CN109982982B - Glass composition for glass fiber, and method for producing glass fiber - Google Patents
Glass composition for glass fiber, and method for producing glass fiber Download PDFInfo
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- CN109982982B CN109982982B CN201780071995.2A CN201780071995A CN109982982B CN 109982982 B CN109982982 B CN 109982982B CN 201780071995 A CN201780071995 A CN 201780071995A CN 109982982 B CN109982982 B CN 109982982B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
- C03C13/001—Alkali-resistant fibres
- C03C13/002—Alkali-resistant fibres containing zirconium
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
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Abstract
The purpose of the present invention is to provide a glass composition for glass fibers, which has excellent alkali resistance and excellent productivity. The glass composition for glass fibers of the present invention is characterized by containing SiO in terms of oxide-equivalent mass% as a glass composition250％～65％、Al2O30％～5％、CaO 0％～10％、Na2O 10％～20％、K2O 0％～5％、ZrO2More than 15% and not more than 20%, TiO20.1％～10％、B2O30.1％～10％。
Description
Technical Field
The present invention relates to a glass composition for glass fibers having excellent corrosion resistance. In particular, the present invention relates to a glass composition for glass fibers suitable as a reinforcing material such as a calcium silicate plate or GRC (glass fiber reinforced concrete), or a material requiring corrosion resistance such as a battery separator or an asbestos substitute.
Background
Conventionally, as a reinforcing material for GRC, SiO as described in patent document 1 has been used2-ZrO2-R2O (R is any of Li, Na and K) series ZrO-containing2The alkali-resistant glass fiber of (1).
The glass fiber is also used as a reinforcing material for calcium silicate sheets, a corrosion resistant material for battery separators, and the like.
GRC is a structural material for buildings formed into a plate shape by injecting a mixture of glass fibers, cement, aggregate, an admixture, water, and the like cut into a predetermined length into a mold using a spray gun or the like. The glass fiber used for the GRC is required to maintain strength satisfying reliability even in concrete over several decades.
The glass fiber as described above is obtained by continuously forming and spinning molten glass into a fiber shape using, for example, a bushing device made of a noble metal. The tip plate has a vessel shape for retaining molten glass, and a plurality of nozzles are disposed along a vertical direction at the bottom thereof. The glass fiber is adjusted to the spinning temperature (the viscosity of the glass is about 10)3dPa · s temperature, also referred to as forming temperature) is drawn from a nozzle at the bottom of the bushing into a fiber shape.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (Kokoku) No. 49-40126
Patent document 2: japanese Kokai publication Hei-2009-513470
Patent document 3: japanese examined patent publication No. 57-16940
Disclosure of Invention
Problems to be solved by the invention
Patent document 1 discloses that a glass composition contains a large amount of ZrO from the viewpoint of improving alkali resistance2The glass composition of (1). However, if ZrO is contained in a large amount2The spinning temperature of the glass becomes high. When the spinning temperature of glass is high, the damage of the bushing device made of noble metal becomes severe, the replacement frequency of the bushing becomes high, and the production cost of glass fiber becomes high. In addition, if ZrO is contained in a large amount2The liquid phase temperature rises, and the difference between the spinning temperature and the liquid phase temperature tends to decrease. If the difference between the spinning temperature and the liquid phase temperature is small, the glass is likely to be devitrified at the nozzle at the bottom of the bushing, and there is a problem that continuous production of glass fibers is difficult.
Further, patent document 2 discloses reduction of ZrO2And contains a certain amount of TiO2While maintaining the alkali-resistant glass composition. However, the glass fiber described in patent document 2 also has a high glass spinning temperature.
Further, patent document 3 discloses reduction of ZrO2And contains a certain amount of B2O3And a glass composition having a reduced spinning temperature. However, the glass fiber described in patent document 3 has a small difference between the glass spinning temperature and the liquid phase temperature, and has a problem that continuous production is difficult.
In this way, it is difficult to obtain a glass composition for glass fibers having excellent alkali resistance and excellent productivity.
The present invention has been made in view of the above circumstances, and an object thereof is to provide a glass composition for glass fibers which has excellent alkali resistance and excellent productivity.
