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Патент USA US3053682

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3,053,672
United States Patent O?ice
Patented vSept. 11, 1962
2
1
formed by the recited components within the area de
3,053,672
GLASS COMPOSITION
Dominick Labino, Grand Rapids, Ohio, assignor to Johns
Manville Corporation, New York, N.Y., a corporation
?ned substantially by the following percentages by weight.
Constituents:
Range
Si02
46-54
of New York
B203
No Drawing. Filed Dec. 19, 1960, Ser. No. 76,454
8 Cl. (Cl. 106-50)
A1203
This invention relates to a glass composition and more
particularly to an improved glass composition ‘for the 10
manufacture of glass ?bers.
Present commercial manufacturing procedures for the
production of glass ?bers typically comprise two general
___ .
8-13
1l—-l5
Na2O+K2O
________________________ __ 0.s~2.5
CaO ____
15-22
MgO
0-2
13:10
1-5
ZnO ___
CaF2
1-5
_____
0.1-2.5
methods. One method comprises mechanically attenuat
V The compositions given above are calculated from batch
ing streams or ?laments of molten to soft glass ?owing or 15 and may vary insigni?cantly because of loss of volatile
materials during melting. Also, the percentage given for
drawn from ori?ces in a glass melting furnace to produce
the A1203 constituent includes any Fe2O3, TiOz or other
continuous ?bers or threads of ?ne diameter. The other
members of this chemical group that may be included in
general method, comprising gas attenuation, typically
the glass in small amounts as impurities with the batch
consists of further attenuating primary glass ?bers, formed
by the foregoing-mentioned mechanical drawing and at 20 materials.
A glass within the approximate range of the formula
tenuating techniques, with a high temperature and high
tions given provides a melt with improved viscosity char
velocity gas stream or jet. According to this latter proce
acteristics and a substantially lower liquidus temperature
dure the high temperature of the gas softens the primary
than those of any other glass compositions utilized in the
?ber and the velocity of its stream or jet further attenuates
the soft continuous ?ber of ?laments producing a ?brous 25 commercial production of glass ?bers, particularly conti
nous ?bers or ?laments. The low liquidus temperature
product of very ?ne diameter and short length which is
or pointof these glasses, i.e., about 1700° F., eliminates
generally known as the so-called staple or “wool” glass
devitri?cation or formation of crystals during ?ber forma
?ber. Thus, the effectiveness or efficiency of such cur
tion and attenuation by permitting working of the molten
rent commercial manufacturing procedures comprising
drawing and attenuating molten to soft glass melts, is de 30 to soft material at temperatures where crystals do not
form. Moreover, these glasses ‘generally exhibit very slow
pendent to a substantial degree upon certain properties or
crystal growth in comparison to commercial glass ?ber
characteristics of the composition of the particular glass
compositions. The inclusion of small but effective quanti
such as melting, softening, and working temperatures,
ties of both BaO and ZnO in the glass compositions of this
breadth of the range of workable viscosities, and liquidus
35 invention results in these very desirable forming and
temperature, etc.
Working properties as well as providing compositions hav
It is a primary object of this invention to provide a
ing good resistance and durability to moisture and/or
novel glass composition having improved and unique
chemical attack when in the form of ?ne ?bers.
properties which render it particularly adaptable to cur
The following examples of glass compositions and of
rent glass ?ber manufacturing procedures, and which fa
40 ?bers composed of the same are given for the purpose of
cilitate the same.
illustration and comparison with the prior art, and are
It is also an object of this invention to provide a glass
simply exemplary and not to be construed as limiting the
composition having improved viscosity characteristics and
novel glass composition or glass ?bers of this invention:
very low liquidus temperature which substantially elimi
nates formation of crystals due to devitri?cation during
45
?ber forming and attenuation.
Examples
It is a further object of this invention to provide a glass
composition having a low softening point temperature and
H
V 2
s
a relatively broad working range permitting ease of work
Constituents
'
'
ing and high production rates.
It is a still further object of this invention to provide a
glass composition having a liquidus temperature substan
tially below its relatively low working temperature range,
whereby the glass melt can be worked at a temperature
above that where crystals form.
It is also an object of this invention to provide a glass
composition and in turn glass ?bers having a high degree
of durability and resistance to moisture and‘ chemical at~
tack.
These and other objects and advantages apparent from
the hereinafter detailed description are obtained by a rela 60
Softening point, °F ____________________ __w_
Liquidus Temp, °F ______________________ __
tals .
7 Essential working or forming properties of typical glass
tively narrow range of glass compositions which include
compositions of this invention, identi?ed as the composi
small but effective amounts of oxides of barium and zinc.
tions of Examples 1, .2 and 3, are given in Table I for
The glass compositions of this invention comprise those
comparison with the like properties of an extensively
3,053,672
4;
3
employed commercial glass ?ber composition having the
following formula, in percentage by weight.
What I claim is:
1. A glass consisting essentially of the following in
percent by weight:
Constituents:
SiOZ _________________________________ __ 53.0
sio2 ___________________________________ -_
B203 _________________________________ __ 10.0
B203
A1203 ________________________________ __ 14.3
Al2O3
46—54
__________________________________ __
18-13
_________________________________ __
11-15
Na2O+K2O ___________________________ __
0.5
CaO _________________________________ __
14.8
CaO __________ __. _______________________ -_
15-22
MgO __________________________________ __
0-2
MgO
________________________________ __
4.4
CaFz
________________________________ __
3.0
Na2O+K2O
10
Softening Point, ° F _______ __
Liquidus Temp, ° F ....... ..
