CROSS-REFERENCE TO RELATED APPLICATIONS
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present invention relates to a glass fiber, a composition for producing the same,
and a composite material comprising the same.
Description of the Related Art
[0003] Glass fiber is an inorganic fiber material that can be used to reinforce resins to
produce composite materials with good performance. As a reinforcing base material
for advanced composite materials, high-performance glass fibers were originally used
mainly in the aerospace industry or the national defense industry. With the progress
of science and technology and the development of economy, high-performance glass fibers
have been widely used in civil and industrial fields such as wind blades, pressure
vessels, offshore oil pipes and auto industry. In consequence, it has become an urgent
challenge to develop a glass fiber that has higher strength and modulus, better forming
properties, lower production risks and costs and that, meanwhile, is suitable for
large-scale production with refractory-lined furnaces so as to greatly improve the
cost performance of the resulting high-performance glass fiber.
[0004] S-glass is the earliest high-performance glass that is based on an MgO-Al
2O
3-SiO
2 system. According to ASTM, S-glass is a type of glass comprised mainly of such oxides
as magnesia, alumina and silica, and a typical solution is S-2 glass developed by
the US. The total weight percentages of SiO
2 and Al
2O
3 in the S-2 glass reaches 90% and the weight percentage of MgO is about 10%; the melting
temperature of the glass is up to over 1600°C and the forming temperature and liquidus
temperature up to 1571°C and 1470°C, respectively. Thus, the S-2 glass is difficult
to melt and refine, and an excessive amount of bubbles is present in the molten glass;
also, the crystallization rate of S-2 glass is fast. Therefore, it is impossible to
realize large-scale production of S-2 glass with refractory-lined furnaces, and is
even difficult to achieve a direct-melt production. All these lead to small production
scale, low efficiency and high cost for the production of S-2 glass fiber. Relevant
data shows that the elastic modulus of S-2 glass is typically 89-90GPa.
[0005] France developed R glass that is based on an MgO-CaO-Al
2O
3-SiO
2 system; however, the total contents of SiO
2 and Al
2O
3 remains high in the traditional R glass, thus causing difficulty in fiber formation
as well as a great risk of crystallization. The forming temperature of the R glass
reaches 1410°C and its liquidus temperature up to 1350°C. At the same time, there
is no effective solution in the tradition R glass to improve the crystallization performance,
as the ratio of Ca to Mg is inappropriately designed that leads to a significant loss
of glass properties and a high crystallization rate. All these factors have caused
difficulty in effectively attenuating glass fiber and consequently in realizing large-scale
industrial production. Relevant data shows that the elastic modulus of the traditional
R glass is typically 87-90GPa.
[0006] Japanese patent No.
JP8231240 discloses a glass fiber composition comprising the following components expressed
as percentage amounts by weight: 62-67% SiO
2, 22-27% Al
2O
3, 7-15% MgO, 0.1-1.1% CaO and 0.1-1.1% B
2O
3. Compared with S glass, the amount of bubbles in molten glass of this composition
is significantly lowered, but the difficulty of fiber formation remains high, and
the forming temperature is over 1460 °C.
[0007] The American patent No.
PCT/US2009/068949 discloses a high-performance glass fiber composition, which contains the following
components expressed as percentage amounts by weight: 62-68% SiO
2 , 22-26% Al
2O
3 , 8-15% MgO and 0.1-2% Li
2O. Compared with S glass, the forming properties of this composition is significantly
improved by introducing a high content of Li
2O, but the liquidus temperature is still high, generally more than 1360 °C, resulting
in a small and even negative ΔT value which means the great difficulty of fiber formation.
Moreover, the excessive amount of Li
2O introduced will have some negative effects, which not only greatly increases the
cost of raw materials, but also seriously affects the corrosion resistance and electrical
insulation properties of glass fiber.
[0008] The Chinese patent application
WO 2016/165506 discloses a high modulus glass fiber composition. In particular, the glass fiber
composition of Example A2 comprises (in Wt.%) SiO
2 59.3%, Al
2O
3 17.1%, CaO 7.6%, MgO 10.4%, SrO 0.3%, Na
2O 0.21%, K
2O 0.34%, Li
2O 0.45%, TiO
2 0.43%, Fe
2O
3 0.44%, Y
2O
3 3.1%. The Chinese patent application
WO 2016/165531 discloses a high-performance glass fiber composition, the composition in Example
A7 comprises the following components (in Wt.%): SiO
2 59.3%, Al
2O
3 17.4%, MgO 10.6%, CaO 8.2%, Sm
2O
3 1.5%, Gd
2O
3 0.3%, Na
2O 0.23%, K
2O 0.38%, Li
2O 0.65%, TiO
2 0.53%, Fe
2O
3 0.44%, SrO 0%.
[0009] In general, the above-mentioned prior art for producing glass fiber faces such difficulties
as high forming temperature, high difficulty in refining molten glass, excessive amount
of bubbles, high liquidus temperature, high crystallization rate, and a narrow temperature
range (ΔT) for fiber formation. Thus, the glass fiber production in the prior art
generally fails to enable an effective large-scale production at low costs.
SUMMARY OF THE INVENTION
[0010] It is one objective of the present disclosure to provide a composition for producing
a glass fiber. The resulting glass fiber has relatively high modulus and improved
forming properties; meanwhile, the composition for producing a glass fiber significantly
lowers the liquidus temperature, crystallization rate and bubble amount of the glass,
and broadens the temperature range for fiber formation.
[0011] The composition for producing a glass fiber of the present invention is particularly
suitable for large-scale production with refractory-lined furnaces.
