CN111704361B - High-refractive-index high-performance glass fiber composition, glass fiber and composite material thereof - Google Patents
High-refractive-index high-performance glass fiber composition, glass fiber and composite material thereof Download PDFInfo
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- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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Abstract
The high-refractive-index high-performance glass fiber composition, the glass fiber and the composite material comprise 55.2 to 59.2 weight percent of SiO 2 (ii) a 11.6-15.6wt% of Al 2 O 3 (ii) a 21.5-23.3wt% CaO;0-0.5wt% MgO;3.5-5.9% of Y 2 O 3 +Bi 2 O 3 + BaO;3.5-4.9wt% of Y 2 O 3 (ii) a 0.1-0.9wt% of Bi 2 O 3 0.1 to 1.5wt% BaO;0-0.4wt% of TiO 2 (ii) a 0-0.3wt% Fe 2 O 3 ；Li 2 O、Na 2 O and K 2 The sum of the mass percent of O is 0.3-1.5wt%. The refractive index of the high-refractive-index high-performance glass fiber is 1.580-1.590, the high-refractive-index high-performance glass fiber has good matching property with the refractive index of polycarbonate resin, and the color is lighter; the high-refractive-index high-performance glass fiber impregnated yarn has tensile strength of more than 2600MPa, tensile modulus of more than 87GPa and good dimensional stability. The forming temperature of the high-refractive-index high-performance glass fiber is not more than 1210 ℃, and the upper limit temperature of crystallization is not more than 1150 ℃.
Description
Technical Field
The invention belongs to the technical field of modification of high polymer materials, and particularly relates to a high-refractive-index high-performance glass fiber composition, and glass fibers and a composite material thereof.
Background
The glass fiber is an inorganic non-metallic material with excellent performance, has the advantages of high tensile strength, high strength, good temperature resistance and corrosion resistance, heat insulation, sound insulation, non-combustion and the like, and is widely applied to various fields of electronics, electricity, automobiles, aviation, ships, environmental protection, chemical engineering, buildings and the like.
Polycarbonate (PC) is used as a thermoplastic resin, has good transparency, no toxicity, weather resistance, heat resistance, impact resistance, fatigue resistance and electrical performance, is a universal engineering plastic with the highest growth speed among the use frequencies of five engineering plastics, and is widely applied to the fields of office equipment such as glass assembly industry, automobile industry, electronics, electrical appliance industry, industrial mechanical parts, optical disks, packaging, computers and the like, medical treatment and health care, films, leisure and protective equipment and the like. With the further expansion of the application range of PC resin, in order to compensate the defect of insufficient mechanical strength, glass fiber is used to enhance the mechanical property and dimensional stability of PC resin. However, the refractive index of PC resin is higher, usually greater than 1.58, while the refractive index of ordinary glass fiber is usually 1.54-1.56, which are different from each other, if ordinary glass fiber is directly added, the light transmission of the product is reduced, and the light transmission of the product is reduced more obviously with the increase of the content of ordinary glass fiber.
In the development process of alkali-free glass fiber, the improvement of the mechanical properties of the glass fiber is considered, and the research on the improvement of the refractive index and the transparency of the glass fiber is not much.
Japanese patent laid-open No. 5-155638 discloses a glass fiber composition for reinforcing polycarbonate resin, which comprises (by weight): siO 2 2 54-62％，Al 2 O 3 8-12％，CaO 18-22％，TiO 2 0.5-1.9％，MgO 0-5％，ZnO 0-5％，BaO 0-5％，ZrO 2 0.6-5％，Li 2 O+Na 2 O+K 2 O0-1%, the refractive index of the glass fiber is 1.5700-1.6000, and 0.5-1.9% TiO is added 2 Although the refractive index of the glass fiber can be increased, tiO is used as the refractive index 2 The content of more than 0.5% causes the glass fiber product to have light yellow and low transparency.
