JP2003500330A - Glass fiber composition - Google Patents

Abstract

(57) Abstract: The present invention provides a glass fiber composition comprising: 52 to 62 wt% of SiO _2, 0 to 2 wt% of Na ₂ O, 16 to 25 wt% of CaO,. 8 to 16 wt% of Al ₂ O _3, 0.05 to 0.80 wt% of Fe ₂ O _3, 0 to 2 wt% of K ₂ O, MgO of 1.7 to 2.6, of 0-10 wt% B ₂ O _3, 0-2 wt% of TiO _2, 0-2 wt% of BaO, 0 to 2 wt% of ZrO _2, and 0-2 wt% of SrO, and further, is selected from the group consisting of: that comprises at least one material: 0.05-1.5 wt% of Li ₂ O, 0.05 to 1.5 wt% of ZnO, 0.05 to 3 wt% of MnO, and 0.05 to 3 wt% of MnO _2, wherein the glass composition, our molding temperature below 2280 ° F based on NIST 714 reference standard Beauty 2155 having a ° F below the liquefaction temperature.

Description

Detailed Description of the Invention

(Cross-Reference of Related Patent Applications) This application is filed on May 28, 1999, in US provisional application No. 60,136.
Claim the profit of No. 538.

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to glass compositions for making glass fibers, and more particularly to glass compositions having low liquefaction and molding temperatures.

2. Technical Considerations The most common glass composition for making continuous glass fiber strands for textiles and glass fiber reinforcement is “E” glass. The requirements regarding what type of composition constitutes an E-glass composition are set forth in ASTM
Included in D578-98. The advantage of using E-glass is that its liquefaction temperature is well below its molding temperature (ie, typically above 100 ° F (56 ° C), typically 150 ° F (83 ° C) and 200 ° C). ° F (between 111 ° C)). As used herein, the terms "molding temperature" and "T _FORM " mean the temperature of a glass whose viscosity is log3 or 1000 poise,
And the terms "liquefaction temperature" and "T _LIQ " refer to the solid phase (crystal) and liquid phase (melt)
Means the temperature at which is in equilibrium. The difference between T _FORM and T _LIQ (herein,
"Delta T" or "ΔT") is a general measure of the crystallization potential of a given molten composition. In the glass fiber molding industry, ΔT is maintained at a temperature of at least 90 ° F (50 ° C) to prevent devitrification of the molten glass in the bushing region of the glass fiber molding operation.

Boron and fluorine containing glasses have been developed to meet these operating conditions. More specifically, boron and fluorine are included in the glass batch material to act as a fluid during the glass melting operation. However, these materials volatilize during melting and boron and fluorine emissions are released to the atmosphere. Since boron and fluorine are considered pollutants, their release is tightly controlled by environmental controls, which in turn require careful control of furnace operation and the use of expensive pollutant control equipment. And In response, low boron and / or low fluorine E-glass has been developed. As used herein, "low boron"
Means that the glass composition is less than or equal to 5% by weight of boron, and preferably is free of boron, "low fluorine" means that the glass composition is less than or equal to 1% by weight of fluorine, and preferably , Means that it does not contain fluorine.

For example, US Pat. No. 3,929,497 contains titanium dioxide in the range of 0.5 to 5% by weight and Fe ₂ O ₃ in the range of 5 to 15% by weight, is boron-free and fluorine-free. A glass composition not containing is disclosed.

US Pat. No. 4,199,364 describes Li ₂ O in the range of 0.1 to 1.5% by weight.
And a boron-free and fluorine-free glass composition, which comprises, and may also include barium oxide. The liquefaction temperature of this composition is 2200 ° F.

US Pat. No. 4,542,106 discloses glass compositions containing 1-5% by weight of TiO ₂ , boron-free and fluorine-free. The fiber also has a seed count of less than 5 seeds per cubic centimeter of glass.
count) and has an electrical leakage of 2.8 nanoamps or less.

US Pat. No. 5,789,329 contains up to 0.9% by weight TiO ₂ and has a boron-free and fluorine-free content with a ΔT of at least 100 ° F. (56 ° C.). No glass composition is disclosed.

For more information on glass compositions and methods for making the glass compositions, see K. K. Loewenstein, The Manufacturi
ng Technology of Continuous Glass Fi
Bres (3rd edition, 1993), 30-44, 47-60, 115-122, and 126-135, and F.M. T. Wallenberger (editor),
Advanced Inorganic Fibers: Processes,
Structure, Properties, Applications (20
00), 81-102 and 129-168, which are hereby incorporated by reference.

