Cross-Reference to Related Application
[0001] This application claims the benefits of United States Provisional Application No.
60/406,315 entitled "Low-Temperature, Fluoride Free Fiber Glass Compositions and Products
Made Using Same" filed August 27, 2002, which is herein incorporated by reference
in its entirety.
BACKGROUND OF THE INVENTION
2. Field of the Invention
[0002] This invention relates to low temperature; fluoride free glass fiber compositions,
and products made using such glass fibers, and in particular, to fluoride-free boron-containing
E-glass fiber compositions having the temperature properties of a fluoride and boron
containing E-glass fiber composition, and to products using such glass fibers, e.g.
glass fiber reinforced plastic composites.
3. Discussion of the Technical Problem
[0003] In the art of producing glass fibers or fiber glass, it is recognized that fluoride
is a flux during batch melting and aids in lowering melt viscosity of the glass thereby
lowering the fiber-forming temperature. Although fluoride aids in the melting of glass
batch, there are drawbacks. More particularly, fluoride is volatile at the glass melting
and fining temperatures, and emission control equipment is sometimes used to prevent
fluoride from being discharged into the environment.
[0004] It has been recognized that E-glass compositions can be made without fluoride and
with less than 3.0 weight percent boron ("weight percent"). EP Patent Application
No. 0.832 046 published April 5, 2000, titled "BORON-FREE GLASS FIBERS" discloses
a boron free glass composition having fluoride in the range of 0 to 0.5 weight percent.
The examples of the EP Application have a forming temperature at 1000 poise ranging
from 1259°C to 1266°C and a forming window ranging from 72°C to 96°C. PCT Application
No. WO 01/32576 A1 published May 10, 2001, titled "GLASS YARNS, COMPOSITE THEREOF,
METHOD FOR MAKING SAME AND REINFORCEING GLASS COMPOSITION", discloses a fiber glass
composition having less than 1 weight percent fluoride and 0.5 to 3 weight percent
boron. The examples of the PCT Application have a forming temperature at 1000 poise
ranging from 1200°C to 1350°C with forming window ranging from as low as 5°C to 75°C
with most of the compositions have forming window around 40°C. Although the glass
compositions of the EP and PCT Applications are acceptable for their intended purpose
there are limitations. More particularly, the glasses have a high forming temperature,
e.g. above 1195°C. Glass compositions that have high forming temperatures require
greater energy usage and result in shorter bushing life. The small forming window,
e.g. less than 50°C, increases the tendency of the glass fibers to devitrify causing
fiber breaks.
[0005] Therefore, it can be seen that using fluoride as a melting aid has drawbacks, and
fluoride-free boron-containing fiber glass compositions presently available have drawbacks
as well. It would be advantageous to provide fluoride-free, boron-containing fiber
glass compositions that have thermal properties, e.g. forming temperatures below 1190°C
and a forming window greater than 50°C, similar to prior art fluoride and boron-containing
fiber glass compositions.
SUMMARY OF THE INVENTION
[0006] This invention relates to fluoride or fluorine-free glass compositions. As appreciated
by those skilled in the art, fluorine is present in the glass as a fluoride, e.g.
calcium fluoride and/or sodium fluoride. Since fluorine is present in the glass as
a fluoride, all forms of fluorine in the glass will be referred to as "fluoride".
Analytically, the concentration of fluoride in the glass is conventionally reported
as F2. The source of deliberate additions of fluoride to glass is usually a fluorspar
component in the batch mixture. The concentration of fluoride (F2) in commercial fiber
glass is typically in the range of 0.5 to 0.7 weight percent when fluoride is deliberately
included as a fluxing agent. Fluoride in low weight percent, e.g. less than 0.1 weight
percent and typically between 0.02 and 0.06 weight percent is also present in the
glass as an impurity from one or more of the other batch materials. In the practice
of this invention, the amount of fluoride present in the glass is limited to impurity
levels, i.e., less than about 0.1 weight percent, even if deliberately added. Therefore,
for the purposes of this invention, "fluoride free" means less than about 0.1 weight
percent fluoride.
[0007] In the present invention the fluoride-free, boron-containing glass has a forming
temperature no greater than 1190°C, and in some embodiments the forming temperature
is no greater than 1185°C. The glasses of the present invention are also characterized
by a forming window of at lease 50°C. "Forming temperature" is the temperature of
the glass at which the viscosity of the glass is 1000 poise (commonly expressed as
the "log 3 viscosity"). Liquidus temperature is the temperature at which minute solid
phase (crystals) is in equilibrium with the liquid phase of the glass melt. The forming
window is the difference between the forming temperature and the liquidus temperature.