Means for solving the problems
The inventors of the present invention have conducted extensive studies and found that: when the glass composition for glass fibers contains ZrO in an amount of not less than a certain amount2Containing TiO in the glass composition2And B2O3As an essential component, the liquidus temperature can be significantly reduced without increasing the glass spinning temperature, and the difference between the glass spinning temperature and the liquidus temperature can be significantly increased. And further found that: since it contains ZrO in an amount of not less than a certain amount2Therefore, even if TiO is added2And B2O3And the acid resistance, the alkali resistance and the water resistance are not greatly influenced.
That is, the glass composition for glass fibers of the present invention is characterized by containing SiO in terms of oxide-converted mass% as a glass composition250～65％、Al2O30～5％、CaO 0～10％、Na2O10～20％、K2O0～5％、ZrO2More than 15% and not more than 20%, TiO20.1～10％、B2O30.1～10％。
Surprisingly, when containing more than a certain amount of ZrO2By containing B in the glass composition2O3And TiO2Both of these are considered to be eutectic with the crystal containing Na, Zr, and Si, and the liquid phase temperature is significantly lowered. As a result, the glass composition for glass fiber of the present invention has excellent alkali resistance, and the difference between the spinning temperature and the liquidus temperature of the glass is large, and the productivity is excellent.
The difference between the spinning temperature and the liquidus temperature of the glass composition for glass fibers of the present invention is preferably 115 ℃ or more. The "spinning temperature" means that the viscosity of the glass is 103Temperature of dPa · s. Thus, a glass composition for glass fibers having excellent productivity can be obtained.
In the glass composition for glass fibers of the present invention, B is a mass ratio in terms of oxides2O3/TiO2The value of (A) is preferably 0.01 to 95. Thus, glass having excellent alkali resistance, a larger difference between the spinning temperature and the liquidus temperature of the glass, and excellent productivity can be obtainedA glass composition for glass fibers.
In the glass composition for glass fibers of the present invention, B2O3+TiO2The content of (b) is preferably 1 to 20% by mass. Here, "B" is2O3+TiO2"means B2O3With TiO2The total amount of (a). Thus, a glass composition for glass fibers having excellent alkali resistance, a larger difference between the spinning temperature and the liquidus temperature of the glass, and excellent productivity can be produced more reliably.
In the glass composition for glass fibers of the present invention, B2O3The content of (B) is preferably 0.5 to 7.8 mass%. Thus, the spinning temperature and the liquidus temperature can be reduced, and a glass composition for glass fibers having excellent alkali resistance can be obtained.
In the glass composition for glass fiber of the present invention, Li2The content of O is preferably 0 to 0.2 mass%. Thus, the production cost can be reduced.
In the glass composition for glass fiber of the present invention, Na2O+K2The content of O is preferably 10 to 20%. Here, "Na2O+K2O "is Na2O and K2The total amount of O. This can reduce the viscosity of the glass, and can provide a glass composition for glass fibers having excellent meltability and moldability.
In the glass composition for glass fiber of the present invention, the spinning temperature is preferably 1270 ℃ or lower. This enables fiberization at a low temperature, which reduces melting costs, and also enables longer service life of fiberizing equipment such as bushings, which reduces production costs.
In the glass composition for glass fiber of the present invention, the liquidus temperature is preferably 1150 ℃ or lower. This makes spinning easy, and therefore, a glass composition for glass fibers having excellent productivity can be obtained.
The glass composition for glass fibers of the present invention preferably has a glass mass reduction rate of 4% or less when immersed in 100ml of a 10 mass% aqueous solution of NaOH at 80 ℃ for 90 hours. The glass having a specific gravity of 1 part by mass and classified into a particle size of 300 to 500 μm was used for the evaluation. Thus, glass fibers having high reliability as reinforcing materials for composite materials such as calcium silicate boards and GRC can be easily obtained.
The glass composition for glass fibers of the present invention preferably has a glass mass reduction rate of 4% or less when immersed in 100ml of a 10 mass% aqueous HCl solution at 80 ℃ for 90 hours. The glass having a specific gravity of 1 part by mass and classified into a particle size of 300 to 500 μm was used for the evaluation. Thus, glass fibers having high reliability as a corrosion resistant material such as a battery separator can be easily obtained.
The glass fiber of the present invention is characterized by containing the glass composition for glass fiber.
The method for producing glass fibers of the present invention is characterized in that a raw material batch, which is SiO in terms of mass% in terms of oxides as a glass composition, is melted in a glass melting furnace, and the resulting molten glass is continuously drawn out from a bushing and molded into a fiber shape2 50～65％、Al2O30～5％、CaO 0～10％、Na2O 10～20％、K2O 0～5％、ZrO2More than 15% and not more than 20%, TiO2 0.1～10％、B2O30.1-10% of the above-mentioned components.