Since the actual fiber molding operation is carried out at high temperatures, there are high energy costs associated with its manufacture. In addition, the high temperatures accelerate the decomposition of the refractory materials used in glass melting furnaces as well as the bushings used to mold the fibers.
Bushings contain precious metals that cannot be recovered from the glass because the bushings corrode. The lowest possible molding and liquefaction temperature to provide the necessary ΔT to ensure that it does not interfere with the glass fiber molding operation, while reducing energy costs and heat loads to the furnace refractory and bushings. It is advantageous to make glass fibers in Reducing the molding temperature and liquefaction temperature of the glass composition also provides environmental benefits (eg, a reduction in the amount of fuel needed to produce the energy required for fiber molding operations, as well as a reduction in fuel gas temperature). But not limited thereto) can be obtained. In addition, to reduce or eliminate the environmental pollutants associated with these substances,
This is advantageous if the glass composition is a low fluorine and / or low boron composition, preferably free of fluorine and / or free of boron.

SUMMARY OF THE INVENTION The present invention provides a glass fiber composition, which comprises 52-62 wt% S.
iO _2, 0 to 2 wt% of Na ₂ O, 16 to 25 wt% of CaO, 8 to 16 wt% of Al ₂ O _3, 0.05~0.80 wt% of Fe ₂ O _{3, 0~2} Wt% K ₂ O, 1.
7-2.9 wt% MgO, 0-10 wt% B ₂ O ₃ , 0-2 wt% TiO ₂
, 0-2 wt% BaO, 0-2 wt% ZrO ₂ , and 0-2% SrO, wherein the glass composition is 228 based on NIST 714 reference standard.
It has a molding temperature of 0 ° F or less and a liquefaction temperature of 2155 ° F or less. 1 of the present invention
In one non-limiting embodiment, the glass fiber composition further comprises 0.05-1
． 5 wt% Li ₂ O, 0.05-1.5 wt% ZnO, 0.05-3 wt%
Of MnO, and 0.05 to 3 wt% MnO ₂ at least one material selected from the group consisting of.

The present invention also provides a glass fiber composition consisting essentially of: 5
2-62 wt% of SiO _2; 0 to 2 wt% of Na ₂ O; 16 to 25 wt% of CaO
8 to 16 wt% Al ₂ O ₃ ; 0.05 to 0.80 wt% Fe ₂ O ₃ ; 0 to 2 wt% K ₂ O; 2.2 to 2.9 wt% MgO; 0 10 wt% of B ₂ O _3; 0~
2 wt% TiO ₂ ; 0-2 wt% BaO; 0-2 wt% ZrO ₂ ; and 0
~ 2 wt% SrO. Here, the glass composition has a forming temperature of 2280 ° F or less and a liquefying temperature of 2155 ° F or less based on the NIST 714 reference standard.

[0013]   The novel invention is as follows: 52-62 wt% SiO₂0-2 wt% Na₂O
16-25% by weight CaO; 8-16% by weight Al₂O₃0.05-0.80
Wt% Fe₂O₃0-2% by weight K₂O; 1.7-2.6 wt% MgO; 0
-10 wt% B₂O₃0-2% by weight TiO₂0-2 wt% BaO; 0-
2 wt% ZrO₂And 0-2% by weight of SrO, and the following: 0.0
5 to 1.5 wt% Li₂O; 0.05-1.5 wt% ZnO; 0.05-3
Wt% MnO; and 0.05-3 wt% MnO₂Selected from the group consisting of
A glass fiber composition further comprising at least one material is provided. here
And the glass composition has a temperature of 2280 ° F. or less based on NIST 714 reference standard.
It has a molding temperature and a liquefaction temperature of 2155 ° F or less. One non-limiting of the invention
In an exemplary embodiment, SiO₂The content is 57 to 59% by weight, and Na₂Including O
Content is up to 1% by weight, CaO content is 22 to 24% by weight, Al ₂ O₃The content is 12 to 14% by weight, and Fe₂O₃Content up to 0.4% by weight
And K₂The O content is up to 0.1% by weight and the composition is
, Containing at least one material selected from the group consisting of: 0.2-1 weight
% Li₂O; 0.2-1 wt% ZnO; up to 1 wt% MnO; and single
MnO up to amount%₂.

DETAILED DESCRIPTION OF THE INVENTION Suitable for textiles and glass fiber reinforcement, the basic composition of the glass fiber of the present invention has the following main components (% by weight) based on the total weight of the final glass composition: )
including.

[0015]

[Equation 1] Numerical values discussed herein (eg, but not limited to, weight percent of material, time or temperature) are approximate and variations due to various factors well known to those skilled in the art (eg, , Metrics, devices and techniques, but are not limited to these). For example, herein, if the range of SiO ₂ is described as 52 to 62% by weight, this range is from about 52 to about 62 wt%, and the formation temperature of the glass composition, 22
If it is stated that it should be below 80 ° F (1249 ° C), this temperature is about 2280 ° F.

MgO is also the main component of the glass composition of the present invention. It has been found that the heating and melting characteristics of the glass fiber composition, in particular the liquefaction temperature, can be controlled and, in particular, optimized by controlling the amount of MgO. This is the purpose of the present invention and will be discussed in more detail below.