[0012] To achieve the above objective, in accordance with one embodiment of the present
disclosure, there is provided a composition for producing glass fiber, the composition
comprising percentage amounts by weight, as follows:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0013] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the weight percentage ratio C2= (CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205.
[0014] In a class of this embodiment, the composition comprises the following components
expressed as percentage amounts by weight:
| SiO2 |
58.1-60.5% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-12.5% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79% |
[0015] In addition, the combined weight percentage of the components listed above is greater
than 99.5%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.435-0.525, and the weight percentage ratio C2= (CaO+MgO)/(SiO
2+Al
2O
3) is 0.215-0.295.
[0016] In a class of this embodiment, the composition comprises the following components
expressed as percentage amounts by weight:
| SiO2 |
58.1-60.5% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-11.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| F2 |
<0.4% |
| SiO2+Al2O3 |
75.4-79% |
[0017] In addition, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.435-0.525, and the weight percentage ratio C2= (CaO+MgO)/(SiO
2+Al
2O
3) is 0.215-0.295.
[0018] In a class of this embodiment, the combined weight percentage of Al2O
3+MgO is 26.1-31 %.
[0019] In a class of this embodiment, the combined weight percentage of Al2O
3+MgO is 26.3-30.3%.
[0020] In a class of this embodiment, the combined weight percentage of Al2O
3+MgO is 26.3-30%.
[0021] In a class of this embodiment, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.44-0.515.
[0022] In a class of this embodiment, the weight percentage ratio C2= (CaO+MgO)/(SiO
2+Al
2O
3) is 0.225-0.29.
[0023] In a class of this embodiment, the weight percentage ratio C3= (MgO+SrO)/CaO is 0.8-1.6.
[0024] In a class of this embodiment, the weight percentage ratio C3= (MgO+SrO)/CaO is 0.83-1.5.
[0025] In a class of this embodiment, the weight percentage ratio C3= (MgO+SrO)/CaO is greater
than 1 and less than or equal to 1.4.
[0026] In a class of this embodiment, the content of SiO2 is 58.1-60.5% in percentage amounts
by weight.
[0027] In a class of this embodiment, the content of SiO2 is 58.1-59.9% in percentage amounts
by weight.
[0028] In a class of this embodiment, the composition contains one or more components selected
from the group consisting of ZrO
2, CeO
2, B
2O
3 and F
2 with the combined weight percentage less than 1%.
[0029] In a class of this embodiment, the composition contains Li
2O with a content not greater than 0.55% in percentage amounts by weight.
[0030] In a class of this embodiment, when the weight percentage ratio (CaO+MgO)/Al
2O
3 is greater than 1 and the weight percentage ratio (MgO+SrO)/CaO is greater than 0.9,
the composition can be free of Li
2O.
[0031] In a class of this embodiment, the composition contains SrO with a content of 0.1-1.5%
in percentage amounts by weight.
[0032] In a class of this embodiment, the composition contains SrO with a content of 0.5-1.3%
in percentage amounts by weight.
[0033] In a class of this embodiment, the composition contains Na
2O with a content not greater than 0.65% in percentage amounts by weight.
[0034] In a class of this embodiment, the composition contains MgO with a content greater
than 11% and less than or equal to 12.5% in percentage amounts by weight.
[0035] In a class of this embodiment, the composition comprises the following components
expressed as percentage amounts by weight:
| SiO2 |
58.1-59.9% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-11.8% |
| CaO |
8.1-11.3% |
[0036] In addition, the composition has a glass liquidus temperature not greater than 1250°C.
[0037] In a class of this embodiment, the composition has a glass liquidus temperature not
greater than 1240°C.
[0038] In a class of this embodiment, the combined weight percentage of Na
2O+K
2O is 0.15-0.85%.
[0039] In a class of this embodiment, the composition contains Na
2O in a content not greater than 0.5% in percentage amounts by weight.
[0040] In addition, "the composition can be free of Li
2O" means that the composition contains no Li
2O or essentially contains no Li
2O, or alternatively, Li
2O is present in the composition, if ever, only in trace quantity with the weight percentage
of 0-0.01%.
[0041] According to another aspect of this invention, a glass fiber produced with the composition
for producing a glass fiber is provided.
[0042] According to yet another aspect of this invention, a composite material incorporating
the glass fiber is provided.
[0043] Compared with those of S glass and R glass, the main inventive points of the composition
for producing a glass fiber according to this invention lie in that, by introducing
a high content of MgO, appropriately lowering the contents of Al
2O
3 and SiO
2, adjusting the content of CaO, controlling the contents of SiO
2+Al
2O
3 and of alkali metal oxides and keeping tight control on the ratios of (Al
2O
3+MgO)/SiO
2, (CaO+MgO)/(SiO
2+Al
2O
3) and (MgO+SrO)/CaO respectively, the composition can: 1) produce a mixture of crystal
phases consisting of cordierite, anorthite, diopside and/or enstatite for glass devitrification,
where all these crystal phases in certain proportions are competing for growth, so
that the rate of ions rearrangement and bonding is greatly reduced and the growth
rate of a single phase is retarded; thus, the devitrification rate of glass and the
upper limit of crystallization temperature are effectively inhibited; 2) enhance the
synergistic effect among magnesium ions, aluminum ions and alkali metal oxides, so
as to achieve a better stacking structure and an increased glass modulus that is close
to or even higher than that of S glass; and 3) significantly reduce the fiberizing
and refining difficulties of glass and acquire an optimal temperature range for fiber
formation, thus making it particularly suitable for high performance glass fiber production
with refractory-lined furnaces.
