CN1187176A - Boron-free glass fibers - Google Patents
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- CN1187176A CN1187176A CN96194508A CN96194508A CN1187176A CN 1187176 A CN1187176 A CN 1187176A CN 96194508 A CN96194508 A CN 96194508A CN 96194508 A CN96194508 A CN 96194508A CN 1187176 A CN1187176 A CN 1187176A
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Abstract
Boron-free glass fibers suitable for textile and reinforcements are described. The glass fibers have compositions consisting essentially of SiO2, CaO, Al2O3, and MgO. In a preferred embodiment, the glass contains essentially no fluorine, sulfate, or titania. These glass fiber compositions advantageously have broad or large values for delta T (i.e., the difference between the log (3) or forming temperature --the temperature at which the glass has a viscosity of approximately 1000 poise-- and the liquidus temperature), e.g., a delta T of at least about 125 DEG F (52 DEG C), more preferably of at least about 150 DEG F (66 DEG C).
Description
This application is a continuation-in-part application of U.S. patent application serial No. 08/568,008 filed on 6.12.1995, and said U.S. patent application No. 08/568,008 is a continuation-in-part application of U.S. patent application serial No. 08/469,836 filed on 6.6.1995.
The present invention relates to continuous glass fibers having a boron-free, i.e., substantially boron-free, glass composition. The glass fibers of the present invention are useful as reinforcing and textile glass fibers.
The standard glass composition used to make continuous glass fiber strands is "E" glass, which dates back to 1940. Although for the past 50 years, the E-glass generally described in US2,334,961 remains the most commonly used glass for making woven and reinforced glass fibers. The most important advantage of E-glass is that its liquidus temperature is up to 200 degrees Fahrenheit (93 ℃) below its forming temperature, which is a temperature at which the viscosity of the glass is typically close to 1000 poise.
E-glass can be melted and refined at lower temperatures. E-glass has a viscosity operable over a relatively low broad temperature range, a lower liquidus temperature range, and a lower devitrification rate. Typically, these glass compositions can be used to manufacture glass fibers at an operating temperature of 1900-. Industry for continuous glass manufacture, it is common to maintain the fiberizing temperature above about 100 degrees Fahrenheit (38 ℃) in its liquidus temperature to avoid devitrification in the glass delivery system and glass electrofusion platinum crucibles.
In the mid seventies boron and fluorine containing glasses were developed which could meet these operating conditions. See US 4026715. However, boron and fluorine in the glass melt are volatile components that contribute significantly to the overall output of the glass melting operation.
Glass compositions free of boron or fluorine are known, for example from british patent specification 520427. However, the known boron-and fluorine-free glass compositions suffer from said problems.
Of the kind described in British patent specification 520427Woven glass needs to be melted and shaped under high temperature operating conditions that are practically impossible. Devitrification (crystallization) often occurs during glass electrofusion of platinum crucibles or during forming. For example, British patent specification 520247 describes a substantially alkali-free glass composition containing CaO, MgO, Al2O3And SiO2It can also beBy adding B2O3、CaF2、P2O5Or small amounts of bases, e.g. Na2O、K2O or lithium oxide. However, only a small amount of these glasses are fiberized and only boron-containing glasses can be fiberized in a continuous fiberizing process without difficulty. Glass 1 on page two of the british reference is a boron-free glass that can be formed in a continuous fiber forming process by virtue of the 100 degrees fahrenheit (38 ℃) difference between its liquidus temperature and forming temperature, but its 2350 degrees fahrenheit (1288 ℃) forming temperature is too high to be formed according to earlier known processes. The viscosity of glass 2 in this British reference is 1000 poise at a temperature only 87 degrees Fahrenheit (31 ℃) above the liquidus temperature. This can lead to devitrification during continuous glass fiber manufacturing. British patent 520247 states that this glass is preferably used for insulating glass wool, which can be shaped with a smaller liquidus temperature and forming temperature difference than continuous fibres. The glass 3 in this british reference has a liquidus temperature in excess of the forming temperature of 52 degrees fahrenheit (11 ℃) and crystallizes in a glass electrofusion platinum crucible during continuous fiber operation.