Often, additional materials are added to the glass composition to modify the melting properties of the glass. For example, without limiting the invention, Li ₂ O, ZnO ₂ , MnO
And MnO ₂ can be added to the glass fiber composition to lower the T _LIQ . In one non-limiting embodiment of the glass fibers of the present invention, the glass composition can include one or more of these materials in the following amounts.

[0018]

[Equation 2] Levels of these materials below 0.05 wt% are at or below Trump's level, so it is believed that they do not substantially affect the melting properties of the glass.

[0019]   Boron is T_LIQAnother that may be added to the glass fiber composition to lower the
It is a material. However, as mentioned above, the inclusion of boron produces particles,
Depending on the level of particles, the slag is discharged into the melting furnace exhaust gas before it is released into the environment.
It may need to be removed from the stream. B in the glass fiber composition₂O₃of
The amount can be as high as 10% by weight, but of one non-limiting embodiment of the invention.
The glass composition contains 3% by weight or less of B.₂O₃, Preferably 2% by weight or less of B₂O₃,
And more preferably, 1% by weight or less of B₂O₃including. Another non-limiting of the invention
In embodiments, the glass composition is essentially free of boron. That is, this
This is a trace amount of B₂O₃(This means that up to 0.05% by weight of B ₂ O₃Is considered to be) and preferably B₂O₃Does not include at all.

The glass fiber composition may include other components, and the present invention provides for other materials in the glass fiber composition (eg, 0 to 2 wt% TiO ₂ , BaO, respectively).
, ZrO ₂ and SrO) are intended to be included.

Further, although not limited to the present invention because of the environmental issues discussed above, the glass composition is preferably a low fluorine composition (ie, 0.30 wt% or less fluorine), and Preferably it does not contain fluorine. That is, it is a trace amount or less of fluorine (which is considered herein to be up to 0.05% by weight of fluorine).
And preferably no fluorine at all.

The glass compositions disclosed herein may also include minor amounts of other materials such as melting and refining aids, playing materials or impurities. For example, without limiting the invention, melting and refining aids (eg, SO ₃ ) are useful during the manufacture of the glass, but their residual amount in the glass may vary and the properties of the glass product may vary. Has no significant impact. Further, the small amount of additives described above may be included in the glass composition as a playing card material or impurities contained in the main ingredient.

Commercially available glass fibers of the present invention can be prepared in a conventional manner well known in the art by blending the raw materials used to provide the particular oxides that form the composition of the fibers. Can be prepared. For example, typically, SiO ₂
Sand is used for, Al ₂ O ₃ for clay, CaO for lime or limestone, and MgO and some CaO for dolomite. As discussed above, the glass may contain other additives that are added to modify the glass properties, as well as minor amounts of melting and refining aids, playing materials or impurities.

After mixing the ingredients in the appropriate proportions to provide the desired weight of each ingredient for the desired glass, the batch is mixed with conventional glass fibers as is well known to those skilled in the art. Melting in the melting furnace and the resulting molten glass are passed along a conventional forehearth into a glass fiber molding bushing located along the bottom of the forehearth. During the glass melting stage, the glass is typically heated to a temperature of at least 2550 ° F (1400 ° C). The molten glass is then drawn or drawn through the holes in the bottom of the bushing. A stream of molten glass is thinned into filaments by winding a strand of filaments onto a shaped tube placed on a rotatable collet of a winder. Alternatively, the fiber forming apparatus may be, for example, but not limited to those skilled in the art, a forming device for fibers or strands of synthetic fabric, such as, but not limited to, a spinneret, in which fibers are drawn from a nozzle. Can be. A typical forehearth and glass fiber molding apparatus is described in K.K. Loewenstein,
The Manufacturing Technology of Cont
Inous Glass Fibers, (3rd edition, 1993), 85-10
See pages 7 and 115-135, which are incorporated herein by reference.

Tables 1-7 show laboratory examples of glass fiber compositions showing the effect of MgO on the liquefaction temperature of the glass composition. Boron and fluorine were not included in these compositions. The glass fiber compositions shown in Tables 1-7 were prepared from reagent grade oxides such as pure silica or calcia.
The batch size for each example was 1000 grams. The individual batch ingredients were weighed, mixed and placed in a sealed bottle. This sealed bottle is then
The ingredients were placed on a paint shaker for 15 minutes to effectively mix the ingredients. A portion of this batch was then placed in a platinum crucible (up to 3/4 the volume of the crucible was filled). The crucible was then placed in a furnace and placed at 2600 ° F (1425 ° C) for 15
Heated for minutes. The remaining batch is then placed in this heated crucible and 260
Heat to 0 ° F (1425 ° C) for 15-30 minutes. Then, the temperature of this furnace is increased to 27
Raised to 00 ° F (1482 ° C) and held at this temperature for 4 hours. The molten glass was then fritted in water and dried. Molding temperature, i.e.
The temperature of the glass at a viscosity of 100 poise was determined by ASTM method C965-81 and the liquefaction temperature was determined by ASTM method C829-81.