Chinese patent CN200580015038.5 discloses a glass fiber for reinforcing polycarbonate resin, which comprises B 2 O 3 And no B 2 O 3 Two types. Wherein contains B 2 O 3 The glass fiber component comprises (by weight percent): siO 2 2 50-60％，Al 2 O 3 10-15％，CaO 15-25％，TiO 2 2-10％，B 2 O 3 2-8％，MgO 0-5％，ZnO 0-5％，BaO 0-5％，ZrO 2 0-5％，Li 2 O+Na 2 O+K 2 O0-2%, and the refractive index of the glass fiber is 1.580-1.590. Does not contain B 2 O 3 The glass fiber component comprises (by weight percent): siO 2 2 50-60％，Al 2 O 3 10-15％，CaO 15-25％，TiO 2 4.1-5％，MgO 0-5％，ZnO 0-5％，BaO 0-5％，ZrO 2 0-5％，Li 2 O+Na 2 O+K 2 O 0-2％，ZnO+Y 2 O 3 1-5％，TiO 2 +ZnO+BaO+ZrO 2 6-8%, the refractive index of the glass fiber is 1.583-1586, but TiO 2 The content is obviously higher, so that the glass fiber product is bright yellow and the transparency is seriously influenced.
Chinese patent CN200910002941.8 discloses a similar glass fiber for reinforcing polycarbonate resin, which comprises the following main components (by weight percent): siO 2 2 50-60％，Al 2 O 3 10-15％，CaO 15-25％，TiO 2 3-5％，MgO 0-5％，ZnO 0-5％，BaO 0-5％，ZrO 2 0-5％，Li 2 O+Na 2 O+K 2 O 0-2％，ZrO 2 2-5%, the refractive index of the glass fiber can reach 1.583-1.586, although the refractive index of the glass fiber can be improved, the use amount of TiO2 is more, so that the color of a glass product is obviously yellow, the production difficulty is large, and the application range of the glass product is limited.
Disclosure of Invention
The invention provides a high-refractive-index high-performance glass fiber composition, a glass fiber and a composite material thereof, which have the advantages of high refractive index, excellent mechanical property and very good light transmittance, and can be widely applied to the field with high requirements on mechanical property and transparency.
The technical scheme of the invention is as follows:
the high-refractive-index high-performance glass fiber composition comprises the following components in percentage by mass:
wherein, Y is 2 O 3 The mass percentage of the TiO is 3.5-4.9wt percent 2 、Na 2 O、K 2 O is introduced as an impurity, not separately added, and the Li 2 O、Na 2 O、K 2 The sum of the mass percentage of O is not more than 1.5wt percent.
Preferably, Y is 2 O 3 、Bi 2 O 3 The sum of the mass percent of BaO is 3.5-5.9wt percent, wherein the Bi is 2 O 3 The content of (b) is 0.1-0.9wt%, wherein the content of BaO is 0.1-1.5wt%.
Preferably, said TiO is introduced as an impurity 2 The mass percentage of the components is controlled to be 0-0.4wt%.
Preferably, the Fe 2 O 3 The mass percentage of the components is controlled to be 0-0.3wt%.
Preferably, the Li 2 O、Na 2 O、K 2 The mass percentage of O is controlled to be 0.3-1.5wt%
Preferably, the SiO 2 The mass percentage of the components is controlled to be 55.2-59.2wt%.
Preferably, the Al is 2 O 3 The mass percentage content of the components is controlled to be 11.6-15.6wt percent,
preferably, the weight percentage of CaO is controlled to be 21.5-23.3wt%.
Preferably, the MgO content is controlled to 0-0.5wt%.
The content of each component of the high-refractive-index high-performance glass fiber composition is preferably as follows in percentage by mass:
wherein, Y is 2 O 3 Is 3.5 to 4.9 weight percent, and the Bi 2 O 3 The mass percentage of the BaO is 0.1-0.9wt%, wherein the mass percentage of the BaO is 0.1-1.5wt%.
The high-refractive-index high-performance glass fiber is prepared from the high-refractive-index high-performance glass fiber composition, and the refractive index of the high-refractive-index high-performance glass fiber is 1.580-1.590.
A high-refractive-index high-performance glass fiber reinforced composite material comprises the high-refractive-index high-performance glass fiber.