Forming window is a common measure of the crystallization potential of a given melt
composition. The smaller the difference between the forming temperature and the liquidus
temperature, the greater is the crystallization potential.
[0008] In a non-limiting embodiment of the invention, a glass composition includes the following
ingredients in the following weight percents ("weight percent")
| SiO2 |
50 - 54 percent |
| Al2O3 |
12-15 percent |
| CaO |
22-25 percent. |
| MgO |
1-4 percent |
| B2O3 |
5-8 percent |
| (Na2O + K2O) |
less than 2 percent |
| Fe2O3 |
0.1 - 0.5 percent |
| F2 |
less than 0.1 percent |
the glass having a forming window of at least 50°C and a forming temperature no greater
than 1190°C (or no greater than 1185°C).
[0009] In another non-limiting embodiment, the glass may include:
| SiO2 |
50 to 54 weight percent |
| Al2O3 |
12 to 15 weight percent |
| CaO |
22 to 25 weight percent |
| MgO |
1 to 4 weight percent |
| SrO |
0 to 3 weight percent |
| (MgO + SrO) |
1 to 4 weight percent |
| B2O3 |
5 to 8 weight percent |
| F2 |
less than 0.1 weight percent, |
wherein the glass has a forming window of at least 50°C and a forming temperature
no greater than 1190°C (or no greater than 1185°C).
[0010] The glass compositions of certain non-limiting embodiments of the invention have
the following relationship of the ingredients:
[0011] The sum of the weight percent of CaO + MgO + SrO ("RO") may be 24.75 to 26.25 percent,
and in some embodiments 25 to 26 percent.
[0012] The ratio of the weight percent of RO/(SiO
2+Al
2O
3) may be 0.30 to 0.45, and in some embodiments 0.35 to 0.40.
[0013] The ratio of the weight percent of (R
2O + RO + B
2O
3)/(SiO
2 + Al
2O
3) may be 0.40 to 0.55, and in some embodiments 0.44 to 0.50. "R
2O" is the sum of the weight percent of Na
2O + Li
2O + K
2O.
[0014] In another non-limiting embodiment of the invention the fluoride-free glass composition
may comprise the following constituents ("weight percent"):
| SiO2 |
52.86 to 54.33 weight percent |
| B2O3 |
5.15 to 6.05 weight percent |
| Al2O3 |
13.44 to 14.14 weight percent |
| CaO |
23.42 to 24.16 weight percent |
| MgO |
1.17 to 1.5 weight percent |
| SrO |
0 to 0.15 weight percent |
| MgO + SrO |
1.40 to 1.65 weight percent |
Optionally, the glass composition above may additionally include:
| Total iron (expressed as Fe2O3) |
0.29 to 0.37 weight percent |
| SO3 |
greater than 0 weight percent, |
| K2O |
0.09 to 0.1 weight percent |
| TiO2 |
0.5 to 0.6 weight percent |
| Na2O |
0.4 to 0.9 weight percent |
| ZrO2 |
less than 0.1 weight percent |
[0015] The glass compositions of the invention may be used to make continuous glass fiber
strand or chopped fiber glass reinforcements.
DISCUSSION OF THE INVENTIION
[0016] All numbers expressing dimensions, physical characteristics, and so forth, used in
the specification and claims are to be understood as being modified in all instances
by the term "about". Accordingly, unless indicated to the contrary, the numerical
values set forth in the following specification and claims can vary depending upon
the desired properties sought to be obtained by the present invention. At the very
least, and not as an attempt to limit the application of the doctrine of equivalents
to the scope of the claims, each numerical parameter should at least be construed
in light of the number of reported significant digits and by applying ordinary rounding
techniques. Moreover, all ranges disclosed herein are to be understood to encompass
any and all subranges subsumed therein. For example, a stated range of "1 to 10" should
be considered to include any and all subranges between (and inclusive of) the minimum
value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum
value of 1 or more and ending with a maximum value of 10 or less, e.g., 5.5 to 10.
[0017] As used in the following discussion regarding the high temperature properties of
the glass, the terms "melting temperature" (or "T
M" mean the temperature of the glass at which the viscosity of the glass is log1.7
or 50 poise. "T
F" means the forming temperature as defined above. "T
L" means the "liquidus temperature" as defined above. The forming window, i.e., the
difference between T
F and T
L, may also be referred to herein as "ΔT." In the commercial production of glass fiber,
a minimum AT of least 50°C (90°F) is considered desirable in order to prevent devitrification
of the molten glass during a glass fiber forming operation, in particular in the bushing
area.