Chemical
Durability,
2
Com
mercial
Glass
Fiber
Com
position
3
15
Wt.
1.30
1-5
C210
2, 050
tals
1. 39
2. A glass consisting essentially of the following in
percent by weight:
_____________________________________ __ 48.0
____________________________________ __
12.4
A1203 ____________________________________ __ 13.9
MgO
5;:
14,700
__________________________________ __
NaZO-l-KZO
N o crys-
1, 700
Loss .... __
1-5
ZnO
B203
Fiber in Water:
Percent
__________________________________ __
S102
l. 468
1,435
SZWater ________________ _-
BaO
CaF2 __________________________________ __ 0.1_2.5
Table I
1
____________________________ __ 0.5-2.5
1.12
26, r200
______________________________ __
1.7
_____________________________________ __.
18.3
____________________________________ __
0.3
BaO
_____________________________________ __
2.0
ZnO
_____________________________________ __.
1.0
____________________________________ __
1.8
caFz
3. A glass consisting essentially of the following in per
A further useful and improved property of the glass
cent by weight:
compositions of this invention is the relative light trans
mission of ?bers composed of the same when employed 30 SiOZ _____________________________________ .._ 48.0
B203 ____________________________________ __ 12.4
in reinforced polyester plastic materials. The percent
A1203 ____________________________________ __ 13.9
light transmission through a 1A5" thick reinforced poly
Na2O+K2O ______________________________ __
1.7
ester sheet composed of 40% by Weight of resin and 60%
C210 _____________________________________ .. 16.8
by weight of a glass ?ber composed of the composition
of Example 1 is 78 to 82%, whereas the transmission 35 Mg() ____________________________________ -_ 0.3
BaO _____________________________________ __
2.0
for an identical product containing a like proportion of
ZnO _____________________________________ __
3.0
glass ?bers of the commercial formulation given herein
before is 65 to 78%.
CQFZ
The durability of the glass composition of this inven
____________________________________ .._
4. A glass consisting essentially of the following in
tion in the form of ?ne diameter ?bers to chemical attack 40 percent by weight:
by water and the signi?cant effect of the essential ZnO
constituent upon the composition in this respect is dem
5102 _____________________________________ __
onstrated by submerging several samples of glass ?ber
B203
48.9
____________________________________ __ 11.5
products of 1 micron average diameter and of composi
tions differing only as to the relative proportions of ZnO 45
and C210 in water for a period of 1 hour and determining
Na20+K2O
CaO ______________________________________
______________________________ .._
_._ 20.2
the resultant weight loss in percent by weight. The glass
MgO
?ber compositions and the effects of the same are as
follows:
50
A1203 ____________________________________ -_ 14.0
____________________________________ __
0.3
BaO _____________________________________ __
2.1
ZnO _____________________________________ __
l.l
CaF2
1.0
____________________________________ __
Table 11
5. A glass in the form of ?ne ?bers consisting essen
+1% CaO
and —1%
Constituents
tially of the following in percent by weight:
\llixamplé
1 0. 1 1
ZnO From
Example 1
’
SiO2 ___________________________________ __
0
Example 1
46-54
8—-13
A1203 __________________________________ __
Il-IS
Na2O+K2O ____________________________ __ 0.5-2.5
60
B203
__________________________________ __
CaO
___________________________________ __
15~22
MgO __________________________________ __
0—2
BaO
__________________________________ ..
1-5
ZnO ___________________________________ __
l-5
Cal-72 __________________________________ __ 0.1-2.5
Percent Weight Loss 1 hr. in
water _________________________ __
6. A glass in the form of ?ne ?bers consisting essential~
65
From the foregoing it is apparent that the ZnO com
ponent contributes substantially to the durability when it
replaces CaO which is usually considered a stabilizing 70
component in glass of this type.
sio2 _____________________________________ __ 48.0
B203 ______________________________________ __ 12.4
A1203 ____________________________________ __ 13.9
Na2O+K2O _______________________________ __
1.7
CaO _____________________________________ __
It should be understood that the present disclosure is
for the purpose of illustration only and that this inven
tion includes all modi?cations and equivalents which fall
within the scope of the appended claims.
ly of the following in percent by Weight:
MgO
75
18.8
____________________________________ __
0.3
BaO
_____________________________________ __
2.0
ZnO
_____________________________________ __
1.0
can2 _____________________________________ __
1.8
3,053,672
5
6
7. A ‘glass in the form of ?ne ?bers consisting essential
B203 _____________________________________ __ 11.5
Iy of the following in percent by weight:
SiO2
_.._
B203
A1203
A1203 ___
CaO ._____
MgO _____
BaO
2110
CaO
_ 12.4
___.__ 13.9
Na2O+K2O _______________________________ __
1.7
16.8
___
____ __
0.3
2.0
_____________________________________ __
3.0
CaFz _____________________________________ __
1.8
10
8. A glass in the form of ?ne ?bers consisting essential
ly of the following in percent by weight:
15
SiOz _____________________________________ __ 48.9
14.0
Na2O+K2O _______________________________ .._
_ 48.0
1.0
_____________________________________ __ 20.2
MgO ______________________________________ __
0.3
BaO
2.1
_____________________________________ __
ZnO _____________________________________ __
1.1
‘CaFg _____________________________________ _._
1.0
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,640,784
2,877,124
2,882,173
2,961,328
Tiede et a1 _____________ __ June 2,
Welsch ______________ _._ Mar. 10,
Welsch ______________ __ Apr. 14,
Babcock et a1 _________ __ Nov. 22,
1953
1959
1959
1960
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