The weight percentages of the components of the compositions shown in Tables 1-7 are based on the weight percentages of each component in the batch. The weight% of the batch is generally considered to be approximately the same as the weight% of the melted sample, except for the glass batch materials (eg, boron and fluorine) that have volatilized during melting. For boron, the wt% B ₂ O ₃ in the laboratory sample is believed to be 5-10% less than the wt% B ₂ O ₃ in the batch composition. For fluorine, the weight percent fluorine in the laboratory melt is believed to be about 50% less than the weight percent fluorine in the batch composition. It is further envisioned that glass fiber compositions made from commercial grade materials and melted under conventional operating conditions will have similar batch weight% and melt weight% as described above. However, in conventional melting operations, the material is exposed to high melting temperatures for less than the 4 hours exposure for laboratory melting, so that the batch weight percent of the volatile components of this composition is And that the melt weight% is actually closer to each other than the batch weight% and melt weight% of the melt in the laboratory.

[0027]   Viscosity at high temperature (T_FORM) Is determined by the National Institute
Offered by of Standards and Testing (NIST)
Based on a glass sample compared to a physical standard. In Tables 1 to 7, T _FORM NIST 717A (which is a borosilicate glass standard) or N
Comparison with any of IST 714 (which is a soda lime glass standard))
Based on. Either standard can be used, but see NIST 714.
The territorial standard is considered more reliable. Because NIST borosilicate standard 7
17A can degrade at temperatures above 2154 ° F (1177 ° C),
Because it was observed. T based on these two different standards_FORMComparing
Generally, T based on NIST 714_FORMIs based on NIST 717A_{FO RM} 20 ° F to 25 ° F (11 ° C to 16 ° C) higher. T_LIQConforms to the NIST standard
Therefore, it is not affected.

[0028]   Examples 1 to 7 in Table 1 show 1% by weight of TiO.₂A typical glass frame that further includes
The amount of MgO in the fiber molding composition was changed from 1.82% by weight to 3% by weight.
The change in liquefaction temperature in the case of exposure is shown. In Examples 8 to 14 and Table 3 in Table 2.
Examples 15 to 30 are 1.5 wt% or 1.1 wt% TiO, respectively.₂,
And 0.90 wt% Li₂Typical glass fiber molding that further contains O
Liquid of the composition when the amount of MgO is changed from 1.7% by weight to 3.5% by weight
The change in oxidization temperature is shown. Examples 31-38 in Table 4 are 0.5 wt% TiO. ₂ And 0.90 wt% Li₂Typical glass fiber molding that further contains O
When the amount of MgO in the composition is changed from 1.7% by weight to 3.12% by weight
The change in liquefaction temperature is shown. Examples 39-49 in Table 5 are 1.1 wt% Ti.
O₂, 0.45 wt% Li₂O, and further comprising 0.45 wt% ZnO
The amount of MgO in the typical glass fiber molding composition was 1.7 wt% to 3.1 wt.
The change of the liquefaction temperature when changing to the amount% is shown. Examples 47-5 in Table 6
4 is 1.1% by weight TiO₂And further comprising 0.90 wt% ZnO.
The amount of MgO in the typical glass fiber molding composition was 1.7 wt% to 3.1 wt.
The change of the liquefaction temperature when changing to the amount% is shown. Examples 59 to 6 in Table 7
6 is 1.1 wt% TiO₂, 0.30% by weight Na₂O, L of 0.60% by weight
i₂O and 0.25 wt% Fe₂O₃Typical glass fiber, including
-When the amount of MgO in the molding composition is changed from 1.7% by weight to 3.1% by weight.
The change in the liquefaction temperature in the case of Further, the molding temperature of the selected glass composition is also
Included in Tables 1-7.

[0029]   Tables 1 to 7 also show the ratio SiO₂/ RO is included. This is CaO and M respectively
SiO relative to the sum of the calcia content and the magnesia content expressed as gO ₂ Is the ratio of silica content in the batch expressed as

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

[0034]

[Table 5]

[0035]

[Table 6]

[0036]

[Table 7] 1 and 2 represent curves illustrating the relationship between the formation temperature of the compositions shown in Tables 1-7 and the amount of MgO, as discussed in more detail below. These curves are quadratic polynomial curves generated using Microsoft® Excel 97SR-2 (f). Each of these curves shows that the amount of MgO affects the liquefaction temperature, and in particular that there is a eutectic melting point, or minimum, in the liquefaction temperature vs. the amount of MgO, which means that the amount of MgO changes the glass fiber formation. It is shown that it can be controlled to produce a minimum liquefaction temperature for the composition.