[0018] The fiber glass compositions of the invention have thermal properties similar to
the thermal properties of fluoride and boron-containing glasses, e.g. melting temperatures
below 1420°C; forming temperatures no greater than 1190°C, and a forming window not
less than 50°C.
[0019] As is known to those of skill in the art, additional optional ingredients may be
added to glass composition to alter certain properties of the glass without departing
from the practice of the present invention. Other materials may be present in the
batch materials as impurities. These ingredients include but are not limited to FeO
and/or Fe
2O
3 (collectively referred to as "iron"), Na
2O, Li
2O, and K
2O. Iron may be present in amounts of 0.005 to 1.5 weight percent, preferably 0.01
to 1 weight. percent and more preferably 0.05 to 0.8 weight percent. Na
2O, Li
2O or K
2O may be present in amounts of 0 to 2 weight percent, or 0 to 1.5 weight percent,
or 0 to 1 weight percent. Further, sulfate (or SO
3) may be present as a melting and fining aid in amounts of greater than 0 weight percent.
[0020] Boron and fluoride are conventionally added to the glass batch to lower the melting
temperature of the batch. As the weight percent of the boron in the batch increases
while keeping the other ingredients in the batch relatively constant in their proportions
to each other, the melting temperature of the batch decreases. The drawback with using
boron is that it raises environmental issues and is generally only used when specified
as an ingredient in the glass composition, e.g. in E-glass compositions. E-glass compositions
are discussed below. As the weight percent of fluoride in the batch increases while
keeping the other ingredients in the batch relatively constant in their proportions
to each other; the melting temperature of the batch decreases. A drawback with using
fluoride is that it raises environmental issues and is usually added as a batch ingredient
to reduce the melting temperature of the batch and to reduce the viscosity of the
glass.
[0021] Varying the ingredients of the batch materials without additives, such as boron and
fluoride, can also reduce the viscosity of the glass. More particularly, it is known
that pure silica is the highest melting glass former. A pure silica melt does not
have a well defined melting point, but gradually solidifies and forms a glass as it
cools to room temperature and its viscosity drops from greater than log 4 (10,000)
poise at 2500°C (4532°F). Pure calcia, magnesia and alumina melts are known to have
very low viscosities of 0.5 to 2 poise at their respective melting points. These materials
do not solidify into a glass but rather crystallize instantly at their sharply defined
melting point.
[0022] Based on these material properties, it can be inferred that as SiO
2, which is the largest oxide component of the glass composition in terms of weight
percent, is reduced in a given composition of this type, the melt viscosity and the
resulting log 3 forming temperature drops. If CaO, which is the second largest component
of the glass composition in terms of weight percent, or MgO and /or SrO is increased
in such a composition, the effect of the sum of the weight percent of CaO + MgO +
SrO defined as RO on the glass properties will be twofold. It will not only increase
the fluidity of the resulting melt (i.e. decrease its viscosity) and it will increase
the crystallizability of the resulting melt (i.e. increase its liquidus temperature),
having the effect of reducing ΔT.
[0023] For example, increasing the ratio of the weight percent of RO to the weight percent
of the sum of SiO
2 and Al
2O
3 (RO/(SiO
2 + Al
2O
3)) while keeping proportions of the other ingredients in the batch constant decreases
the melting temperature and visa versa. As can be appreciated by one skilled in the
art of making glass fibers, the ratio of RO/(SiO
2 + Al
2O
3) is controlled to lower melt viscosity or melting and forming temperature; however,
the lowering of the melt viscosity has to be realized without significantly increasing
liquidus temperature. As discussed above, to ensure a safe fiber forming process,
the fiber forming window, i.e., (T
F - T
L) should be maintained at 50°C (90°F) or greater. In some embodiments of the invention,
the ratio of RO/(SiO
2 + Al
2O
3) of the glass compositions ranges from 0.30 to 0.45, and in other embodiments from
0.35 to 0.40.