In the method for producing glass fibers of the present invention, the raw material mixture is preferably prepared so that the difference between the spinning temperature and the liquidus temperature of the obtained glass becomes 115 ℃ or more.
In the method for producing glass fibers of the present invention, it is preferable to use B in a mass ratio in terms of oxides2O3/TiO2A raw material batch prepared so that the value of (D) is 0.01 to 95.
This can further increase the difference between the glass spinning temperature and the glass liquidus temperature without increasing the melting temperature, and therefore can improve productivity.
Detailed Description
The glass composition for glass fibers of the present invention will be described below. Unless otherwise specified, in the description of the content range of each component,% represents mass%.
SiO2Is a main component forming a skeleton structure of the glass, and is also a component for improving acid resistance of the glass. SiO 22The content of (B) is 50 to 65%, preferably 55 to 60%, more preferably 57 to 60%. If SiO2When the content of (b) is too small, the mechanical strength of the glass tends to be low, and the acid resistance of the glass tends to be low. If SiO2When the content (b) is too large, the viscosity of the glass increases and the energy required for melting the glass increases. Further, the damage of the bushing made of noble metal becomes more serious, the replacement frequency becomes high, and the production cost becomes high. Further, the alkali resistance of the glass is lowered.
Al2O3Is a component for improving the chemical durability and mechanical strength of the glass. On the other hand, Al2O3And also a component for increasing the viscosity of the glass. Al (Al)2O3The content of (B) is 0 to 5%, preferably 0 to 3%, more preferably 0 to 1%. If Al is present2O3When the content (b) is too large, the viscosity of the glass increases and the energy required for melting the glass increases.
CaO is a component that lowers the viscosity of the glass. The content of CaO is 0 to 10%, preferably 0 to 5%, more preferably 0 to 4%, and further preferably 0 to 3%. If the content of CaO is too large, crystals containing Zr, Si, Na, and Ca are likely to precipitate in the glass, the liquidus temperature of the glass becomes high, the difference between the spinning temperature and the liquidus temperature becomes small, and productivity is lowered.
Na as an alkali metal oxide2O and K2O is a component for lowering the viscosity of the glass and improving the meltability or formability of the glass. On the other hand, the alkali metal oxide is a component which lowers the water resistance of the glass when it is contained in an excessively large amount. Na (Na)2O+K2The amount of O is 10 to 20%, preferably 10 to 18%, more preferably 12 to 18%, and further preferably 15 to 17%. If Na2O+K2When the amount of O is too small, the viscosity of the glass increases, and the energy required for melting the glass increases. Further, the damage of the bushing made of noble metal becomes more serious, the replacement frequency becomes high, and the production cost becomes high. If Na2O+K2When the amount of O is too large, the water resistance of the glass is lowered.
Na2O is a component for lowering the viscosity of the glass and improving the meltability or formability of the glass. Na (Na)2The content of O is 10 to 20%, preferably 10 to 18%, more preferably 12 to 18%, most preferably 12 to 17%. If Na2When the content of O is too small, the viscosity of the glass increases, and the energy required for melting the glass increases. Further, the damage of the bushing made of noble metal becomes more serious, the replacement frequency becomes high, and the production cost becomes high. If Na2When the content of O is too large, the liquidus temperature of the glass becomes high, the difference between the spinning temperature and the liquidus temperature becomes small, and the productivity is lowered. In addition, the water resistance of the glass is reduced.
K2O is a component for improving the melting property and the formability of the glass by lowering the viscosity of the glass. K2The content of O is 0 to 5%, preferably 0 to 3%, most preferably 0 to 2%. If K2When the content of O is too large, the water resistance of the glass is lowered. Further, the raw material batch easily absorbs moisture, and easily forms aggregates (so-called "lumps") of raw material powder. When the aggregate of the raw material powder is formed, the solubility of the raw material batch is deteriorated, and undissolved zirconia tends to remain in the glass fiber, which is not preferable.