[0044] Specifically, the composition for producing a glass fiber according to the present
invention comprises the following components expressed as percentage amounts by weight:
| |
SiO2 |
57.4-60.9% |
| |
Al2O3 |
>17% and ≤19.8% |
| |
MgO |
>9% and ≤12.8% |
| |
CaO |
8.3-11.1% |
| |
SrO |
0-1.6% |
| |
Na2O+K2O |
0.1-1.1% |
| |
Li2O |
0-0.55% |
| |
Fe2O3 |
0.05-1% |
| |
TiO2 |
<0.8% |
| |
SiO2+Al2O3 |
≤79.4% |
[0045] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the weight percentage ratio C2= (CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205.
[0046] The effect and content of each component in the composition for producing a glass
fiber is described as follows:
In a typical S glass system, the combined content of SiO
2 and Al
2O
3 by weight percentage can be up to 90%, with about 65% for SiO
2 and about 25% for Al
2O
3, and the content of MgO is about 10%. Given so high contents of SiO
2 and Al
2O
3, the melting temperature of glass would accordingly be very high and the fiber fomation
would be difficult, and meanwhile there will be many structural gaps in the glass
network. In additon, with a shortage of sufficient free oxygen, more alumina would
enter the network structure, resulting in a large number of aluminum ions, together
with megnesium ions, filling in the network gaps, and thus the risk of crystallization
and phase separation is increased; besides, as there is no effecitve competition in
the crystallization process, the crystallization tendency of cordierite will be very
strong, the upper limit temperature and rate of crystallization are both high and
the grain size of crystals is large. All the forementioned problems and risks are
addressed with the configuration of the composition for producing a glass fiber in
this invention.
[0047] SiO
2 is a main oxide forming the glass network and has the effect of stabilizing all the
components. In the composition for producing a glass fiber of the present invention,
the content range of SiO2 is 57.4-60.9%. The lower limit is set at 57.4%, so that
the resulting glass would have sufficient mechanical properties; and the upper limit
is set at 60.9%, which is obviously different from that of S glass and helps to prevent
excessively high viscosity and liquidus temperature that would otherwise cause difficulty
for large-scale production. Preferably, the SiO
2 content range in this invention can be 58.1-60.5%, and more preferably can be 58.1-59.9%.
[0048] Al
2O
3 is another main oxide forming the glass network. When combined with SiO
2, it can have a substantive effect on the mechanical properties of the glass and a
significant effect on preventing glass phase separation and on crystallization resistance.
The content range of Al
2O
3 in this invention is greater than 17% and less than or equal to 19.8%. In order to
ensure sufficient mechanical properties, especially modulus, the Al
2O
3 content should be greater than 17%, which is obviously different from that of E glass.
However, the Al
2O
3 content should not be excessively high. Its content being over 20% would significantly
increase the risks of glass phase separation and crystallization, thus resulting in
too high a liquidus temperature and crystallization rate which are not suitable for
large-scale production. Therefore, the Al
2O
3 content should not be greater than 19.8%, which is obviously different from that
of S glass. Preferably, the Al
2O
3 content can be 17.1-19.4%, more preferably 17.1-18.8%.
[0049] In addition, the combined content of SiO
2+Al
2O
3 in this invention can be lower than or equal to 79.4%, preferably lower than or equal
to 79%, and more preferably can be 75.4-79%. By keeping a tight control on the contents
of SiO2 and Al
2O
3 respectively and on their total amount, the composition for producing a glass fiber
according to the present invention can not only decrease the gap ratio of the network
structure and reduce the fiberizing difficulty and crystallization risk, but also
acquire sufficiently high mechanical properties, particularly high modulus that could
be close to or even higher than that of S glass, thus making it suitable for large-scale
production with refractory-lined furnaces under relatively low temperatures.
[0050] In the prevent invention, CaO, MgO and SrO primarily have the effect of improving
the mechanical properties of glass, controlling the glass crystallization and regulating
the viscosity and hardening rate of molten glass. Researches show that, as CaO is
generally absent from an S glass composition where there is a shortage of sufficient
free oxygen, a high content of MgO would not provide an adequate amount of free oxygen
for aluminum ions, but instead tend to retain oxygen ions near itself when filling
in the network gaps. By contrast, the composition for producing a glass fiber of this
invention introduces CaO with a content range of 8.1-11.3%.
[0051] With such introduction, calcium ions would provide considerable free oxygen while
filling in the network gaps, and form a synergistic effect in stacking structure together
with magnesium ions. Thus, a more compact structural stacking would be achieved, a
mixture of crystal phases is obtained during the crystallization process that consists
of cordierite (Mg
2Al
4Si
5O
18), anorthite (CaAl
2Si
2O
8), diopside (CaMgSi
2O
6) and/or enstatite (CaMgSi
2O
6), and the hardening rate of molten glass as well as the cooling effect during fiber
attenuation will be optimized. However, in view of a high content of MgO, the introduced
amount of CaO should not be greater than 11.3%.
[0052] That is because, on the one hand, an excessive amount of calcium ions would cause
diopside and/or anorthite to be the main crystal phases, thus significantly weakening
the competition between cordierite and these two phases, and no satisfactory control
on the crystallization temperature and rate could be achieved; on the other hand,
a high total amount of CaO and MgO also would not help to offer high mechanical properties
of glass. At the same time, the content of CaO should not be lower than 8.1% as too
low a content would not be able to provide either considerable free oxygen or sufficient
amount of calcium ions that would otherwise produce an effective synergistic effect
in structural stacking together with a high content of magnesium ions, and thus the
crystal phases of diopside and anorthite obtained during glass crystallizaiton are
not sufficient to compete for growth against cordierite. The content range of CaO
is 8.1-11.3%.