[0024] In addition to changing the ratio RO/(SiO
2 + Al
2O
3) to provide an adequate fiber forming window and a low forming temperature, i.e.
less than 1190°C and preferably less than 1185°C, in the instance when the glass composition
contains boron, e.g. in the case of E-glass compositions, and alkalis, e.g. but not
limiting to the invention Na
2O, Li
2O, and K
2O further tuning of the thermal properties can be realized by changing the ratio of
the sum of the weight percent of Na
2O, Li
2O, K
2O, RO and B
2O
3 to the sum of the weight percent of SiO
2 and Al
2O
3 ((R
2O + RO + B
2O
3)/(SiO
2 + Al
2O
3) where R
2O = Na
2O + Li
2O + K
2O). The (R
2O + RO + B
2O
3) /(SiO
2 + Al
2O
3) ratio is another ratio used to characterize a given melt. In some embodiments of
invention, the (R
2O + RO + B
2O
3) /(SiO
2 + Al
2O
3) ratio of the glass composition may range from 0.40 to 0.55, and in other embodiments
it may range from 0.44 to 0.48.
[0025] Lower Al
2O
3 levels will typically result in lower crystallization potential, and a higher Al
2O
3 level will typically result in a higher crystallization potential for a given melt.
With respect to Al
2O
3/SiO
2 ratio, a decreasing ratio would be accompanied by a reduction in the crystallization
potential of the melt.
[0026] Each of these compositional features of the glass reflect the relative balance between
the fluidity (i.e. viscosity) of the glass melt and its crystallization potential,
as will be discussed later in more detail. The physical melt properties of interest
are the melting temperature, forming temperature and the liquidus temperature since
one non-limiting embodiment of the present invention is to provide a fluoride free,
boron containing glass composition having a forming temperature and a ΔT similar to
a fluoride and boron-containing electronic E-glass so that the compositions are interchangeable
without making major changes in the fiber forming process.
[0027] The E-glass composition is defined in ASTM Designation: D 578 - 00 entitled
Standard Specification for Glass Fiber Strands as a family of glasses composed primarily of the oxides of calcium, aluminum, and
silicon. The following chemical composition of E-glass applies to glass fiber products
for electronic applications such as printed circuit boards:
| Component |
% by Weight |
| B2O3 |
5 to 10 |
| CaO |
16 to 25 |
| Al2O3 |
12 to 16 |
| SiO2 |
52 to 56 |
| MgO |
0 to 5 |
| Na2O and K2O |
0 to 2 |
| TiO2 |
0 to 0.8 |
| Total FeO and Fe2O3 |
0.05 to 0.4 |
| Fluoride (F2) |
0 to 1.0. |
[0028] Samples 1 to 10 were made as follows. Batches, approximately 1000 grams per formulation,
were prepared using commercial ingredients. Table 1 shows the composition of the batch
materials for Samples 1 to 10. Fluorspar was added to the batch for Samples 6 to 9
to provide the fluoride and quicklime was added to the batch for Samples 7 and 8 to
provide CaO.
[0029] The ingredients were thoroughly mixed and charged into a platinum crucible. The batch
materials were heated to, and maintained for four hours at, a temperature of 1450°C
to melt the materials and ensure melt homogeneity. After melting, the molten glass
was poured onto a stainless steel plate and two buttons were cut-from the hot glass
for subsequent testing discussed below. Each button had a 2 inches (5.08 centimeter)
diameter.
[0030] The weight percent of the ingredients in the glass samples except for boron was measured
using the x-ray fluorescence (XFR) method, and the weight percent of boron was measured
using the neutron absorption method. The measurements presented in the following discussion
are the average of two measurements. Table 2 lists the weight percent of the ingredients
in the glass buttons. Samples 1 to 5 and 10 had impurity amounts of fluoride, more
particularly, fluoride in the range of 0.02 to 0.08 weight percent; Samples 6 through
9 had fluoride in amounts in the range of 0.11 to 0.27 weight percent, and are not
examples of the present invention.
[0031] A piece of glass weighing about 70 grams of each sample composition was used to determine
liquidus temperature, and a piece of glass weighing about 500 grams of each sample
composition was used to determine melt viscosity as a function of temperature. The
forming temperature, i.e. the glass temperature at a viscosity of 1000 poise, was
determined by ASTM method C965-81, and the liquidus temperature by ASTM method C829-81.
Table 3 summarizes the high-temperature properties, liquidus (T
L), forming (T
F), forming window (T
F-L), and melting (T
M) of Samples 1 to 10.
[0032] The results of the measurements demonstrate the invention achieved low-melting fiber
glass compositions having no more than trace amounts of fluoride, e.g., below 0.1
weight percent, and boron in amounts in the range of about 5 to 8 weight percent without
adversely impacting the fiber forming window. At least 5 weight percent B
2O
3 is required by the specification for electronic E-glass, minimizing boron content
within that range may be advantageous in some cases, so certain embodiments of the
invention employ B
2O
3 in amounts of 5 to about 7 weight percent or 5 to about 6 weight percent.