In the present invention, silica (SiO) 2 ) Formed of glass network structuresOne of the main oxides, which mainly serves to improve the mechanical strength, chemical stability and thermal stability of the glass. In a certain range, siO in glass 2 The higher the content, the better the mechanical strength of the glass, but the higher the melting temperature and fiber forming temperature of the glass, the greater the production difficulty. Taken together, the SiO of the present invention 2 The mass percentage content is 55-60wt%, preferably 55.2-59.2wt%.
In the present invention, alumina (Al) 2 O 3 ) With SiO 2 The glass and the Al jointly form a glass network structure, the higher the content of the glass is, the more excellent the mechanical strength, particularly the elastic modulus of the glass is, but the high-temperature viscosity of the glass is obviously increased, and the Al generally 2 O 3 When the content exceeds 16%, the viscosity of the glass becomes too high, the glass is difficult to be formed into fibers, and the problem of devitrification is liable to occur. Thus, al according to the invention 2 O 3 The content is 10 to 16wt%, preferably 11.6 to 15.6wt%.
In the invention, calcium oxide (CaO) and magnesium oxide (MgO) both belong to alkaline earth metal oxides and have the functions of adjusting the high-temperature viscosity of the glass and improving the crystallization tendency of the glass, but the atomic weight and the ionic radius of Ca are larger relative to Mg and Ca, so that the effect of improving the refractive index of the glass is more obvious. Meanwhile, in the alkali-free glass system, the total content of CaO and MgO is generally not more than 25%, preferably less than 24%. The invention is preferably to add CaO selectively in order to ensure a higher refractive index, mgO is generally not added specifically, but in view of the cost of the mineral raw material, the invention allows the introduction of a small amount of MgO in the form of a mineral raw material impurity. Experiments prove that the comprehensive effect is best when the CaO content is controlled to be 20-24wt% and the MgO content is controlled to be 0-1.5 wt%. The preferable mass percentage of CaO is 21.5-23.3wt%, and the preferable mass percentage of MgO is 0-0.5wt%.
The glass fiber of the invention is specially added with yttrium oxide (Y) 2 O 3 ) May further contain Bi 2 O 3 And BaO. Y is 2 O 3 、Bi 2 O 3 BaO and BaO both belong to elements with larger atomic radius and atomic mass, and have the effects of reducing the high-temperature viscosity of the glass and improving the refractive index of the glass in the glass. Experiments also find thatWhen one of the substances is added alone, Y 2 O 3 The effect is obviously better than that of Bi 2 O 3 And BaO; when two or three substances are added simultaneously, a synergistic effect can be generated, the adjustment range of the refractive index is optimized, the crystallization tendency is reduced, and the difficulty of wire drawing operation is improved. Y in the glass fiber of the present invention 2 O 3 +Bi 2 O 3 The mass percentage of BaO is 3.1-6.9%; preferably 3.5 to 5.9wt%. Among them, more preferred among the glass fibers of the present invention, Y 2 O 3 3.5 to 4.9 weight percent of Bi 2 O 3 The mass percentage content is 0.1-0.9wt%, and the mass percentage content of BaO is 0.1-1.5wt%.
In glass, titanium dioxide (TiO) 2 ) The effect of improving the refractive index is very obvious, and a plurality of glasses with higher refractive index contain higher TiO 2 But at the same time TiO 2 There is also a pronounced coloring effect, with the glass appearing yellowish when its content exceeds 0.5% by weight and already appearing very distinctly bright yellow when its content exceeds 1% by weight. Therefore, the present invention does not substantially contain TiO 2 However, to reduce the cost of the raw material, the present invention allows the introduction of small amounts of TiO in the form of impurities in the mineral raw material 2 . To avoid impurity TiO 2 Effect on glass color, tiO in the glass fibers of the invention 2 The mass percentage content is limited to 0-1 wt.%, preferably 0-0.4 wt.%.
In the glass fiber, a small amount of Fe 2 O 3 The performance is not greatly affected, but if the content is higher, the glass is yellowed or greened. Typically to reduce the cost of the mineral feedstock, small amounts of incorporation are generally permitted. In the present invention, fe 2 O 3 It is introduced mainly as a mineral raw material impurity without special addition. However, in order to control the color of the glass, fe is contained in the glass fiber of the present invention 2 O 3 The mass percentage content is limited to 0-0.6 wt.%, preferably 0-0.3 wt.%.