US4542106 to Spoull describes boron and fluorine free glass fiber compositions. Typically, they contain 58-60% SiO2，11-13％Al2O321-23% of CaO, 2-4% of MgO and 1-5% of TiO2. The glass fiber composition may also contain alkali metal oxides and trace amounts of Fe2O3Except for the absence of boron and fluorine and the presence of substantial amounts of TiO2In addition, the glasses have creepage characteristics, so they can be used in standard E and "621" glasses (621 glasses are generally described in US 2571074). U.S. Pat. No. 3,47627 to Erickson et al also describes fiberizable glass compositions, which glass compositionsThe product is free of boron and fluorine and contains a large amount of TiO2. The compositions of Erickson et al consist essentially of 54.5-60% SiO2、9-14.5％Al2O3、17-24％CaO、2-4％TiO21.5-4% of MgO and 1-5.5% of ZnO, SrO or BaO. However, there are disadvantages to using large amounts of titanium dioxide. For example, large amounts of titanium oxide can produce undesirable color in the glass.
In order to reduce the cost of manufacturing glass fibers and reduce environmental pollution without increasing production costs, there is a need in the art for improvements in glass compositions that are substantially free of boron and fluorine, but avoid undesirable coloration while having the advantages of E-glass and that can be readily fiberized in a continuous fiberizing process.
The object of the present invention is thereforeto obtain glass fibres which meet economic and environmental requirements and which have excellent properties. Another object is to produce glass fiber compositions with little or no boron and fluorine which can be fiberized without great difficulty. These and other objects and advantages are achieved by the glass fiber of the present invention.
We have found that the level of sulphate must be reduced in the batch to effectively melt and form glass having a composition generally similar to that described in british patent 520247. However, the glass compositions of the present invention unexpectedly result in a larger difference between the forming temperature and the liquidus temperature (i.e., a wider delta T value). We have improved glass compositions and also have employed a process which allows us to successfully fiberize glass with specific properties.
The glass fibers suitable for use in the weaving and reinforcement of glass fibers of the present invention have a glass composition consisting essentially of:
amount of ingredients (% by weight)
SiO259.0-62.0
CaO 20.0-24.0
Al2O312.0-15.0
MgO 1.0-4.0
F20.0-0.5
Na2O 0.1-2.0
TiO20.0-0.9
Fe2O30.0-0.5
K2O 0.0-2.0
SO30.0 to 0.5 total of all ingredients, including any trace impurities in the composition, to 100%. The glass has a viscosity of 1000 poise at 2100 DEG F, 2500 DEG F (1149 DEG F, 1371 ℃) and a liquidus temperature at least 100 DEG F (38 ℃) below the fiberizing temperature. In addition to their high temperature operating conditions, these glasses can be formed into fibers without devitrification during formation into electrofused platinum crucibles or during forming.
In a preferred embodiment, the weight percentage of MgO is between 2.0 and 3.5%.
In another preferred embodiment, SiO is present in these compositions2、CaO、Al2O3MgO and R2O( ) The amount of (A) is:
amount of ingredients (% by weight)
SiO259.0-61.0
CaO 21.5-22.5
Al2O312.7-14.0
MgO 2.5-3.3
Na2O+K2O 0.1-2.0
TiO20.0-0.6 viscosity of these glasses at 2200-The glass has a liquidus temperature at least 125 degrees Fahrenheit (52 ℃) below a temperature at which the viscosity is 1000 poise.
More preferably, SiO2、CaO、Al2O3MgO and R2The amount of O is:
amount of ingredients (% by weight)
SiO259.5-60.5
CaO 21.7-22.3
Al2O313.0-13.5
MgO 2.7-3.3
Na2O+K2O 0.5-1.0
In a particularly preferred embodiment, TiO2The amount of (b) is not more than 0.6% by weight, more preferably not more than 0.04% by weight. In another preferred embodiment, the TiO is2In an amount of not more than 0.6% by weight and F2The amount of (a) is substantially 0. In another preferred embodiment, the amount of sulfate, fluorine and titanium dioxide is substantially 0.