[0033] Table 4 shows the major constituents and ratios of the constituents of Samples 1
to 10. Samples 1 to 5 and 10 incorporate features of the invention.
[0034] The glass made in accordance to the teachings of the invention may be used to make
any type of product that uses glass. For example, but not limiting thereto, glass
fibers made using the glass compositions of the invention may be used to make woven
glass fiber cloth and printed circuit boards having woven fiber glass cloth. The art
of making glass fibers, woven fiber glass cloth and printed circuit boards using woven
fiber glass cloth are well known in the art and no further discussion is deemed necessary.
Table 1. Batch Formulations of Samples 1 to 10
| Batch Formulation |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
| CLAY |
270.20 |
265.20 |
274.80 |
265.20 |
269.50 |
| COLEMANITE |
95.60 |
80.60 |
70.70 |
37.90 |
37.10 |
| ULEXITE |
38.20 |
38.20 |
38.20 |
80.20 |
86.20 |
| FLUORSPAR |
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
| ROUGE |
0.60 |
0.60 |
0.60 |
0.60 |
0.70 |
| LIMESTONE |
265.60 |
258.90 |
267.40 |
265.60 |
260.50 |
| DOLOMITE |
13.10 |
18.00 |
18.90 |
18.00 |
18.00 |
| SILICA |
281.10 |
281.70 |
285.40 |
281.70 |
274.30 |
| SODIUM SULFATE |
2.00 |
2.00 |
2.00 |
2.00 |
0.90 |
| SODA ASH |
0.00 |
0.00 |
0.00 |
0.00 |
3.70 |
| RUTILE |
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
| QUICKLIME |
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
| Total (g) |
966.40 |
945.20 |
958.00 |
951.20 |
950.90 |
| Batch Formulation |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Example 10 |
| CLAY |
268.90 |
287.68 |
283.54 |
268.60 |
282.60 |
| COLEMANITE |
29.45 |
27.13 |
28.27 |
25.63 |
23.80 |
| ULEXITE |
92.60 |
110.72 |
110.96 |
95.80 |
101.70 |
| FLUORSPAR |
4.85 |
5.35 |
2.675 |
7.28 |
0.00 |
| ROUGE |
0.65 |
0.85 |
0.98 |
0.63 |
0.70 |
| LIMESTONE |
262.65 |
177.37 |
176.98 |
263.73 |
288.20 |
| DOLOMITE |
12.20 |
14.40 |
17.85 |
9.30 |
12.50 |
| SILICA |
275.35 |
311.80 |
314.20 |
275.88 |
286.80 |
| SODIUM SULFATE |
0.90 |
0.78 |
0.79 |
0.90 |
0.90 |
| SODA ASH |
3.40 |
2.85 |
2.78 |
3.25 |
2.80. |
| RUTILE |
0.00 |
0.00 |
0.00 |
0.00 |
0.00 |
| QUICKLIME |
0.00 |
61.07 |
61.03 |
0.00 |
0.00 |
| Total (g) |
950.95 |
1000.00 |
1000.05 |
950.98 |
1000.00 |
Table 3. Fiber Processing Properties of Samples 1 to 10
| Glass ID |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5 |
| Liquidus, TL (°C) |
1097 |
1101 |
1119 |
1105 |
1102 |
| Forming, TF (°C) |
1163 |
1171 |
1180 |
1169 |
1166 |
| Window, TF-TL (°C) |
66. |
70 |
61 |
64 |
64 |
| Melting, TM (°C) |
1397 |
1410 |
1419 |
1409 |
1406 |
| Glass ID |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Example 10 |
| Liquidus, TL (°C) |
1092 |
1110 |
1099 |
1115 |
1110 |
| Forming, TF (°C) |
1156 |
1161 |
1163 |
1169 |
1163 |
| Window, TF-TL (°C) |
64 |
61 |
64 |
54 |
53 |
| Melting, TM (°C) |
1396 |
1405 |
1408 |
1404 |
1399 |
Table 4. Corresponding Ratios of Major Glass Components of Samples 1 to 10
| Major Constituents and Ratios |
Example 1 |
Example 2 |
Example 3 |
Example 4 |
Example 5. |
| RO |
25.43 |
25.38 |
25.38 |
25.68 |
25.02 |
| R2O |
0.51 |
0.52 |
0.50 |
0.76 |
0.76 |
| RO/(Al2O3+SiO2) |
0.38 |
0.37 |
0.37 |
0.38 |
0.37 |
| Al2O3/SIO2 |
0.25 |
0.25 |
0.26 |
0.26 |
0.26 |
| (B2O3+RO+R2O)/(Al2O3+SiO2) |
0.47 |
0.47 |
0.46 |
0.48 |
0.46 |
| Major Constituents and Ratios |
Example 6 |
Example 7 |
Example 8 |
Example 9 |
Example 10 |
| RO |
24.75 |
24.81 |