[0053] In the composition for producing a glass fiber of the present invention, the content
range of MgO can be greater than 9% and less than or equal to 12.8%. In order to ensure
sufficiently high mechanical properties, especially modulus, the MgO content is set
to be greater than 9%, which is obviously different from the corresponding value of
E glass. Meanwhile, the inventors find that, when the content of MgO in the composition
is further increased to be over 10%, which defines the approximate value of MgO for
S glass, or even over 11%, the crystallization temperature and rate have not been
noticeably increased and are still much lower than those of S glass. This is perhaps
because in an S glass system, an increased amount of MgO would result in the fast
growth of cordierite as the single crystal phase during crystallization, but in the
composition of this invention, an increased amount of MgO would help to create competitive
growth among different crystal phases, without having significant negative impacts
on the crystallization performance of glass as long as it is kept within an appropriate
range. However, when the MgO content reaches 12.5%, the above advantages will be greatly
diminished, and when it comes over 12.8%, the risk of phase separation may occur,
rendering it unsuitable for large-scale production. Therefore, the content of MgO
should not be greater than 12.8%. Preferably, the content range of MgO can be 9.1-12.5%.
In some embodiments, preferably the content range of MgO can be 9.1-11.8%, and in
some other embodiments, preferably the content range of MgO can be greater than 11%
but less than or equal to 12.5%.
[0054] Meanwhile, considering the differences of ionic radius and field strength between
Al
3+ ions and Mg
2+ ions, and considering the common demand of these two ions for free oxygen and network
gap filling, it is necessary to reasonbly control the ratios of each of the two ions
to silicon oxide, so that a better structural stacking and higher resistance to glass
crystallizaiton could be achieved. In the composition for producing a glass fiber
of the present invention, the range of weight percentage ratio C1=(Al
2O
3+MgO)/SiO
2 can be 0.43-0.56, more preferably can be 0.435-0.525, and still more preferably can
be 0.44-0.515. In the composition for producing a glass fiber of the present invention,
the combined content range of Al
2O
3+MgO can be 26.1-31%, more preferably can be 26.3-30.3%, and still more preferably
can be 26.3-30%.
[0055] In order to produce a mixture of crystal phases consisting of cordierite, anorthite,
diopside and/or enstatite, where the dominant role of a single phase can be avoided
and all these crystal phases in certain proportions are competing for growth so that
the rate of ions rearrangement and bonding is significantly reduced, the growth rate
of a single crystal phase is retarded, and thus the devitrification rate of glass
and the upper limit of crystallization temperature are effectively inhibited, in the
composition for producing a glass fiber of the present invention, the range of the
weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) can be greater than 0.205, preferably can be 0.215-0.295, and still more preferably
can be 0.225-0.29.
[0056] In the composition for producing a glass fiber of the present invention, the content
range of SrO can be 0-1.6%. Many researches show that, when their ratios are rational,
the technical effect of the CaO, MgO and SrO ternary mixed alkali earth effect is
noticeably better than that of the CaO and MgO binary mixed alkali earth effect. With
such ternary mixed effect, a compact stacking structure forms more easily and thereby
the glass has better crystallization, mechanical and optical properties. Since the
ionic radiuses of Mg
2+, Ca
2+ and Sr
2+ sequentially become bigger and their ion field strengths sequentially become lower,
in order to achieve a compact stacking structure, the matching between the numbers
of three types of ions becomes very important. What is particularly noteworthy is
that, an appropriate amount of SrO is introduced in the glass fiber composition of
the present invention, and, by way of a rationally adjusted ratio of C3= (MgO+SrO)/CaO,
the temperature and rate of the glass crystallization can be effectively controlled
and the hardening rate of molten glass can be optimized. Preferably, the content range
of SrO can be 0.1-1.5%, more preferably can be 0.5-1.3%. The inventors find that,
in the glass system according to the present invention, when the SrO content is within
0.5-1.3%, the glass will have a better ternary mixed alkali earth effect and a better
cost performance ratio.
[0057] In addition, the range of the weight percentage ratio C3=(MgO+SrO)/CaO can be 0.8-1.6,
preferably can be 0.83-1.5, and still more preferably greater than 1 and less than
or equal to 1.4.
[0058] Both K
2O and Na
2O can reduce glass viscosity and are good fluxing agents. They can also provide considerable
free oxygen and produce a good synergistic effect in combination with aluminum and
magnesium ions, so as to create a more compact stacking structure. In the composition
for producing a glass fiber of the present invention, the total content range of Na
2O+K
2O can be 0.1-1.1%, preferably can be 0.15-1%, and more preferably can be 0.15-0.85%.
Besides, in order to ensure the corrosion resistance of glass fiber and excellent
cooling effect on the fiber cones, the content range of Na
2O can be lower than or equal to 0.65%, preferably lower than or equal to 0.5%.
[0059] Fe
2O
3 facilitates the melting of glass and can also improve the crystallization performance
of glass. However, since ferric ions and ferrous ions have a coloring effect, the
introduced amount should be limited. Therefore, in the composition for producing a
glass fiber of the present invention, the content range of Fe
2O
3 can be 0.05-1%, preferably 0.05-0.65%.
[0060] TiO
2 can not only reduce the glass viscosity at high temperatures, but also has a certain
fluxing effect. However, since titanium ions in combination with ferric ions can have
a certain coloring effect, which will affect the appearance of glass fiber-reinforced
articles and cause the noticeable increase of glass density, the introduced amount
should be limited. Therefore, in the composition for producing a glass fiber of the
present invention, the content range of TiO
2 is lower than 0.8%, preferably lower than or equal to 0.75%, and more preferably
lower than or equal to 0.6%.
[0061] In addition, the above components are the main components of the composition according
to the present invention, with the total weight percentage greater than 99%.