In a particularly preferred embodiment, continuous fibers having approximately the following glass composition can be prepared: 60.1% SiO2；22.1％CaO；13.2％Al2O3；3.0％MgO；0.2％K2O；0.2％Fe2O3；0.1％F2；0.5％TiO2And 0.6% Na2And O. The temperature characteristics of the glass are log3 at about 2300 degrees Fahrenheit (1260 ℃), a liquidus temperature at about 2200 degrees Fahrenheit (1200 ℃) and a delta T at about 150 degrees Fahrenheit (66 ℃). This glass also has approximately the following properties: a specific gravity (of the fiber, according to ASTM D1505) of about 2.62 g/ml; tensile strength (virgin, non-infiltrated laboratory-prepared single fiber, ASTM D2101) at 23 ℃ was approximately 3100 ℃ 3800MPa (450 ℃ 550 kpsi); modulus of elasticity (Acoustic method)About 80-81GPa (MPsi); elongation at break (original, non-infiltrated laboratory-made single fiber, ASTM D2101) was about 4.6%; refractive index (original, non-infiltrated laboratory-prepared single fiber, oil immersion method) of about1.560-1.562; a coefficient of thermal linear expansion (of annealed glass block, ASTM C336) of about 6.0 ppm/deg.C from 0 to 300 deg.C; a softening point (ASTM C338) of about 916 ℃; an annealing point (ASTM C336) of about 736 ℃; a strain point (ASTM C336) of about 691 ℃; a dielectric constant (of annealed glass block, ASTM D150) of about 7.0 at 23 ℃ and 1 MHz; a dispersion factor (of annealed glass blocks, ASTM D150) of about 0.001 at 23 ℃ and 1 MHz; the bulk resistance (of the annealed glass block, ASTM D257, calculated frommeasurements at elevated temperature 120 ℃., 500 ℃, according to log resistance ═ a/temperature + B) was about 8.1 "10" 26; dielectric strength (of annealed glass block, ASTM D149) at 4.8mm thickness was about 8 kV/mm; the percentage of the original strength (original, non-infiltrated individual fibers prepared in the laboratory) after 28 days exposure to 5% NaOH at 23 ℃ was about 30.
The glass fiber composition of the present invention is substantially free of boron. By "substantially free" is meant that the composition contains at most trace amounts of the recited components, such as by impurities in the starting materials. In a preferred embodiment, the glass fibers are also substantially free of fluorine. In another preferred embodiment, the glass fibers are also substantially free of titanium dioxide.
In general, the glass fibers of the present invention can be prepared in the manner described below. The ingredients may be mixed in suitable amounts and in conventional manner and may be prepared from suitable ingredients or materials (e.g. sand for SiO)2Quicklime for CaO and dolomite for MgO) and optionally also traces of other ingredients, thus obtaining suitable weight percentages of the final composition. The mixed batch materials are then melted in a furnace or melter and the resulting molten glass is flowed along the work zone and into a fiber-forming electrofusion platinum crucible at the bottom of the work zone. And drawing the molten glass downwards through a material hole on the bottom or the top plate of the electric melting platinum crucible. The stream of molten glass flowing over the top plate of the electrofusion platinum crucible is attenuated into filaments by winding them around a forming tube mounted on the spinner of the winder. The fibers may be further processed in a conventional manner to suit the desired application.
The temperature of the glass in the furnace, the work zone and the electrofused platinum crucible is selected to properly adjust the viscosity of the glass. The operating temperature may be maintained by suitable means, such as a control device. Preferably, the temperature at the front end of the melter may be automatically controlled to help avoid devitrification.
The use of sulfate in the furnace operation can help avoid devitrification or blistering problems in the glass. When producing large scale melts, we have found that it is important to add carbon to the batch to control the amount of bubbles in the furnace. Preferably, the ratio of sulfate to carbon (SO) in the batch3/C) is different from E glass, about 0.6-1.7, and E glass has at most SO3and/C is 3.0-10.0. The ratio of sulfate to carbon is preferably controlled in the furnace to maintain the bubbles at a controlled level and to allow heat to penetrate into the glass from the gas burner. It should be understood that the composition is preferably substantially sulfate-free. This is because, like carbon, sulfate is completely removed from the glass during melting.
In addition, the addition of a small amount of base can help to improve the melting rate of the batch. For example, about 0.70% Na may be added2O to aid in melting.
The working zone is designed so that the glass is maintained above the liquidus temperature throughout the working zone. The working area should be constructed to provide uniform heating of the glass to avoid devitrification of the cold spot.
The improved glass composition can be easily formed into fibers by modifying the existing electrofused platinum crucible technology. See, for example, U.S. Pat. Nos. 5,055,119, 4,846,865 and 5,312,470, the disclosures of which are incorporated herein by reference. With these improved electrofusion platinum crucible techniques, fibers can be formedat high temperatures with a small difference in forming and liquidus temperatures. Generally, electrofusion platinum crucibles should be designed to provide a long life and resistance to collapse, which is related to the pressure and temperature of the glass on the top plate. For example, electrofusion platinum crucibles may be made from refractory alloy compositions, for example, which contain about 22-25% rhodium and platinum. The stiffness of the top panel can be increased by using structural and mechanical reinforcement structures, such as T-shaped gussets. Electrofusion platinum crucible deceive should have a high degree of corrosion resistance, which can be achieved by making the expanded metal from platinum.