In order to reduce the melting temperature of the glass fiber and improve the fiber forming difficulty, a small amount of Li can be added into the glass fiber 2 O, the mass percent content of which is 0-1wt%. The glass fiber of the invention also contains a small amount of alkali metal oxideSubstance Na 2 O and K 2 O, which also helps to reduce the difficulty of glass fiber production. Na in the glass composition of the present invention 2 O and K 2 The total content of O is controlled between 0 and 0.8 weight percent. Meanwhile, the Li 2 O、Na 2 O and K 2 The sum of the O contents by mass is preferably 0.3 to 1.5wt%.
In the present invention, a preferred embodiment of the glass fiber is: 55.2-59.2wt% SiO 2 (ii) a 11.6-15.6wt% of Al 2 O 3 (ii) a 21.5-23.3wt% CaO;0-0.5wt% MgO;3.5-5.9% of Y 2 O 3 +Bi 2 O 3 + BaO;3.5-4.9wt% of Y 2 O 3 (ii) a 0.1-0.9wt% of Bi 2 O 3 0.1 to 1.5wt% BaO;0-0.4wt% TiO 2 (ii) a 0-0.3wt% Fe 2 O 3 ；
Li 2 O、Na 2 O and K 2 The sum of the mass percent of O is 0.3-1.5wt%. The refractive index of the glass fiber is 1.580-1.590, the glass fiber has good matching property with the refractive index of polycarbonate resin, and the color is lighter; the glass fiber impregnated yarn has tensile strength of more than 2600MPa, tensile modulus of more than 87GPa and good dimensional stability. The glass fiber forming temperature is not more than 1210 ℃, and the upper limit temperature of crystallization is not more than 1150 ℃.
The method for preparing the glass fiber is not particularly limited, and the glass fiber can be prepared by a tank furnace method or an electric melting furnace method which are well known to those skilled in the art.
The tank furnace method or the electric melting furnace method specifically comprises the following steps: calculating the required raw material adding proportion according to the actual formula of the glass; quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain qualified batch; conveying the batch to a kiln head bin of the tank furnace or the electric melting furnace, and delivering the batch to the tank furnace or the electric melting furnace by a feeder at a constant speed; heating the batch materials at 1300-1500 ℃ in a tank furnace, melting, clarifying and homogenizing to form qualified molten glass; cooling the molten glass to the molding temperature through the operation channel, and then flowing out through a platinum bushing to form glass filaments; rapidly drawing the glass fiber into glass fiber with a set diameter under the high-speed traction of a wire drawing machine, and winding the glass fiber into a spinning cake by the wire drawing machine after spray cooling, impregnating compound coating and beam collecting; and then on a short cutting production line, cutting the silk cake into short strands with required length, and drying, granulating, sieving and the like to obtain the short glass fiber yarn.
Compared with the prior art, the invention has the advantages that:
1. the high-refractive-index high-performance glass fiber composition disclosed by the invention can reduce TiO to the maximum extent on the basis of ensuring that the refractive index of a glass fiber product is maintained at 1.580-1.590 2 In an amount of, or even not including, tiO 2 Therefore, the prepared high-refractive-index high-performance glass fiber has excellent transparency, and the composite material reinforced by the high-refractive-index high-performance glass fiber also has good transparency, particularly the glass fiber reinforced PC composite material, and the high-refractive-index high-performance glass fiber does not influence the natural color of PC resin, so that the high-refractive-index high-performance glass fiber can be widely applied to occasions with high requirements on color, particularly transparency.
2. The high-refractive-index high-performance glass fiber prepared from the high-refractive-index high-performance glass fiber composition has good mechanical properties, the tensile strength of the dipped yarn is as high as 2600MPa or more, and the tensile modulus is as high as 87GPa or more, so that the glass fiber reinforced composite material, particularly the glass fiber reinforced PC composite material, can be kept more favorably in structural strength and dimensional stability.