[0062] In addition, the glass fiber composition of the present invention can also include
small amounts of other components with a total content lower than 1%. Furthermore,
the glass fiber composition of the present invention can include one or more components
with a total content lower than 1% selected from the group consisting of ZrO
2, CeO
2, B
2O
3 and F
2. Furthermore, the glass fiber composition of the present invention can include Li
2O with a content range of 0-0.55%, as Li
2O can significantly reduce the glass viscosity and improve the glass melting performance.
Also, a small amount of Li
2O provides considerable free oxygen, which helps more aluminum ions to form tetrahedral
coordination, enhances the network structure of the glass and further improves the
crystallization performance of glass. However, an excessive amount of Li
2O would be very costly and, with high ionic field strength and strong accumulation
effect, the lithium ions in combination with magnesium ions would easily form a synergistic
accumulation effect, which adversely affects the crystallization rate of glass. Furthermore,
the glass fiber composition of the present invention can include Li
2O with a content lower than or equal to 0.55%. Furthermore, the glass fiber composition
of the present invention can include F
2 with a content lower than 0.4% and generally in the form of impurities contained
in the glass raw materials.
[0063] Furthermore, the content of the main components of the composition for producing
a glass fiber of the present invention can be greater than 99.3%, more preferably
can be greater than 99.5%.
[0064] Furthermore, in order to control the production costs, the composition for producing
a glass fiber of the present invention can be free of Li
2O, particularly when the weight percentage ratio (CaO+MgO)/Al
2O
3>1 and the weight percentage ratio (MgO+SrO)/CaO>0.9. Absense of Li
2O in this case will not have negative impacts on the properties and melting performance
of the glass. Furthermore, the composition for producing a glass fiber of the present
invention has a liquidus temperature lower than or equal to 1260 °C, preferably lower
than or equal to 1250 °C, and more preferably lower than or equal to 1240 °C.
[0065] In the composition for producing a glass fiber of the present invention, the beneficial
effects produced by the aforementioned selected ranges of the components will be explained
by way of examples through the specific experimental data.
[0066] The following are examples of preferred content ranges of the components contained
in the composition for producing a glass fiber according to the present invention.
Composition 1
[0067] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
58.1-60.5% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-12.5% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79% |
[0068] In addition, the combined weight percentage of the components listed above is greater
than 99.5%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.435-0.525, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is 0.215-0.295.
Composition 2
[0069] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
58.1-60.5% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-11.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| F2 |
<0.4% |
| SiO2+Al2O3 |
75.4-79% |
[0070] In addition, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.435-0.525, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is 0.215-0.295.
Composition 3
[0071] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
| Al2O3+MgO |
26.3-30.3% |
[0072] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205.
Composition 4
[0073] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
58.1-60.5% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-12.5% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79% |
[0074] In addition, the combined weight percentage of the components listed above is greater
than 99.5%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.44-0.515, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is 0.215-0.295.
Composition 5
[0075] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
58.1-60.5% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-12.5% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79% |
[0076] In addition, the combined weight percentage of the components listed above is greater
than 99.5%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.435-0.525, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is 0.225-0.29.
Composition 6
[0077] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
|
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0078] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205, and the weight percentage ratio C3= (MgO+SrO)/CaO is 0.83-1.5.
Composition 7
[0079] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0080] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205, and the composition contains Li
2O with a content lower than or equal to 0.55% by weight.
Composition 8
[0081] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0082] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205, and when the weight percentage ratio (CaO+MgO)/Al
2O
3 is greater than 1 and the weight percentage ratio (MgO+SrO)/CaO greater than 0.9,
the composition is free of Li
2O.
Composition 9
[0083] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0.5-1.3% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0084] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205.
Composition 10
[0085] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>9% and ≤12.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Na2O |
≤0.65% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0086] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205.
Composition 11
[0087] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
57.4-60.9% |
| Al2O3 |
>17% and ≤19.8% |
| MgO |
>11% and ≤12.5% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.1-1.1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79.4% |
[0088] In addition, the combined weight percentage of the components listed above is greater
than 99%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205.
Composition 12
[0089] The composition for producing a glass fiber according to the present invention comprises
the following components expressed as percentage amounts by weight:
| SiO2 |
58.1-59.9% |
| Al2O3 |
17.1-18.8% |
| MgO |
9.1-11.8% |
| CaO |
8.1-11.3% |
| SrO |
0-1.6% |
| Na2O+K2O |
0.15-1% |
| Li2O |
0-0.55% |
| Fe2O3 |
0.05-1% |
| TiO2 |
<0.8% |
| SiO2+Al2O3 |
≤79% |
[0090] In addition, the combined weight percentage of the components listed above is greater
than 99.5%, the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.435-0.525, the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is 0.215-0.295, and the composition has a liquidus temperature lower than or equal
to 1250°C.
DETAILED DESCRIPTION OF THE INVENTION
[0091] In order to better clarify the purposes, technical solutions and advantages of the
examples of the present invention, the technical solutions in the examples of the
present invention are clearly and completely described below. Obviously, the examples
described herein are just part of the examples of the present invention and are not
all the examples. All other exemplary embodiments obtained by one skilled in the art
on the basis of the examples in the present invention without performing creative
work shall all fall into the scope of protection of the present invention. What needs
to be made clear is that, as long as there is no conflict, the examples and the features
of examples in the present application can be arbitrarily combined with each other.