23.61 |
25.01 |
25.44 |
| R2O |
1.12 |
1.02 |
1.08 |
1.00 |
1.02 |
| RO/(Al2O3+SiO2) |
0.37 |
0.37 |
0.34 |
0.37 |
0.38 |
| Al2O3/SiO2 |
0.26 |
0.26 |
0.24 |
0.27 |
0.27 |
| (B2O3+RO+RO2)/(Al2O3+SiO2) |
0.48 |
0.47 |
0.44 |
0.46 |
0.48 |
[0035] It will be appreciated by those skilled in the art that changes can be made to the
embodiments of the invention described above without departing from the broad inventive
concept of the invention. Based on the description of the embodiments of the invention,
it can be appreciated that this invention is not limited to the particular embodiments
disclosed, but it is intended to cover modifications that are within the spirit and
scope of the invention, as defined by the appended claims.
1. A glass composition for fiber forming comprising, in percent by weight of total composition:
| SiO2 |
50-54 percent |
| Al2O3 |
12-15 percent |
| CaO |
22-25 percent |
| MgO |
1-4 percent |
| B2O3 |
5-8 percent |
| Na2O + K2O |
less than 2 percent |
| Fe2O3 |
0.1- 0.5 percent |
| F2 |
less than 0.1 percent |
the glass having a forming window of at least 50°C and a forming temperature no greater
than 1190°C.
2. The glass composition according to claim 1, wherein the B2O3 content is 5 to 6 weight percent.
3. The glass composition according to claim 1 further including SrO, wherein MgO + SrO
is 1 to 4 weight percent.
4. The glass composition according to claim 3 wherein MgO + SrO is from 1 to 3 weight
percent.
5. The glass composition according to claim 1 wherein the constituents have the following
relationship and the following values:
| RO = CaO + MgO + SrO |
|
| RO/(SiO2 + Al2O3) |
from 0.30 to 0.45 |
6. The glass composition according to claim 1 wherein the constituents have the following
values:
| (R2O + RO + B2O3)/(SiO2 + Al2O3) |
from 0.45 to 0.50 |
where R2O = weight percent of NaO
2 + Li
2O + K
2O, when present in glass, and RO = CaO + MgO + SrO.
7. The glass composition according to claim 5 wherein the constituents are in the following
weight percent:
| SiO2 |
52 to 54 weight percent |
| Al2O3 |
13 to 15 weight percent |
| CaO |
23 to 25 weight percent |
| MgO |
1 to 3 weight percent |
| SrO |
0 to 3 weight percent |
| MgO + SrO |
1 to 3 weight percent |
8. The glass composition according to claim 7, further including:
| total iron |
0.05 to 0.8 weight percent |
| SO3 |
greater than 0 weight percent. |
9. The glass composition according to claim 4, wherein the constituents comprise:
| SiO2 |
52.86 to 54.33 weight percent |
| B2O3 |
5.15 to 6.05 weight percent |
| Al2O3 |
13.44 to 14.14 weight percent |
| CaO |
23.42 to 24.16 weight percent |
| MgO |
1.17 to 1.5 weight percent |
| SrO |
0.12 to 0.15 weight percent |
| MgO + SrO |
1.29 to 1.65 weight percent |
10. The glass composition according to claim 9 additionally comprising:
| Total iron |
0.29 to 0.37 weight percent |
| SO3 |
greater than 0 weight percent. |
| K2O |
0.09 to 0.11 weight percent |
| TiO2 |
0.54 to 0.62 weight percent |
| Na2O |
0.41. to 0.91 weight percent |
| ZrO2 |
less than 0.1 weight percent |
11. The glass composition according to claim 10, wherein the constituents have the following
values:
| Al2O3/SiO2 |
from 0.25 to 0.27 |
| RO = CaO MgO + SrO |
from 25.02 to 25.68 |
| RO/(SiO2 + Al2O3) |
from 0.37 to 0.38 |
| (R2O + RO + B2O3)/(SiO2 + Al2O3) |
from 0.46 to 0.48 |
wherein R
2O = weight percent of Na
2O + Li
2O + K
2O
12. The glass composition according to claim 1, wherein the forming temperature is no
more than 1185°C.