3. The high-refractive-index high-performance glass fiber composition has good fiber forming performance when being used for preparing high-refractive-index high-performance glass fibers, the forming temperature is not more than 1210 ℃, the upper limit temperature of crystallization is not more than 1150 ℃, the production difficulty is equivalent to that of general boron-free and fluorine-free alkali-free glass fibers, the preparation method of the glass fibers is not specially limited, the glass fibers can be prepared according to a tank furnace method or an electric melting furnace method well known by the technical personnel in the field, and the large-scale production can be realized under the existing tank furnace process condition.
Detailed Description
In order to facilitate understanding of the present invention, the present invention will be described in more detail below with reference to specific examples and comparative examples.
In the embodiment and the comparative example of the invention, the high-temperature viscosity of the glass fiber is detected by a BROOKFIELD high-temperature viscometer produced by ORTON company; the glass liquidus temperature is detected by an Orton Model gradient furnace; the refractive index of the glass fiber is measured by GB/T7962.1-2010 standard, and the tensile modulus is measured by ASTM D2343-03 standard.
Wherein T is logη＝3 The temperature at which the glass viscosity is 1000 poise corresponds to the temperature of the glass melt at the time of glass fiber molding, and is also referred to as the glass "glass fiber molding temperature".
T Liquid for treating urinary tract infection The liquidus temperature of glass is represented by a temperature at which the glass crystallization rate is 0, i.e., an upper limit of glass crystallization temperature, and is also referred to as "glass fiber crystallization temperature".
And the components of the compounds in the examples 1-21 are the components of the glass formula, and the components of the compounds in the comparative examples 1 and 2 refer to pages 53-54 of the book of glass fiber and mineral wool, and the numerical values are weight percentages. Because of detection errors, trace impurities which are not analyzed and counted, decimal place values and other factors, the total percentage content of the components in the table may not be completely 100%.
Example 1
By mass percent, 60wt% of SiO 2 10.8wt% of Al 2 O 3 22.4wt% CaO,0.3wt% MgO,0.3wt% TiO 2 4.0wt% of Y 2 O 3 0.3wt% of BaO,0.7wt% of Bi 2 O 3 0.4wt% of Li 2 O,0.7wt% of Na 2 O+K 2 O,0.1wt% Fe 2 O 3 Calculating the addition proportion of the required raw materials according to the formula, quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain a qualified batch; conveying the batch to a kiln head bin of the tank furnace, and delivering the batch to the tank furnace by a feeder at a constant speed; heating the batch at 1300-1500 ℃, melting, clarifying and homogenizing in a tank furnace to form qualified high-refractive-index high-performance glass melt 1; cooling the high-refractive-index high-performance glass melt 1 to the molding temperature through an operation channel, and then flowing out through a platinum bushing to form a high-refractive-index high-performance glass wire 1; the glass fiber 1 is drawn rapidly under the high speed of the wire drawing machineRapidly drawing the glass fiber into high-refractive-index high-performance glass fiber 1 with a set diameter (13 +/-1 um), spraying and cooling, coating a sizing agent, and winding the fiber into a high-refractive-index high-performance spinning cake 1 by a wire drawing machine after collecting; and then on a short cutting production line, cutting the high-refractive-index high-performance spinning cake into short strands with required length, and carrying out the working procedures of drying, granulating, sieving and the like to obtain the high-refractive-index high-performance chopped glass fiber yarn 1.
The test shows that the forming temperature T of the high-refractivity high-performance glass fiber 1 logη＝3 The upper limit of the crystallization temperature T of the molten glass 1 is 1205 DEG C Liquid for treating urinary tract infection 1114 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn 1 was 1.582, and the tensile modulus was 87.0GPa.