[0092] The basic concept of the present invention is that the components of the composition
for producing a glass fiber expressed as percentage amounts by weight are: 57.4-60.9%
SiO
2, greater than 17% and less than or equal to 19.8% Al
2O
3, greater than 9% and less than or equal to 12.8% MgO, 8.1-11.3% CaO, 0-1.6% SrO,
0.1-1.1% Na
2O+K
2O, 0-0.55% Li
2O, 0.05-1% Fe
2O
3, and lower than 0.8% TiO
2, whererin the range of the combined weight percentage of these components is greater
than 99%, the range of the total weight percentage SiO
2+Al
2O
3 is lower than or equal to 79.4%, the range of the weight percentage ratio C1= (Al
2O
3+MgO)/SiO
2 is 0.43-0.56, and the range of the weight percentage ratio C2=(CaO+MgO)/(SiO
2+Al
2O
3) is greater than 0.205. The composition can not only increase the glass modulus,
improve the forming properties of the glass and reduce the bubble amount of molten
glass, but also significantly lower the liquidus temperature and crystallization rate
of the glass, and broaden the temperature range (ΔT) for fiber formation, thereby
making it particularly suitable for high performance glass fiber production with refractory-lined
furnaces.
[0093] The specific content values of SiO
2, Al
2O
3, CaO, MgO, SrO, Na
2O, K
2O, Li
2O, Fe
2O
3 and TiO
2 in the composition for producing a glass fiber of the present invention are selected
to be used in the examples, and comparisons with S glass, traditional R glass and
improved R glass are made in terms of the following seven property parameters,
- (1) Forming temperature, the temperature at which the glass melt has a viscosity of
103 poise.
- (2) Liquidus temperature, the temperature at which the crystal nucleuses begin to
form when the glass melt cools off -- i.e., the upper limit temperature for glass
crystallization.
- (3) ΔT value, the difference between the forming temperature and the liquidus temperature,
indicating the temperature range at which fiber drawing can be performed.
- (4) Elastic modulus, the modulus defining the ability of glass to resist elastic deformation,
which is to be measured on bulk glass as per ASTM E1876.
- (5) Crystal phase composition, which represents the composition of main crystal phases
in the glass melt to be measured and evaluated by using XRD method. The four main
crystal phases, i.e. cordierite, anorthite, diopside and enstatite are abbreviated
as COR, ANO, DIO and ENS respectively in the tables below. The abbreviations of different
crystals are placed in a top-down manner based on their respective contents. For instance,
in example A1 of Table 1A, the placing of these abbreviations means the contents of
DIO, COR and ANO successively decrease.
- (6) Crystallization area ratio, to be determined in a procedure set out as follows:
Cut the bulk glass appropriately to fit in with a porcelain boat trough and then place
the cut glass bar sample into the porcelain boat. Put the porcelain boat with the
glass bar sample into a gradient furnace for crystallization and keep the sample for
heat preservation for 6 hours. Take the boat with the sample out of the gradient furnace
and air-cool it to room temperature. Finally, examine and measure the amounts and
dimensions of crystals on the surfaces of each sample within the temperature range
of 1050-1150°C from a microscopic view by using an optical microscope, and then calculate
the area ratio of crystallization. A high area ratio would mean a high crystallization
tendency and high crystallization rate.
- (7) Amount of bubbles, to be determined in a procedure set out as follows: Use specific
moulds to compress the glass batch materials in each example into samples of same
dimension, which will then be placed on the sample platform of a high temperature
microscope. Heat the samples according to standard procedures up to the pre-set spatial
temperature 1500°C and then directly cool them off with the cooling hearth of the
microscope to the ambient temperature without heat preservation. Finally, each of
the glass samples is examined under a polarizing microscope to determine the amount
of bubbles in the samples. A bubble is identified according to a specific amplification
of the microscope.
[0094] The aforementioned seven parameters and the methods of measuring them are well-known
to one skilled in the art. Therefore, these parameters can be effectively used to
explain the properties of the composition for producing a glass fiber of the present
invention.
[0095] The specific procedures for the experiments are as follows: Each component can be
acquired from the appropriate raw materials. Mix the raw materials in the appropriate
proportions so that each component reaches the final expected weight percentage. The
mixed batch melts and the molten glass refines. Then the molten glass is drawn out
through the tips of the bushings, thereby forming the glass fiber. The glass fiber
is attenuated onto the rotary collet of a winder to form cakes or packages. Of course,
conventional methods can be used to deep process these glass fibers to meet the expected
requirement.
[0096] Comparisons of the property parameters of the examples of the composition for producing
a glass fiber according to the present invention with those of the S glass, traditional
R glass and improved S glass are further made below by way of tables, where the component
contents of the composition for producing a glass fiber are expressed as weight percentage.
What needs to be made clear is that the total amount of the components in the examples
is slightly less than 100%, and it should be understood that the remaining amount
is trace impurities or a small amount of components which cannot be analyzed.