The above discussion of parameters and equipment is intended to illustrate the process for making the glass fibers of the present invention. It should be understood that the skilled artisan can modify or optimize process parameters and equipment as appropriate for the particular glass fiber being produced and conventional design considerations.
The invention is described below by way of examples. Example 1
Four samples of reinforcing glass fibers were prepared, the average glass composition of which was analyzed to consist essentially of the following constituents (in weight%): 60.01% SiO2、22.13％CaO、12.99％Al2O3、3.11％MgO、0.04％F2、0.63％Na2O、0.55％TiO2、0.25％Fe2O3、0.14％K2O and 0.02% SO3. On average, a forming temperature of 1000 poise (log3)The temperature was 2298 degrees Fahrenheit (1259 degrees Celsius), the liquidus temperature was 2146 degrees Fahrenheit (1174 degrees Celsius), and the forming-liquidus temperature difference (Δ T) was 135 degrees Fahrenheit (57 degrees Celsius). Example 2
Preparing glass fiber by using a laboratory melting furnace and reagents, wherein the glass fiber comprises the following components in percentage by weight: 60.08% SiO2、22.07％CaO、13.21Al2O3、3.01％MgO、0.16％K2O、0.23％Fe2O3、0.05％SO3、0.06％F2、0.52％TiO2And 0.60% Na2And O. The glass obtained had the following temperature properties: log 3-2309 degrees fahrenheit (1265 deg.c), liquidus temperature 2156 degrees fahrenheit (1180 deg.c) and δ T-153 degrees fahrenheit (67 deg.c).
The glass fiber was prepared as follows. About 30 grams of cullet, prepared by melting reagent grade chemicals corresponding to the above ingredients in a platinum crucible, was charged into a 1 inch (2.54 cm) diameter resistively heated platinum crucible. The glass was heated at a temperature of 100 ℃ or higher than the forming temperature for 1 hour. Then, the electrofused platinum is put into useThe temperature of the crucible is lowered to the forming temperature and the fiber is prepared by drawing the glass through a single hole in an electrofused platinum crucible onto a winder. It is worth noting that although a small amount of Sulfate (SO) will be present3) Is added to prevent crystallization/blistering problems in the glass, but during heating of the glass batch, substantially all of the sulfate is driven off along with the blisters. Examples 3 to 8
Glass fibers were prepared in the same manner as in example 2 from the batch compositions (in weight percent) shown in the following table. EXAMPLE No. 345678% SiO259.45 61.05 59.05 59.05 59.45 59.96％CaO 22.69 22.29 24.29 22.29 22.69 22.18％Al2O313.48 13.08 13.08 15.08 13.48 13.19％MgO 3.23 2.83 2.83 2.83 3.23 3.07％K2O 0.63 0.23 0.23 0.23 0.230.25％Fe2O30.36 0.36 0.36 0.36 0.36 0.28％SO30.05 0.05 0.05 0.05 0.05 0.05％F20.04 0.04 0.04 0.04 0.04 0.09％TiO20.04 0.04 0.04 0.04 0.04 0.37％Na2O 0.03 0.03 0.03 0.03 0.43 0.55log3 2308°F 2334°F 2279°F 2353°F 2298°F 2310°F
(1264 deg.C) (1279 deg.C), (1248 deg.C) (1289 deg.C) (1259 deg.C) (1266 deg.C) liquidus temperature of 2180 deg.F 2161 deg.F 2136 deg.F 2227 deg.F 2171 deg.F 2181 deg.C
(1193℃) (1183℃) (1169℃) (1219℃) (1188℃) (1194℃)δT 128°F 173°F 143°F 127°F 127°F 129°F
(53 ℃ C.) (78 ℃ C.) (62 ℃ C.) (53 ℃ C.) (54 ℃ C.) example 9
Preparing a glass fiber having the following composition, wherein fluorine, sulfate and titanium oxide are substantially absent: 61.00% SiO2、22.24％CaO、12.00％Al2O3、3.25％MgO、0.52％K2O、0.30％Fe2O3、0.00％SO3、0.00％F2、0.00％TiO2And 0.69% Na2And O. The glass has the following temperature properties: log 3-2304 degrees fahrenheit (1262 ℃), liquidus 2203 degrees fahrenheit (1206 ℃) and δ T-101 degrees fahrenheit (38 ℃).