More specifically, curve 1 of FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 1-7 of Table 1. A control composition is also included within this curve to extend the MgO range to 3.5 wt%.
This control composition contained 59.37 wt% SiO ₂ , 12.94 wt% Al ₂ O ₃ , 21.00 wt% CaO, 3.5 wt% MgO, 1.42 wt%.
TiO ₂ , 1.01 wt% NaO, and 0.22 wt% Fe ₂ O ₃ and has a T _{LIQ of} 2158 ° F. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 2.2-2.9 wt% MgO and a minimum in 2.45-2.65 wt% MgO. Reach the temperature.

Curve 2 in FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 8-14 of Table 2. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 1.85-2.6 wt% MgO and a minimum in 2.0-2.45 wt% MgO. Reach the temperature.

Curve 3 in FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 15-30 of Table 3. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 1.8-2.5% by weight MgO and a minimum in 2.0-2.3% by weight MgO. Reach the temperature.

Curve 4 of FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 31-38 of Table 4. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 2.3-2.7 wt% MgO and a minimum in 2.35-2.6 wt% MgO. Reach the temperature.

Curve 5 in FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 39-49 of Table 5. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 1.8-2.5% by weight MgO and a minimum in 2.0-2.3% by weight MgO. Reach the temperature.

Curve 6 of FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 50-58 of Table 6. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 2.3-2.7 wt% MgO and a minimum in 2.4-2.6 wt% MgO. Reach the temperature.

Curve 7 of FIG. 1 illustrates the relationship between the liquefaction temperature and the amount of MgO in the glass composition shown in Examples 59-66 of Table 7. As can be seen on the basis of this curve, the liquefaction temperature approaches a minimum in the range of 2.7-3.2 wt% MgO and a minimum in 2.8-3.1 wt% MgO. Reach the temperature.

As seen in curves 1-7, the amount of MgO affects the liquefaction temperature, and, in particular, the amount of MgO is to produce the minimum liquefaction temperature for the glass fiber forming composition. Can be controlled.

FIG. 2 illustrates the relationship between liquefaction temperature and amount of MgO for various combinations of Examples 8-58 in Tables 2-6. More specifically, curve A plots the liquefaction temperature vs. the amount of MgO for the glass compositions shown in Tables 2, 3 and 4, and curve B shows the glasses shown in Tables 3, 5 and 6. The liquefaction curve versus the amount of MgO is plotted for the composition, and curve C plots the liquefaction temperature versus the amount of MgO for the glass compositions shown in Tables 2-6. It is understood that curves A, B and C have combined liquefaction temperatures for different glass compositions. More specifically, the glass composition represented by curve A has the same Li ₂ O level,
The glass composition represented by curve B with different amounts of TiO ₂ has the same amount of Ti.
Has a O _2, different amounts of Li ₂ O and ZnO (although the total amount of Li ₂ O + ZnO are the same), and the glass composition is represented by curve C, TiO _2,
It depends on the amount of Li ₂ O and / or ZnO. But these combinations are
It is provided to illustrate the tendency of the liquefaction temperature as the amount of MgO changes.

With reference to FIG. 2, the liquefaction temperatures for curves A, B and C are 1.7-2.6.
The minimum is approached in the range of 5 wt% MgO, and the minimum temperature is reached in the range of 1.90 to 2.55 wt% MgO.

The glass compositions of Tables 2 to 6 have the lowest liquefaction temperature (curves 2 to 2) than the glass compositions of Table 1.
6, as shown in A, B and C) is expected. This is because all the examples 8-58 in Table 2-6, contain additives, and in particular, Li ₂ O and / or ZnO lowers the liquidus temperature. However, of particular importance is the fact that the minimum liquefaction temperatures for the glass compositions of Tables 2-6 are generally in the MgO range below the MgO range of the glass compositions of Table 1.

Looking at curves 1-7 and AC of FIGS. 1 and 2, the amount of MgO affects the heating and melting profile of the glass fiber forming composition and, in particular, using this MgO content. , It may minimize the liquefaction temperature of the glass fiber forming composition and may allow lower forming temperatures while maintaining the ΔT required to facilitate continuous and uninterrupted glass fiber forming operations. it is obvious.

Examples 67-98 in Table 8 are 2.3-2.55 wt% MgO, and NIS.
7 is an additional example of a glass composition of the present invention having a ΔT of greater than 90 ° F. based on the T714 reference standard. These laboratory samples, as discussed previously,
Based on their batch composition, up to 3% by weight B ₂ O ₃ , up to 0.9% by weight Na ₂ O, up to 1.1% by weight TiO ₂ , up to 0.9% by weight Li ₂ O. 1% by weight
Up to 3% by weight MnO, up to 3% by weight MnO ₂ . These samples were made in the same manner as described in Tables 1-7.