Table 1A
| |
A1 |
A2 |
A3 |
A4 |
A5 |
A6 |
A7 |
| Component |
SiO2 |
60.50 |
59.80 |
59.15 |
59.15 |
58.65 |
59.45 |
59.15 |
| Al2O3 |
17.60 |
17.60 |
17.60 |
18.30 |
18.80 |
17.60 |
17.60 |
| CaO |
9.55 |
10.25 |
10.25 |
9.55 |
9.55 |
9.55 |
11.30 |
| MgO |
10.35 |
10.35 |
11.00 |
11.00 |
11.00 |
11.40 |
9.95 |
| SrO |
- |
- |
- |
- |
- |
- |
- |
| Na2O |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
| K2O |
0.39 |
0.39 |
0.39 |
0.39 |
0.39 |
0.39 |
0.39 |
| Li2O |
- |
- |
- |
- |
- |
- |
- |
| Fe2O3 |
0.44 |
0.44 |
0.44 |
0.44 |
0.44 |
0.44 |
0.44 |
| TiO2 |
0.58 |
0.58 |
0.58 |
0.58 |
0.58 |
0.58 |
0.58 |
| Ratio |
C1 |
0.462 |
0.467 |
0.484 |
0.495 |
0.508 |
0.488 |
0.466 |
| C2 |
0.255 |
0.266 |
0.277 |
0.265 |
0.265 |
0.272 |
0.277 |
| C3 |
1.084 |
1.010 |
1.073 |
1.152 |
1.152 |
1.194 |
0.881 |
| Parameter |
Forming temperature /°C |
1322 |
1312 |
1307 |
1310 |
1308 |
1308 |
1305 |
| Liquidus temperature /°C |
1220 |
1215 |
1217 |
1214 |
1211 |
1219 |
1207 |
| ΔT /°C |
102 |
97 |
90 |
96 |
97 |
89 |
98 |
| Elastic modulus /GPa |
91.6 |
91.5 |
92.4 |
93.0 |
93.8 |
93.1 |
91.2 |
| Crystal phase composition |
DIO COR ANO |
DIO COR ANO |
COR DIO ANO |
COR DIO ANO |
COR ANO DIO |
COR DIO ENS |
DIO ANO COR |
| Crystallization area ratio /% |
21 |
18 |
20 |
18 |
15 |
20 |
13 |
| Amount of bubbles/pcs |
13 |
10 |
9 |
8 |
10 |
9 |
7 |
Table 1B (examples A10, A12 and A13 are not according to the invention)
| |
A8 |
A9 |
A10 |
A11 |
A12 |
A13 |
A14 |
| Component |
SiO2 |
57.40 |
60.10 |
58.55 |
58.55 |
59.55 |
59.10 |
59.10 |
| Al2O3 |
19.80 |
17.10 |
19.40 |
18.60 |
18.80 |
19.80 |
18.40 |
| CaO |
8.45 |
10.40 |
7.30 |
8.10 |
6.40 |
7.50 |
9.25 |
| MgO |
11.20 |
9.75 |
11.30 |
11.00 |
11.80 |
10.80 |
10.80 |
| SrO |
0.50 |
- |
0.75 |
1.00 |
1.00 |
- |
- |
| Na2O |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
0.35 |
0.40 |
| K2O |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
0.24 |
0.34 |
| Li2O |
0.55 |
0.55 |
0.55 |
0.55 |
0.40 |
0.75 |
0.30 |
| Fe2O3 |
0.46 |
0.46 |
0.46 |
0.46 |
0.46 |
0.46 |
0.46 |
| TiO2 |
0.65 |
0.65 |
0.70 |
0.75 |
0.40 |
0.75 |
0.70 |
| F2 |
- |
- |
- |
- |
0.20 |
- |
- |
| Ratio |
C1 |
0.540 |
0.447 |
0.524 |
0.506 |
0.514 |
0.518 |
0.494 |
| C2 |
0.255 |
0.261 |
0.239 |
0.248 |
0.233 |
0.232 |
0.259 |
| C3 |
1.385 |
0.938 |
1.651 |
1.481 |
2.000 |
1.440 |
1.168 |
| Parameter |
Forming temperature /°C |
1305 |
1299 |
1301 |
1299 |
1301 |
1305 |
1300 |
| Liquidus temperature /°C |
1230 |
1215 |
1220 |
1217 |
1212 |
1232 |
1210 |
| ΔT/°C |
75 |
84 |
81 |
82 |
89 |
73 |
90 |
| Elastic modulus /GPa |
93.3 |
91.3 |
93.1 |
92.5 |
93.3 |
93.0 |
92.4 |
| Crystal phase composition |
COR ANO DIO |
DIO ANO COR |
COR ANO DIO |
COR ANO DIO |
COR DIO ANO |
COR DIO ANO |
COR DIO ANO |
| Crystallization area ratio /% |
31 |
23 |
28 |
24 |
21 |
35 |
21 |
| Amount of bubbles/pcs |
9 |
8 |
10 |
9 |
5 |
6 |
8 |
Table 1C (example A21 is not according to the invention)
| |
A15 |
A16 |
A17 |
A18 |
A19 |
A20 |
A21 |
| Component |
SiO2 |
59.70 |
59.70 |
59.70 |
59.70 |
59.70 |
59.70 |
59.70 |
| Al2O3 |
17.80 |
17.80 |
17.80 |
17.80 |
17.80 |
17.80 |
17.80 |
| CaO |
9.80 |
9.50 |
8.70 |
10.85 |
9.55 |
8.15 |
7.45 |
| MgO |
10.40 |
10.40 |
10.40 |
9.10 |
10.40 |
11.80 |
12.50 |
| SrO |
0.20 |
0.50 |
1.30 |
- |
- |
- |
- |
| Na2O |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
0.40 |
| K2O |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
0.34 |
| Li2O |
- |
- |
- |
0.45 |
0.45 |
0.45 |
0.45 |
| Fe2O3 |
0.46 |
0.46 |
0.46 |
0.46 |
0.46 |
0.46 |
0.46 |
| TiO2 |
0.65 |
0.65 |
0.65 |
0.65 |
0.65 |
0.65 |
0.65 |
| Ratio |
C1 |
0.472 |
0.472 |
0.472 |
0.451 |
0.472 |
0.496 |
0.508 |
| C2 |
0.261 |
0.257 |
0.246 |
0.257 |
0.257 |
0.257 |
0.257 |
| C3 |
1.082 |
1.147 |
1.345 |
0.839 |
1.089 |
1.448 |
1.678 |
| Parameter |
Forming temperature /°C |
1312 |
1313 |
1315 |
1311 |
1309 |
1301 |
1294 |
| Liquidus temperature /°C |
1217 |
1213 |
1210 |
1211 |
1219 |
1220 |
1233 |
| ΔT /°C |
95 |
100 |
105 |
100 |
90 |
81 |
61 |
| Elastic modulus /GPa |
92.3 |
92.9 |
94.0 |
91.4 |
92.3 |
93.4 |
93.8 |
| Crystal phase composition |
DIO COR ANO |
DIO COR ANO |
COR DIO ANO |
DIO ANO COR |
DIO COR ANO |
COR DIO ANO |
COR DIO ENS |
| Crystallization area ratio /% |
19 |
16 |
11 |
17 |
24 |
26 |
31 |
| Amount of bubbles/pcs |
10 |
11 |
11 |
10 |
9 |
8 |
8 |
Table 1D
| |
A22 |
A23 |
A24 |
A25 |
S glass |
