in an amount from 0-1% by weight of the total composition,
said Na2O is present in said composition in an amount from 0-2% by weight of the total composition,
said K2O is present in said composition in an amount from 0-1% by weight of the total composition,
said Li2O is present in said composition in an amount from 0-2% by weight of the total composition, and
said ZnO is present in said composition in an amount from 0-2% by weight of the total composition.

8. The composition of claim 1, wherein glass fibers formed from said composition are formed in a metal alloy bushing, said metal alloy bushing containing up to 50% of said bushing one or more precious metals selected from platinum, rhodium, palladium, ruthenium, osmium, iridium and combinations thereof.

9. The composition of claim 1, wherein glass fibers formed from said composition are formed in a metal alloy bushing, said metal alloy bushing containing up to 25% of said bushing one or more precious metals selected from platinum, rhodium, palladium, ruthenium, osmium, iridium and combinations thereof.

10. The composition of claim 1, wherein said composition has a log 3 temperature from about 1750° F. to about 2100° F.

11. The composition of claim 3, wherein said composition has a ΔT from 50° F. to about 250° F.

12. The composition of claim 3, wherein said composition has a ΔT greater than or equal to 100° F.