Li2O is a component which can significantly lower the liquid phase temperature, increase the difference between the spinning temperature and the liquid phase temperature, and improve productivity by adding a small amount of O. However, Li2The raw material cost of O is high, so if Li2An excessive content of O increases the production cost. Further, as the demand of lithium batteries increases, the risk of supply shortage of lithium raw material becomes high, and therefore, if Li is used2If the content of O is too large, there is a risk that the production of the required lithium raw material cannot be ensured. Thus, Li2The content of O is preferably 0 to 0.2%, and Li is preferably not contained from the viewpoint of cost and supply2And O. Here, "Li-free2O "means that Li is not positively contained as a glass composition2The meaning of O does not exclude unavoidable impurities. More specifically, the content of impurities means 0.01% by mass or less. In this way, problems such as uneasy supply of raw materials and high raw material cost can be easily avoided.
ZrO2Is a component for improving the alkali resistance, acid resistance and water resistance of the glass. ZrO (ZrO)2The content of (b) is more than 15% and 20% or less, preferably 15.5 to 19.5%, more preferably 16 to 19%, further preferably 16.5 to 18.5%, most preferably 17 to 18%. If ZrO of2If the content of (b) is too small, the alkali resistance of the glass composition for glass fiber is lowered, and as a result, the durability required for GRC cannot be achieved. If ZrO of2When the content of (B) is too large, the liquidus temperature of the glass becomes high, the difference between the spinning temperature and the liquidus temperature becomes small, and the productivity is lowered.
TiO2The glass is a component which improves the water resistance and alkali resistance of the glass, reduces the spinning temperature and greatly reduces the liquid phase temperature. TiO 22The content of (B) is 0.1 to 10%, preferably 1 to 9%, more preferably 2 to 8%. If TiO2When the content of (b) is too small, the water resistance and alkali resistance of the glass are lowered, the spinning temperature is increased, and the production cost is increased. If TiO2If the content of (A) is too large, TiO-containing particles are likely to precipitate in the glass2The liquid phase temperature of (3) is greatly increased. As a result, the difference between the spinning temperature and the liquid phase temperature is reduced, and productivity is lowered.
B2O3Is a component for reducing the spinning temperature and greatly reducing the liquid phase temperature. B is2O3The content of (B) is 0.1 to 10%, preferably 1 to 9%, more preferably 1 to 7.8%. If B is2O3If the content of (b) is too small, the spinning temperature rises, the difference between the spinning temperature and the liquid phase temperature becomes small, and the productivity is lowered. Furthermore, if B2O3When the content of (A) is too large, the alkali resistance of the glass is lowered.
The glass composition for glass fiber of the present invention contains B2O3And TiO2As an essential component. This is because: as described above, when ZrO is contained in an amount of not less than a certain amount2By containing B in the glass composition2O3And TiO 22Both of these are considered to be eutectic with the crystal containing Na, Zr, and Si, and the liquid phase temperature is significantly lowered. B is2O3/TiO2The value of (A) is used as an index for determining the eutectic point and an index for controlling the alkali resistance of the glassIt is important. B is2O3/TiO2The value of (A) is 0.01 to 95, preferably 0.02 to 92, more preferably 0.05 to 90, still more preferably 0.10 to 85, and particularly preferably 0.12 to 80. If B is2O3/TiO2When the value of (A) is too small, the liquid phase temperature increases, resulting in a decrease in productivity. Furthermore, if B2O3/TiO2When the value of (3) is too large, the alkali resistance is lowered.
In order to more reliably obtain B2O3With TiO2In the presence of B2O3And TiO2When B is used, B is preferably2O3With TiO2The total amount of (A) is limited to a certain range. This can significantly reduce the liquidus temperature and improve productivity. Thus, B2O3+TiO2The value of (b) is 1 to 20%, preferably 2 to 19%, more preferably 3 to 18%, further preferably 4 to 18%, 5 to 17%, 6 to 16%, 6.5 to 15%, particularly preferably 7 to 13%. If B is2O3+TiO2If the value of (b) is too small, the spinning temperature and the liquid phase temperature become high, and the productivity is lowered. If B is2O3+TiO2If the value of (b) is too large, the production cost increases.
The glass composition for glass fiber of the present invention may contain components other than the above (SiO)2、Al2O3、CaO、Na2O、K2O、Li2O、ZrO2、TiO2And B2O3) Other components. Among them, it is desirable to adjust the composition so that the content of the above components becomes 98% or more, particularly 99% or more, in total. The reason for this is that when the total amount of these components is less than 98%, the following disadvantages are likely to occur: mixing of different components which are not intentionally added results in a decrease in alkali resistance, acid resistance, and water resistance, a decrease in characteristics as a product, a decrease in a difference between a spinning temperature and a liquid phase temperature, a decrease in productivity, and the like.