13. A woven fiber glass cloth wherein at least one of the glass fiber has the composition
of claim 1.
14. A printed circuit board comprising a woven fiber glass cloth wherein at least one
of the glass fibers has the composition of claim 1.
1. Eine Glaszusammensetzung zur Faserbildung, enthaltend in Gewichtsprozent der Gesamtzusammensetzung:
| SiO2 |
50 - 54% |
| Al2O3 |
12 - 150% |
| CaO |
22 - 25% |
| MgO |
1 - 4% |
| B2O3 |
5 - 8% |
| Na2O + K2O |
weniger als 2% |
| Fe2O3 |
0,1 - 0,5% |
| F2 |
weniger als 0,1%, |
wobei das Glas ein Formgebungsintervall von wenigstens 50°C und eine Formgebungstemperatur
von nicht mehr als 1190°C aufweist.
2. Glaszusammensetzung nach Anspruch 1, worin der B2O3-Gehalt 5 bis 6 Gew.-% beträgt.
3. Glaszusammensetzung nach Anspruch 1, die zusätzlich SrO enthält, worin MgO + SrO 1
bis 4 Gew.-% beträgt.
4. Glaszusammensetzung nach Anspruch 3, worin MgO + SrO 1 bis 3 Gew.-% beträgt.
5. Glaszusammensetzung nach Anspruch 1, wobei die Bestandteile die folgende Beziehung
und die folgenden Werte aufweisen:
| RO = CaO + MgO + SrO |
|
| RO/(SiO2 + Al2O3) |
0,30 bis 0,45. |
6. Glaszusammensetzung nach Anspruch 1, wobei die Bestandteile die folgenden Werte aufweisen:
| (R2O + RO + B2O3)/(SiO2 + Al2O3) |
0,45 bis 0,50. |
worin R
2O = Gewichtsprozent von Na
2O + Li
2O + K
2O, falls im Glas vorhanden, und RO = CaO + MgO + SrO.
7. Glaszusammensetzung nach Anspruch 5, wobei die Bestandteile die folgenden Gewichtsprozentanteile
haben:
| SiO2 |
52 bis 54 Gew.-% |
| Al2O3 |
13 bis 15 Gew.-% |
| CaO |
23 bis 25 Gew.-% |
| MgO |
1 bis 3 Gew.-% |
| SrO |
0 bis 3 Gew.-% |
| MgO + SrO |
1 bis 3 Gew.-%. |
8. Glaszusammensetzung nach Anspruch 7, die weiterhin enthält:
| Gesamteisen |
0,05 bis 0,8 Gew.-% |
| SO3 |
mehr als 0 Gew.-%. |
9. Glaszusammensetzung nach Anspruch 4, wobei die Bestandteile umfassen:
| SiO2 |
52,86 bis 54,33 Gew.-% |
| B2O3 |
5,15 bis 6,05 Gew.-% |
| Al2O3 |
13,44 bis 14,14 Gew.-% |
| CaO |
23,42 bis 24,16 Gew.-% |
| MgO |
1,17 bis 1,5 Gew.-% |
| SrO |
0,12 bis 0,15 Gew.-% |
| MgO + SrO |
1,29 bis 1,65 Gew.-%. |
10. Glaszusammensetzung nach Anspruch 9, die zusätzlich enthält:
| Gesamteisen |
0,29 bis 0,37 Gew.-% |
| SO3 |
mehr als 0 Gew.-% |
| K2O |
0,09 bis 0,11 Gew.-% |
| TiO2 |
0,54 bis 0,62 Gew.-% |
| Na2O |
0,41 bis 0,91 Gew.-% |
| ZrO2 |
weniger als 0,1 Gew.-%. |
11. Glaszusammensetzung nach Anspruch 10, wobei die Bestandteile die folgenden Werte aufweisen:
| Al2O3/SiO2 |
0,25 bis 0.27 |
| RO = CaO + MgO + SrO |
25,02 bis 25,68 |
| RO/(SiO2 + Al2O3) |
0,37 bis 0,38 |
| (R2O + RO + B2O3)/(SiO2 + Al2O3) |
0,46 bis 0,48, |
worin R
2O = Gewichtsprozent von Na
2O + Li
2O + K
2O.