[0050]

[Table 8] Table 9 contains some glass fiber melt compositions made in commercial glass melting operations. The amount of each component in this table is the weight percentage in the actual melt. The weight percentage of Li ₂ O was determined using wet chemical analysis techniques and the weight percentage of B ₂ O _{3 was} determined by neutron transmission analysis (Neutron Tra).
The weight percentage of the remaining components was determined using X-ray fluorescence analysis (also known as "XRF analysis"), all of which are well known to those skilled in the art.

[0051]

[Table 9] Based on the above, in one non-limiting embodiment of the present invention, the glass fiber composition has a basic composition of SiO ₂ , CaO, Al ₂ O ₃ and Fe ₂ O ₃ , and As discussed, 1% of Na ₂ O and MgO were added as needed.
． It has a content in the range of 7 to 2.9 wt%, preferably 1.8 to 2.9 wt%, and more preferably 1.8 to 2.7 wt%. In another non-limiting embodiment, the glass fiber composition comprises 1.7-2.7 wt%, preferably 1.9.
It has a MgO content ranging from ˜2.65 wt%.

In one non-limiting embodiment of the invention, either no liquefaction temperature reducing additives other than MgO are included, or only trace amounts of these additives (ie, 0).
． For glass compositions containing less than 05 wt%), the range of MgO is 2.2-2.
． 9 wt%, preferably 2.4-2.8 wt%, and more preferably 2.45.
Is about 2.65 wt%. In another embodiment of the glass composition with little or no liquefaction temperature reducing additives other than MgO, the range of MgO is 2.2-2.7 wt%, preferably 2.3-2.6 wt%. %.

In yet another non-limiting embodiment of the present invention, at least 0.05 wt%
In the glass composition containing the entire amount of the liquefaction temperature reducing additive, the MgO content is 1.7 to 2
． 65 wt%, preferably between 1.8 wt% and 2.6 wt%, more preferably 1.9 to 2.55 wt%. In another non-limiting embodiment of the glass composition including the liquefaction temperature reducing additive, the MgO content ranges from 1.7 to 2.5 wt%, preferably between 1.8 wt% and 2.3 wt%. In one non-limiting embodiment of the present invention, the liquefaction temperature reducing additive in the glass fiber composition includes:
The amounts discussed above include, but are not limited to, Li ₂ O, ZnO, MnO, MnO ₂ and / or B ₂ O ₃ .

Other commercial glasses reduce the environmental hazards from the release of these substances by reducing or removing boron and fluorine from the batch, but these glasses are more expensive than conventional E-glass. It should be understood that it is processed at the molding temperature. As a result, they require more energy for production. The present invention provides glass compositions that have little or no boron and / or fluorine and generally have a lower forming temperature than other boron and / or fluorine-poor glass compositions, and boron-free and A fluorine-free glass composition is provided, and more particularly, has a molding temperature close to that of E-glass. In one non-limiting embodiment of the present invention, the molding temperature of the glass composition of the present invention is 2280 ° based on NIST 714 reference standard.
It should be below F (1249 ° C), preferably below 2260 ° F (1238 ° C), more preferably below 2230 ° F (1221 ° C). In one particular, non-limiting embodiment of the invention, the molding temperature is 2200 ° F (1204 ° C) or less based on the NIST 714 reference standard.

Further, in one non-limiting embodiment of the present invention, the liquefaction temperature of the glass composition of the present invention is 2155 ° F (1179 ° C) or less, preferably 2145 ° F (
1174 ° C) or less, more preferably 2130 ° F (1166 ° C) or less.

As discussed above, in the glass fiber molding industry, ΔT is maintained within a range sufficient to avoid devitrification of the molten glass in the bushing region of the glass fiber molding operation and the stagnant region of the glass melting furnace. It should be. In the present invention, ΔT is at least 65 ° F (36 ° C), preferably at least 90 °.
It should be F (50 ° C), and more preferably at least 100 ° F (56 ° C). In addition, although not required, ΔT should be less than or equal to 150 ° F (83 ° C), more preferably 125 ° F (69 ° C) to keep the overall heating and dissolution requirements of the glass fiber composition low. The following is preferable. This maintains a lower molding temperature for a given liquefaction temperature and results in good energy efficiency. If desired, the amounts of SiO ₂ and CaO can be varied to change the molding temperature and provide the desired ΔT. More specifically, reducing the silica content while at the same time maintaining or increasing the calcia content (and thus reducing the SiO ₂ / RO ratio) lowers the molding temperature and therefore ΔT. This mold modification is useful if, for example, ΔT is much higher than 100 ° F. and can be reduced without adversely affecting glass melting and molding operations. Conversely, increasing the silica content while at the same time maintaining or decreasing the calcia content (ie increasing the SiO ₂ / RO ratio) increases the molding temperature and therefore ΔT. This type of change has a very low ΔT,
Useful if it had to be reduced to at least 100 ° F. Silica and / or calcia (and resulting SiO ₂ / R in either direction)
Compositional control of O ratio) is possible until ΔT is obtained, which is considered to facilitate the search for a safe industrial melt formation process.