As components other than the above, for example, H may be contained up to 0.1% respectively2、CO2、CO、H2O、He、Ne、Ar、N2And the like. In addition, additives may be added to the glassAdding noble metal elements such as Pt, Rh, Au and the like to 500 ppm.
In addition, MgO, SrO, BaO, ZnO, P may be contained in a total amount of 2% in order to improve alkali resistance, acid resistance, water resistance, liquid phase temperature2O5、Fe2O3、Cr2O3、Sb2O3、SO3、MnO、SnO2、CeO2、Cl2、La2O3、WO3、Nb2O5、Y2O3And the like.
The glass composition for glass fibers of the present invention has a weight reduction rate of 4% or less, preferably 3.9% or less, more preferably 3.8% or less, further preferably 3.6% or less, and particularly preferably 3% or less, when a glass having a specific gravity of 300 to 500 μm and a particle size of × 1 part by weight is immersed in 100ml of a 10 mass% aqueous solution of NaOH at 80 ℃ for 90 hours. When the glass weight reduction rate in the alkali resistance test is large, the reliability as a reinforcing material for a composite material such as a calcium silicate plate or a GRC is low.
The glass composition for glass fibers of the present invention has a glass weight reduction rate of 4% or less, preferably 3% or less, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1% or less, when a glass having a specific gravity of 300 to 500 μm and a specific gravity of 1 part by weight is immersed in 100ml of a 10 mass% aqueous solution of HCl at 80 ℃ for 90 hours. If the glass weight reduction rate in the acid resistance test is high, the reliability as a corrosion resistant material such as a battery separator is lowered.
The glass composition for glass fibers of the present invention has an alkali elution amount of 0.40mg or less, preferably 0.35mg or less, more preferably 0.30mg or less, and particularly preferably less than 0.30mg as measured by a method according to JIS R3502(1995) as a water resistance test. When the amount of alkali eluted is large, alkali components are eluted from the glass during autoclave treatment, and the glass is likely to be deteriorated.
The glass composition for glass fibers of the present invention has a spinning temperature of 1270 ℃ or lower, preferably 1265 ℃ or lower, more preferably 1260 ℃ or lower, and particularly preferably 1250 ℃ or lower. If the spinning temperature is too high, spinning needs to be performed at a high temperature, and therefore, not only the melting cost increases, but also the damage of the noble metal tip plate increases, the replacement frequency increases, and the production cost increases.
The glass composition for glass fibers of the present invention has a liquidus temperature of 1150 ℃ or less, preferably 1140 ℃ or less, more preferably 1130 ℃ or less, and particularly preferably 1120 ℃ or less. If the liquid phase temperature is too high, devitrification is liable to occur, and productivity is lowered.
The difference between the spinning temperature and the liquidus temperature of the glass composition for glass fibers of the present invention is 115 ℃ or more, preferably 120 ℃ or more, more preferably 130 ℃ or more, further preferably 140 ℃ or more, and particularly preferably 150 ℃ or more. If the difference between the spinning temperature and the liquid phase temperature is small, productivity is lowered.
Next, a method for producing the glass fiber of the present invention will be described by taking a direct melting method (DM method) as an example. The present invention is not limited to the following method, and may be, for example, an indirect molding method (MM method: marble melting method) in which a glass material for fibers molded into a marble shape is remelted by a bushing device and spun. The method is suitable for small-scale production of multiple varieties.
First, SiO is contained in terms of mass% in terms of oxide2 50～65％、Al2O3 0～5％、CaO 0～10％、Na2O 10～20％、K2O 0～5％、ZrO2More than 15% and not more than 20%, TiO20.1～10％、B2O3The glass raw materials are prepared in a manner of 0.1-10% of glass. A glass sheet may be used as a part or all of the glass raw material. The reason why the contents of the respective components are set as described above has been described, and the description thereof is omitted here.
Subsequently, the prepared raw material batch is put into a glass melting furnace, and vitrification, melting, and homogenization are performed. The melting temperature is about 1400-1600 ℃.