As is understood in the art, the above exemplified compositions are not always accurate to 100% (e.g., about and average) of the above ingredients due to statistical convention. Of course, the sum of the actual amounts of all ingredients, including any impurities, in a particular composition is always 100%.
In addition, it should be understood that minor amounts of ingredients, for example in amounts in the range of about 0.05% by weight or less, maybe present in the composition as trace impurities present in the starting materials rather than intentionally added. In addition, these ingredients may be added to the batch composition to aid handling and then removed, thereby resulting in a glass composition that is substantially free of these ingredients. For example, while minor amounts of ingredients such as fluorine and sulfate are exemplified in the various examples, the resulting glass compositions are substantially free of these ingredients, e.g., they are only trace impurities in the raw materials of the silica, calcia, alumina and magnesia ingredients, or they may be treated so that they are substantially removed during the manufacturing process, in the commercial practice of the invention.
As is apparent from the above examples, the glass fiber composition of the present invention has excellent properties such as low viscosity and broad (high) Δ T value. Other advantages and obvious modifications of the invention will become apparent to those skilled in the art from the foregoing description and further embodiments of the invention.
Claims (15)
1. A continuous glass fiber having a composition that is substantially free of boron, and which consists essentially of:
the weight of the ingredients
SiO259.0-62.0
CaO 20.0-24.0
Al2O312.0-15.0
MgO 1.0-4.0
F20.0-0.5
Na2O 0.1-2.0
TiO20.0-0.9
Fe2O30.0-0.5
K2O0.0-2.0
SO30.0-0.5 wherein the composition has (i) a viscosity of 1000 poise at 2100-.
2. The continuous glass fiber according to claim 1, wherein the content of MgO is 2.0 to 3.5% by weight.
3. The continuous glass fiber according to claim 1, comprising:
the weight of the ingredients
SiO259.0-61.0
CaO 21.5-22.5
Al2O312.7-14.0
MgO 2.5-3.3
Na2O+K2O 0.1-2.0
TiO20.0-0.6The molding temperature is 2200 DEG F, 2400 DEG F (1204 DEG 1316 ℃), and the liquidus temperature and the molding temperature areThe difference in degrees is at least 125 degrees fahrenheit (52 ℃).
4. The continuous glass fiber according to claim 3, which comprises:
the weight of the ingredients
SiO259.5-60.5
CaO 21.7-22.3
Al2O313.0-13.5
MgO 2.7-3.3
Na2O+K2O 0.5-1.0
5. The continuous glass fiber according to claim 3, which comprises: 60.1% SiO2；22.1％CaO；13.2％Al2O3；3.0％MgO；0.8％Na2O+K2O。
6. The continuous glass fiber of claim 1, wherein: TiO 22In an amount of not more than 0.6% by weight.
7. The continuous glass fiber of claim 6, wherein the TiO2In an amount of 0.00-0.04% by weight.
8. The continuous glass fiber according to claim 7, wherein F2In an amount of 0.00-0.04% by weight.
9. The continuous glass fiber of claim 1, wherein the composition is substantially free of TiO2。
10. The continuous glass fiber of claim 1, wherein the composition is substantially free of F2。
11. The continuous glass fiber of claim 1, wherein the composition is substantially free of SO3。
12. According to claim 1Continuous glass fibers of which SO3、F2And TiO2Each of the contents of (a) to (b) does not exceed 0.05% by weight.
13. The continuous glass fiber of claim 1, wherein the difference between the forming temperature and the liquidus temperature is at least 150 degrees fahrenheit (66 ℃).
14. The continuous glass fiber according to claim 1, comprising: 60.2% SiO2；22.0％CaO；13.2％Al2O3；3.0％MgO；0.8％Na2O+K2O at a forming temperature of 2200 DEG F, 2400 DEG F (1204 DEG F), 1316 DEG F, and a difference between the forming temperature and the liquidus temperature of at least 125 DEG F (52 ℃).