As discussed above, the SiO ₂ / RO ratio is necessary for the purpose of lowering the overall processing temperature, especially for lowering the molding temperature but facilitating continuous fiber forming operations. Can be manipulated to further aid in achieving the goal of providing Although not limiting the present invention, the glass fiber composition of the present invention has a SiO ₂ content of 2.3 or less, preferably 2.25 or less, more preferably 2.2 or less.
/ RO ratio.

Although the invention has been described with reference to particular embodiments, it is understood that variations and modifications known to those skilled in the art may be within the scope of the invention as defined by the claims. Should be.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the amount of MgO and the liquefaction temperature of the glass fiber composition of the present invention.

FIG. 2 is a graph showing the relationship between the amount of MgO and the liquefaction temperature of the glass fiber composition of the present invention.

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Claims (43)

[Claims] 1. A glass fiber composition comprising: 52 to 62 wt% of SiO _2; 0 to 2 wt% of Na ₂ O; 16 to 25 wt% of CaO; 8 to 16 wt% of Al ₂ O _3; 0.05 to 0.80 wt% of Fe ₂ O _3; 0~2 wt% of K ₂ O; 1.7 to 2.9 wt% of MgO; 0 weight percent of B ₂ O ₃ ; 0-2 wt% of TiO _2; 0-2 wt% of BaO; 0-2 wt% of ZrO _2; and 0-2 wt% of SrO, wherein the wherein the glass composition, NIST 714 reference A glass fiber composition having a molding temperature below 2280 ° F and a liquefaction temperature below 2155 ° F based on standards. 2. The composition comprises: 0.05-1.5 wt% Li ₂ O; 0.05-1.5 wt% ZnO; 0.05-3 wt% MnO; and 0. .05～3 wt% of MnO _2, further comprising at least one material selected from the group consisting of a glass fiber composition of claim 1. 3. The MgO content is 1.9 to 2.65 wt%, the glass composition has a B ₂ O ₃ content of 3 wt% or less, and the glass composition is The glass fiber composition of claim 2 having a SiO ₂ to RO ratio of 2.3 or less. 4. The glass fiber composition according to claim 1, wherein the MgO content is 1.8 to 2.7% by weight. 5. The glass fiber composition according to claim 4, wherein the MgO content is 1.9 to 2.65% by weight. 6. The glass fiber composition according to claim 1, wherein the glass composition has a B ₂ O ₃ content of ₃ % by weight or less. 7. The glass fiber composition of claim 1, wherein the glass composition has a SiO ₂ to RO ratio of 2.3 or less. 8. A glass fiber composition, essentially: 52-62 wt% of SiO _2; 0 to 2 wt% of Na ₂ O; 16 to 25 wt% of CaO; 8 to 16 wt% Al ₂ O ₃ ; 0.05-0.80% by weight Fe ₂ O ₃ ; 0-2% by weight K ₂ O; 2.2-2.9% by weight MgO; 0-10% by weight B ₂ O _3; 0-2 wt% of TiO _2; 0-2 wt% of BaO; 0-2 wt% of ZrO _2; and 0-2 wt% of SrO, consists, wherein the glass composition, A glass fiber composition having a molding temperature of 2280 ° F or less and a liquefaction temperature of 2155 ° F or less based on NIST 714 reference standard. 9. The glass fiber composition according to claim 8, wherein the SiO ₂ content is 55 to 61 wt%, and the Na ₂ O content is up to 1.5 wt%. The CaO content is 20 to 25% by weight, the Al ₂ O ₃ content is 11 to 14% by weight, the Fe ₂ O ₃ content is up to 0.5% by weight,
A glass fiber composition having a K ₂ O content of up to 1% by weight. 10. The glass composition having a B ₂ O ₃ content of ₃ % by weight or less, 2.
The glass fiber composition of claim 9 having a SiO ₂ to RO ratio of 3 or less and a ΔT of at least 65 ° F. 11. The glass fiber composition according to claim 8, wherein the MgO content is 2.4 to 2.7% by weight. 12. The MgO content is 2.45 to 2.65% by weight.
The glass fiber composition according to claim 11. 13. The glass fiber composition of claim 8, wherein the glass composition has a SiO ₂ to RO ratio of 2.3 or less. 14. The glass fiber composition according to claim 8, wherein the glass composition has a B ₂ O ₃ content of ₃ % by weight or less. 15. The glass fiber composition of claim 14, wherein the glass composition is essentially free of boron. 16. The glass fiber composition of claim 8, wherein the glass composition has a forming temperature of 2260 ° F. or less based on NIST 714 reference standard. 17. The glass fiber composition of claim 16, wherein the glass composition has a liquefaction temperature of 2245 ° F. or less. 18. The glass fiber composition of claim 8, wherein the composition has a ΔT of at least 65 ° F. 19. The composition has a ΔT of 150 ° F. or less.