Next, the molten glass is spun to form glass fibers. In detail, the molten glass is supplied to the bushing. The molten glass supplied to the bushing is continuously drawn out in a filament shape from a plurality of bushing nozzles provided on the bottom surface thereof. The thus drawn monofilaments are coated with various treatment agents and collected for every fixed number of filaments, thereby obtaining glass fibers.
The glass fiber of the present invention thus formed is processed into chopped strands, yarns, rovings, and the like, and is used for various applications.
Further, the chopped strands mean: a glass fiber (strand) obtained by bundling glass filaments is cut into a predetermined length. The yarn is a product obtained by twisting a bundle of threads. The roving is a product obtained by winding a plurality of strands into a cylindrical shape.
Examples
The present invention will be described in detail below based on examples. Table 1 shows examples (Nos. 1 to 8) of the present invention and comparative example No.9, respectively.
[ Table 1]
The respective samples in the table were prepared as follows.
First, various glass raw materials such as natural raw materials and chemical raw materials were weighed and mixed so as to have glass compositions shown in the table, to prepare raw material batch mixtures. Subsequently, the raw material batch was put into a platinum-rhodium alloy crucible, and then heated at 1550 ℃ for 5 hours in an indirect heating furnace to obtain molten glass. In order to obtain homogeneous molten glass, the molten glass is stirred several times by using a heat-resistant stirring rod during heating. Then, the obtained molten glass was poured into a refractory mold, formed into a plate-like glass, and subjected to a slow cooling treatment (at a ratio of 10) in a slow cooling furnace13Heating at a temperature 30 to 50 ℃ higher than the dpas s temperature for 30 minutes, and then cooling the temperature region from the annealing point to the strain point at 1 ℃/minute). The spinning temperature, liquid phase temperature, acid resistance, alkali resistance, and alkali elution amount were measured for each of the obtained samples.
The spinning temperature was measured as follows.First, the plate-like glass sample was crushed into an appropriate size and put into an alumina crucible so as not to introduce bubbles as much as possible. Subsequently, the alumina crucible was heated to be in a molten state, and the glass viscosity at a plurality of temperatures was determined by the platinum ball pulling method. Then, a viscosity curve was prepared from the obtained plurality of measured values, and the value was calculated to be 10 by interpolation3Temperature at dPa · s.
The liquid phase temperature was measured as follows. First, the plate-like glass sample is pulverized to adjust the particle size to a range of 300 to 500 μm, and filled in a fire-resistant container to a state having an appropriate bulk density. Next, the refractory container was put into an indirect heating type temperature gradient furnace having a maximum temperature of 1350 ℃. Thereafter, the test piece was taken out from the temperature gradient furnace together with the fire-resistant container, cooled to room temperature, and then the liquid phase temperature was determined by a polarized light microscope.
The difference between the spinning temperature and the liquid phase temperature was calculated from the values of both.
The acid resistance was measured as follows. First, the plate-like glass sample was pulverized, and glass having a particle size of 300 to 500 μm was precisely weighed to have a specific gravity of 1 part by mass, and then immersed in 100ml of 10 mass% HCl solution, followed by vibration at 80 ℃ for 90 hours. Thereafter, the mass reduction rate of the glass sample was measured. The smaller the value, the more excellent the acid resistance.
The alkali resistance was measured as follows. First, the plate-like glass sample was pulverized, and glass having a particle size of 300 to 500 μm was precisely weighed to have a specific gravity of 1 part by mass, and then immersed in 100ml of a 10 mass% NaOH solution, followed by vibration at 80 ℃ for 90 hours. Thereafter, the mass reduction rate of the glass sample was measured. The smaller the value, the more excellent the alkali resistance.
The amount of alkali elution indicating water resistance was measured by a method according to JIS R3502 (1995). The smaller the value, the more excellent the water resistance.
As is clear from table 1: the spinning temperatures of the samples Nos. 1 to 8 were 1270 ℃ or lower, the difference between the spinning temperature and the liquid phase temperature was 115 ℃ or higher, the mass reduction rates as the indicators of the alkali resistance and the acid resistance were all 4% or lower, and the alkali elution amount was 0.40mg or lower.
In contrast, No.9 as a comparative example had a difference between the spinning temperature and the liquid phase temperature of less than 115 ℃ and was difficult to produce stably.
Industrial applicability
The glass fiber of the present invention is suitable as a reinforcing material for calcium silicate sheets, a corrosion resistant material such as a battery separator, and the like.