Traditional R glass |
Improved S glass |
| Component |
SiO2 |
58.10 |
58.70 |
59.90 |
60.40 |
65 |
60 |
63.05 |
| Al2O3 |
19.40 |
18.80 |
17.60 |
17.10 |
25 |
25 |
23.05 |
| CaO |
10.00 |
10.00 |
10.00 |
10.00 |
- |
9 |
- |
| MgO |
10.45 |
10.45 |
10.45 |
10.45 |
10 |
6 |
12.55 |
| SrO |
- |
- |
- |
- |
- |
- |
- |
| Na2O |
0.40 |
0.40 |
0.40 |
0.40 |
- |
- |
- |
| K2O |
0.34 |
0.34 |
0.34 |
0.34 |
- |
- |
- |
| Li2O |
- |
- |
- |
- |
- |
- |
1.35 |
| Fe2O3 |
0.46 |
0.46 |
0.46 |
0.46 |
- |
- |
- |
| TiO2 |
0.60 |
0.60 |
0.60 |
0.60 |
- |
- |
- |
| Ratio |
C1 |
0.514 |
0.498 |
0.468 |
0.456 |
0.538 |
0.517 |
0.565 |
| C2 |
0.264 |
0.264 |
0.264 |
0.264 |
0.111 |
0.176 |
0.146 |
| C3 |
1.045 |
1.045 |
1.045 |
1.045 |
- |
0.667 |
- |
| Parameter |
Forming temperature /°C |
1308 |
1310 |
1313 |
1315 |
1571 |
1430 |
1359 |
| Liquidus temperature /°C |
1216 |
1213 |
1219 |
1225 |
1470 |
1350 |
1372 |
| ΔT/°C |
92 |
97 |
94 |
90 |
101 |
80 |
-13 |
| Elastic modulus /GPa |
92.7 |
92.7 |
91.7 |
91.2 |
90 |
89 |
90 |
| Crystal phase composition |
COR ANO DIO |
COR DIO ANO |
DIO COR ANO |
DIO ANO COR |
COR |
ANO DIO |
COR ENS |
| Crystallization area ratio /% |
19 |
14 |
20 |
24 |
100 |
70 |
85 |
| Amount of bubbles/pcs |
8 |
7 |
10 |
13 |
40 |
30 |
25 |
[0097] It can be seen from the values in the above tables that, compared with the S glass,
traditional R glass and improved S glass, the composition for producing a glass fiber
of the present invention has the following advantages: (1) much higher elastic modulus;
(2) much lower liquidus temperature and much lower crystallization area ratio, which
indicate a low upper limit temperature for crystallization as well as a low crystallization
rate and thus help to reduce the crystallization risk and improve the fiber drawing
efficiency; (3) a much lower forming temperature, which means less difficulty in glass
melting and thus help to enable large-scale production with refractory lined furnaces
at lowered costs; (4) smaller amount of bubbles, which indicates a better refining
of molten glass; and (5) a variety of crystal phases after glass crystallization,
which helps to inhibit the crystallization rate.
[0098] At present, none of the S glass, traditional R glass or improved S glass can enable
the achievement of large-scale production with refractory-lined furnaces.
[0099] Therefore, it can be seen from the above that, compared with the S glass, traditional
R glass and improved S glass, the composition for producing a glass fiber of the present
invention has made a breakthrough in terms of elastic modulus, crystallization temperature,
crystallization rate and refining performance of the glass, with significantly improved
modulus, remarkably reduced crystallization temperature and rate and relatively small
amount of bubbles under the same conditions. Thus, the overall technical solution
of the present invention enables an easy achievement of large-scale production with
refractory-lined furnaces.
[0100] The composition for producing a glass fiber according to the present invention can
be used for making glass fibers having the aforementioned properties.
[0101] The composition for producing a glass fiber according to the present invention in
combination with one or more organic and/or inorganic materials can be used for preparing
composite materials having improved characteristics, such as glass fiber reinforced
base materials.
INDUSTRIAL APPLICABILITY OF THE INVENTION
[0102] The composition for producing a glass fiber of the present invention results in glass
fiber having higher modulus and improved forming properties; meanwhile, the composition
significantly lowers the liquidus temperature, crystallization rate and bubble amount
of the glass, and also broadens the temperature range (ΔT) for fiber formation. Compared
with the current mainstream high-performance glasses, the composition for producing
a glass fiber of the present invention has made a breakthrough in terms of elastic
modulus, crystallization temperature, crystallization rate and refining performance
of the glass, with significantly improved modulus, remarkably reduced crystallization
temperature and rate and relatively small amount of bubbles under the same conditions.
Thus, the overall technical solution of the present invention enables an easy achievement
of large-scale production with refractory-lined furnaces.