The glass fiber composition described in 1. 20. A glass fiber composition comprising: 52 to 62 wt% of SiO _2; 0 to 2 wt% of Na ₂ O; 16 to 25 wt% of CaO; 8 to 16 wt% of Al ₂ O _3; 0.05 to 0.80 wt% of Fe ₂ O _3; 0~2 wt% of K ₂ O; 1.7 to 2.6 wt% of MgO; 0 weight percent of B ₂ O ₃ ; 0-2 wt% of TiO _2; 0-2 wt% of BaO; 0-2 wt% of ZrO _2; and 0-2 wt% of SrO, comprises and following: 0.05-1.5 wt % of Li ₂ O; 0.05 to 1.5 wt% of ZnO; 0.05-3 wt% of MnO; and 0.05-3 wt% of MnO _2, at least one selected from the group consisting of Further comprising a material, wherein the glass composition is 2280 ° F. or less based on NIST 714 reference standard. Molding temperature, and 2155 ° F with the following liquefaction temperature, the glass fiber composition. 21. The glass fiber composition according to claim 20, wherein the MgO content is 1.8 to 2.5% by weight. 22. The glass fiber composition according to claim 21, wherein the MgO content is 1.9 to 2.5% by weight. 23. The glass fiber composition according to claim 22, wherein the SiO ₂ content is 57 to 59 wt% and the Na ₂ O content is up to 1 wt%. The CaO content is 22-24 wt%, the Al ₂ O ₃ content is 12-14 wt%, the Fe ₂ O ₃ content is up to 0.4 wt%, and the K ₂ A glass fiber composition having an O content of up to 0.1% by weight. 24. The composition comprises: 0.2-1 wt% Li ₂ O; 0.2-1 wt% ZnO; up to 1 wt% MnO; and up to 1 wt% MnO ₂ , 24. The glass fiber composition of claim 23, comprising at least one material selected from the group consisting of: 25. The glass fiber composition according to claim 20, wherein the glass composition has a B ₂ O ₃ content of ₂ % by weight or less. 26. The glass fiber composition according to claim 20, wherein the SiO ₂ content is 55 to 61 wt%, and the Na ₂ O content is up to 1.5 wt%. And the CaO content is 20 to 25% by weight, and the A
A glass fiber composition having an l ₂ O ₃ content of 11 to 14% by weight, said Fe ₂ O ₃ content of up to 0.5% by weight and said K ₂ O content of up to 1% by weight. object. 27. The glass fiber composition according to claim 26, wherein the SiO ₂ content is 57 to 59 wt% and the Na ₂ O content is up to 1 wt%. The CaO content is 22 to 24% by weight, and the Al ₂
A glass fiber composition having an O ₃ content of 12 to 14% by weight, said Fe ₂ O ₃ content of up to 0.4% by weight and said K ₂ O content of up to 0.1% by weight. object. 28. The composition comprising: from 0.2 to 1 wt% Li ₂ O; 0.2 to 1 wt% ZnO; up to 1 wt% MnO; up to 1 wt% MnO ₂ . 21. The glass fiber composition of claim 20, further comprising at least one material selected from the group consisting of: 29. The glass fiber composition according to claim 20, wherein the glass composition has a B ₂ O ₃ content of ₃ % by weight or less. 30. The glass fiber composition according to claim 29, wherein the glass composition has a B ₂ O ₃ content of ₂ % by weight or less. 31. The glass fiber composition according to claim 30, wherein the glass composition has a B ₂ O ₃ content of 1% by weight or less. 32. The glass fiber composition of claim 31, wherein the glass composition is essentially free of boron. 33. The glass fiber composition of claim 20, wherein the glass composition has a SiO ₂ to RO ratio of 2.3 or less. 34. The glass fiber composition of claim 33, wherein the glass composition has a SiO ₂ to RO ratio of 2.25 or less. 35. The glass fiber composition of claim 34, wherein the glass composition has a SiO ₂ to RO ratio of 2.2 or less. 36. The glass fiber composition of claim 20, wherein the glass composition has a forming temperature of 2260 ° F. or less based on NIST 714 reference standard. 37. The glass fiber composition of claim 36, wherein the glass composition has a forming temperature of 2230 ° F. or less based on NIST 714 reference standard. 38. The glass fiber composition of claim 37, wherein the glass composition has a molding temperature of 2200 ° F. or less based on NIST 714 reference standard. 39. The glass fiber composition of claim 20, wherein the glass composition has a liquefaction temperature of 2245 ° F. or less. 40. The glass fiber composition of claim 39, wherein the glass composition has a liquefaction temperature of 2230 ° F. or less. 41. The glass fiber composition of claim 20, wherein the composition has a ΔT of at least 65 ° F. 42. The glass fiber composition of claim 41, wherein the composition has a ΔT of at least 90 ° F. 43. The composition of claim 4, wherein the composition has a ΔT of 150 ° F. or less.
The glass fiber composition according to 1.