Claims (13)
1. A glass composition for glass fibers, characterized by containing SiO in terms of oxide-converted mass% as a glass composition2 50％～65％、Al2O3 0％～5％、CaO 0％～10％、Na2O 10％～20％、K2O 0％～5％、ZrO2More than 15% and not more than 20%, TiO24.8％～10％、B2O33.0 to 10% by mass of B in terms of oxide2O3/TiO2The value (b) is 0.63 to 3.33, and the mass reduction rate of the glass after immersion in 100ml of a 10 mass% NaOH aqueous solution at 80 ℃ for 90 hours is 4% or less.
2. The glass composition for glass fiber according to claim 1, wherein the difference between the spinning temperature and the liquidus temperature is 115 ℃ or more.
3. The glass composition for glass fiber according to claim 1 or 2, wherein B is B2O3+TiO2The content of (b) is 7.8 to 20 mass%.
4. The glass composition for glass fiber according to claim 1 or 2, wherein B is B2O3The content of (b) is 3.0 to 7.8 mass%.
5. The glass composition for glass fiber according to claim 1 or 2, characterized in thatCharacterized by that, Li2The content of O is 0 to 0.2 mass%.
6. The glass composition for glass fiber according to claim 1 or 2, wherein Na is2O+K2The content of O is 10 to 20 mass%.
7. The glass composition for glass fiber according to claim 1 or 2, wherein the spinning temperature is 1270 ℃ or lower.
8. The glass composition for glass fiber according to claim 1 or 2, wherein the liquidus temperature is 1150 ℃ or lower.
9. The glass composition for glass fiber according to claim 1 or 2, wherein the amount of alkali eluted is 0.30mg or less in accordance with JIS R3502.
10. The glass composition for glass fiber according to claim 1 or 2, wherein the glass composition has a mass reduction rate of 4% or less after being impregnated in 100ml of a 10 mass% aqueous HCl solution at 80 ℃ for 90 hours.
11. A glass fiber comprising the glass composition for glass fiber according to any one of claims 1 to 10.
12. A method for producing glass fibers, characterized in that a raw material batch is melted in a glass melting furnace, the obtained molten glass is continuously drawn out from a bushing and molded into a fiber shape,
the raw material batch is SiO in terms of mass% in terms of oxide as a glass composition2 50％～65％、Al2O3 0％～5％、CaO 0％～10％、Na2O 10％～20％、K2O 0％～5％、ZrO2More than 15% and not more than 20%, TiO2 4.8％～10％、B2O33.0 to 10% by mass of B in terms of oxide2O3/TiO2Is adjusted to a value of 0.63 to 3.33, and the glass obtained has a mass reduction rate of 4% or less after being immersed in 100ml of a 10% by mass aqueous NaOH solution at 80 ℃ for 90 hours.
13. The method for producing glass fibers according to claim 12, wherein the raw material batch is blended so that the difference between the spinning temperature and the liquidus temperature of the obtained glass becomes 115 ℃ or more.
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|---|---|---|---|
| JP2016-252648 | 2016-12-27 | ||
| JP2016252648A JP6959563B2 (en) | 2016-12-27 | 2016-12-27 | Glass composition for glass fiber, glass fiber and method for producing glass fiber |
| PCT/JP2017/041234 WO2018123327A1 (en) | 2016-12-27 | 2017-11-16 | Glass composition for glass fiber, glass fiber, and method for producing glass fiber |
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| CN109982982B true CN109982982B (en) | 2022-05-17 |
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| US11577990B2 (en) | 2017-12-05 | 2023-02-14 | Nippon Electric Glass Co., Ltd. | Glass fiber and method for producing same |
| CN112125528B (en) * | 2020-10-06 | 2021-09-10 | 滨州信泰节能科技有限公司 | High modulus glass fiber with excellent alkali resistance and preparation method thereof |
| CN112679096A (en) * | 2020-12-31 | 2021-04-20 | 山东天舜环保科技有限公司 | High-performance colored glass fiber and preparation method thereof |
| CN112679097B (en) * | 2021-03-12 | 2021-05-25 | 山东墨匠新材料科技有限公司 | High modulus glass fiber compositions based on lanthanide rare earth materials |
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| JP2018104237A (en) | 2018-07-05 |
| CN109982982A (en) | 2019-07-05 |
| WO2018123327A1 (en) | 2018-07-05 |
| JP6959563B2 (en) | 2021-11-02 |
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