15. The continuous glass fiber according to claim 1, comprising: about 60.1% SiO2(ii) a About22.1% CaO; about 13.2% Al2O3(ii) a About 3.0% MgO; about 0.2% K2O; about 0.6% Na2O; about 0.2% Fe2O3(ii) a About 0.1% SO3+F2And about 0.5% TiO2The forming temperature is about 2300 DEG F2400 DEG F (1204 DEG F1316 ℃), and the difference between the forming temperature and the liquidus temperature is at least about 150 DEG F (52 ℃).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96194508A CN1187176A (en) | 1995-06-06 | 1996-06-06 | Boron-free glass fibers |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/469,836 | 1995-06-06 | ||
| US08/568,008 | 1995-12-06 | ||
| CN96194508A CN1187176A (en) | 1995-06-06 | 1996-06-06 | Boron-free glass fibers |
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| Publication Number | Publication Date |
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| CN1187176A true CN1187176A (en) | 1998-07-08 |
Family
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| CN96194508A Pending CN1187176A (en) | 1995-06-06 | 1996-06-06 | Boron-free glass fibers |
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| CN100522857C (en) * | 2000-09-06 | 2009-08-05 | Ppg工业俄亥俄公司 | Glass fiber forming compositions |
| WO2010099670A1 (en) * | 2009-03-02 | 2010-09-10 | 巨石集团有限公司 | Glass fibre composition |
| CN101597140B (en) * | 2009-07-02 | 2011-01-05 | 重庆国际复合材料有限公司 | High-strength high-modulus glass fiber |
| CN1962760B (en) * | 2005-11-11 | 2011-06-15 | 旭玻璃纤维股份有限公司 | Glass filler for polycarbonate resin, and polycarbonate resin composition |
| CN102417302A (en) * | 2006-06-23 | 2012-04-18 | 日本板硝子株式会社 | Scaly glass |
| CN102491644A (en) * | 2011-11-16 | 2012-06-13 | 泰山玻璃纤维有限公司 | High magnesium content boron-free glass fiber |
| CN102730976A (en) * | 2011-04-11 | 2012-10-17 | 重庆国际复合材料有限公司 | Organic or inorganic fiberglass for enhancement, and composition thereof |
| CN104150779A (en) * | 2014-08-27 | 2014-11-19 | 济南大学 | Boron-free low-dielectric-constant glass fiber with solid waste being raw material and preparation method thereof |
| CN104150781A (en) * | 2014-08-27 | 2014-11-19 | 济南大学 | Boron-free low-dielectric-constant glass fiber with blast furnace slag and quartz sand being raw materials and preparation method thereof |
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1996
- 1996-06-06 CN CN96194508A patent/CN1187176A/en active Pending
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| CN100522857C (en) * | 2000-09-06 | 2009-08-05 | Ppg工业俄亥俄公司 | Glass fiber forming compositions |
| CN1962760B (en) * | 2005-11-11 | 2011-06-15 | 旭玻璃纤维股份有限公司 | Glass filler for polycarbonate resin, and polycarbonate resin composition |
| CN102417302A (en) * | 2006-06-23 | 2012-04-18 | 日本板硝子株式会社 | Scaly glass |
| WO2010099670A1 (en) * | 2009-03-02 | 2010-09-10 | 巨石集团有限公司 | Glass fibre composition |
| CN101597140B (en) * | 2009-07-02 | 2011-01-05 | 重庆国际复合材料有限公司 | High-strength high-modulus glass fiber |
| CN102730976A (en) * | 2011-04-11 | 2012-10-17 | 重庆国际复合材料有限公司 | Organic or inorganic fiberglass for enhancement, and composition thereof |
| CN102491644A (en) * | 2011-11-16 | 2012-06-13 | 泰山玻璃纤维有限公司 | High magnesium content boron-free glass fiber |
| CN104150779A (en) * | 2014-08-27 | 2014-11-19 | 济南大学 | Boron-free low-dielectric-constant glass fiber with solid waste being raw material and preparation method thereof |
| CN104150781A (en) * | 2014-08-27 | 2014-11-19 | 济南大学 | Boron-free low-dielectric-constant glass fiber with blast furnace slag and quartz sand being raw materials and preparation method thereof |
| CN104150781B (en) * | 2014-08-27 | 2017-02-15 | 济南大学 | Boron-free low-dielectric-constant glass fiber with blast furnace slag and quartz sand being raw materials and preparation method thereof |
| CN104150779B (en) * | 2014-08-27 | 2017-02-15 | 济南大学 | Boron-free low-dielectric-constant glass fiber with solid waste being raw material and preparation method thereof |
| EP3674269B1 (en) * | 2018-06-22 | 2025-01-01 | Jushi Group Co., Ltd. | Glass fiber composition, and glass fiber and composite material thereof |
| CN115806391A (en) * | 2022-12-15 | 2023-03-17 | 清远忠信世纪电子材料有限公司 | Low-expansion-coefficient glass fiber and preparation method thereof |
| CN115806391B (en) * | 2022-12-15 | 2024-03-29 | 清远忠信世纪电子材料有限公司 | Glass fiber with low expansion coefficient and preparation method thereof |
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