12. Glaszusammensetzung nach Anspruch 1, worin die Formgebungstemperatur nicht mehr als
1185°C beträgt.
13. Gewebtes Glasfasertuch, worin wenigstens eine der Glasfasern die Zusammensetzung nach
Anspruch 1 aufweist.
14. Leiterplatte, enthaltend ein gewebtes Glasfasertuch, worin wenigstens eine der Glasfasern
die Zusammensetzung nach Anspruch 1 aufweist.
1. Composition de verre pour la formation de fibres comprenant, en % en poids de la composition
totale :
| SiO2 |
50-54 % |
| Al2O3 |
12-15 % |
| CaO |
22-25 % |
| MgO |
1-4 % |
| B2O3 |
5-8 % |
| Na2O + K2O |
moins de 2% |
| Fe2O3 |
0,1-0,5 % |
| F2 |
moins de 0,1 %, |
le verre ayant une fenêtre de formation d'au moins 50°C et une température de formation
de pas plus de 1190°C.
2. Composition de verre suivant la revendication 1, dans laquelle la teneur en B2O3 est 5 à 6 % en poids.
3. Composition de verre suivant la revendication 1, comprenant de plus du SrO, dans laquelle
MgO + SrO constitue de 1 à 4 % en poids.
4. Composition de verre suivant la revendication 3, dans laquelle MgO + SrO est de 1
à 3 % en poids.
5. Composition de verre suivant la revendication 1, dans laquelle les constituants ont
la relation suivante et les valeurs suivantes :
| RO = CaO + MgO + SrO |
|
| RO/(SiO2 + Al2O3) |
de 0,30 à 0,45. |
6. Composition de verre suivant la revendication 1, dans laquelle les constituants ont
les valeurs suivantes :
| (R2O + RO + B2O3)/(SiO2 + Al2O3) |
de 0,45 à 0,50 |
où R
2O = % en poids de Na
2O + Li
2O + K
2O, lorsque présent dans le verre, et RO = CaO + MgO + SrO.
7. Composition de verre suivant la revendication 5, dans laquelle les constituants sont
dans les % en poids suivants :
| SiO2 |
52 à 54 % en poids |
| Al2O3 |
13 à 15 % en poids |
| CaO |
23 à 25 % en poids |
| MgO |
1 à 3 % en poids |
| SrO |
0 à 3 % en poids |
| MgO + SrO |
1 à 3 % en poids. |
8. Composition de verre suivant la revendication 7, comprenant de plus :
| Fer total |
0,05 à 0,8 % en poids |
| SO3 |
plus de 0 % en poids. |
9. Composition de verre suivant la revendication 4, dans laquelle les constituants comprennent
:
| SiO2 |
52,86 à 54,33 % en poids |
| B2O3 |
5,15 à 6,05 % en poids |
| Al2O3 |
13,44 à 14,14 % en poids |
| CaO |
23,42 à 24,16 % en poids |
| MgO |
1,17 à 1,5 % en poids |
| SrO |
0,12 à 0,15 % en poids |
| MgO + SrO |
1,29 à 1,65 % en poids. |
10. Composition de verre suivant la revendication 9, comprenant de plus :
| Fer total |
0,29 à 0,37 % en poids |
| SO3 |
plus de 0 % en poids |
| K2O |
0,09 à 0,11 % en poids |
| TiO2 |
0,54 à 0,62 % en poids |
| Na2O |
0,41 à 0,91 % en poids |
| ZrO2 |
moins de 0,1 % en poids. |
11. Composition de verre suivant la revendication 10, dans laquelle les constituants ont
les valeurs suivantes :
| Al2O3/SiO2 |
de 0,25 à 0,27 |
| RO = CaO + MgO + SrO |
de 25,02 à 25,68 |
| RO/(SiO2 + Al2O3) |
de 0,37 à 0,38 |
| (R2O + RO + B2O3)/(SiO2 + Al2O3) |
de 0,46 à 0,48, |
où R
2O = % en poids de Na
2O + Li
2O + K
2O.
12. Composition de verre suivant la revendication 1, dans laquelle la température de formation
n'est pas supérieure à 1185°C.
13. Toile de fibres de verre tissée, dans laquelle au moins une des fibres de verre a
la composition de la revendication 1.
14. Carte à circuit imprimé comprenant une toile de fibres de verre tissée, dans laquelle
au moins une des fibres de verre a la composition de la revendication 1.