Example 2
By mass percent, 59.2wt% of SiO 2 11.6wt% of Al 2 O 3 22.4wt% CaO,0.3wt% MgO,0.3wt% TiO 2 4.0wt% of Y 2 O 3 0.3wt% of BaO,0.7wt% of Bi 2 O 3 0.4wt% of Li 2 O,0.7wt% of Na 2 O+K 2 O,0.1wt% Fe 2 O 3 Calculating the addition proportion of the required raw materials according to the formula, quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain a qualified batch; conveying the batch to a kiln head bin of the tank furnace, and delivering the batch to the tank furnace by a feeder at a constant speed; heating the batch at 1300-1500 ℃, melting, clarifying and homogenizing in a tank furnace to form qualified high-refractive-index high-performance glass liquid 2; the high-refractive-index high-performance glass liquid 2 is cooled to the molding temperature through the operation channel and then flows out through the platinum bushing to form a high-refractive-index high-performance glass wire 2; the glass fiber 2 is rapidly drawn into high-refractive index high-performance glass fiber 2 with a set diameter (13 +/-1 um) under the high-speed traction of a drawing machine, and is wound into a high-refractive index high-performance spinning cake 2 by the drawing machine after being subjected to spray cooling, impregnating compound coating and bundling; and then on a short cutting production line, cutting the high-refractive-index high-performance spinning cake 2 into short strands with required length, and carrying out the working procedures of drying, granulating, sieving and the like to obtain the high-refractive-index high-performance chopped glass fiber yarn 2.
Tested, high foldingShaping temperature T of high-refractive-index glass fiber 2 logη＝3 1201 ℃ and the upper limit of the crystallization temperature T of the molten glass Liquid for medical purpose The glass fiber strand had a refractive index nD/20 ℃ of 1.583 and a tensile modulus of 87.4GPa at 1119 ℃ in the chopped glass fiber strand 2.
Example 3
57.2wt% of SiO 2 13.6wt% Al 2 O 3 22.4wt% CaO,0.3wt% MgO,0.3wt% TiO 2 4.0wt% of Y 2 O 3 0.3wt% of BaO,0.7wt% of Bi 2 O 3 0.4wt% of Li 2 O,0.7wt% of Na 2 O+K 2 O,0.1wt% Fe 2 O 3 Calculating the addition proportion of the required raw materials according to the formula, quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain a qualified batch; conveying the batch to a kiln head bin of the tank furnace, and delivering the batch to the tank furnace by a feeder at a constant speed; heating the batch at 1300-1500 ℃, melting, clarifying and homogenizing in a tank furnace to form qualified high-refractive-index high-performance glass liquid 3; the high-refractive-index high-performance glass liquid 3 is cooled to the molding temperature through the operation channel and then flows out through a platinum bushing to form a high-refractive-index high-performance glass wire 3; the glass fiber 3 is rapidly drawn into high-refractive index high-performance glass fiber 3 with a set diameter (13 +/-1 um) under the high-speed traction of a drawing machine, and is wound into a high-refractive index high-performance spinning cake 3 by the drawing machine after being subjected to spray cooling, impregnating compound coating and bundling; then on a short cutting production line, the high-refractive-index high-performance spinning cake 3 is cut into short strands with required length, and the high-refractive-index high-performance short glass fiber yarn 3 is obtained after the procedures of drying, granulating, sieving and the like.
The test shows that the forming temperature T of the glass fiber 3 with high refractive index and high performance logη＝3 1194 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for medical purpose 1127 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn 3 was 1.586, and the tensile modulus was 88.4GPa.
Example 4
The difference from example 3 is that SiO is added in mass percent 2 The amount of Al added was changed to 55.2wt%, based on the total weight of Al 2 O 3 The amount of addition was changed to 15.6wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1186 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The glass fiber yarn had a refractive index nD/20 ℃ of 1.585 of 1134 ℃ and a tensile modulus of 88.5GPa.
Examples 1 to 4 above are for SiO 2 And Al 2 O 3 The variation range of (A) is verified through experiments, and the test results are analyzed to show that the variation range of (A) is consistent with SiO 2 Improved component content, high refractive index and high performance glass fiber forming temperature T logη＝3 Also higher, and Al 2 O 3 The higher the content of the component (A), the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The higher the glass modulus, the less the glass refractive index is affected and the slightly increased.
Example 5
The difference from example 3 is that SiO is added in mass percent 2 The amount of Al added was changed to 58.2wt%, based on the total weight of Al 2 O 3 The amount of CaO added was changed to 14.4wt%, and the amount of CaO added was changed to 20.6wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1198 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The glass chopped strand had a refractive index nD/20 ℃ of 1.573 and a tensile modulus of 88.3GPa at 1132 ℃.
Example 6
The difference from example 3 is that SiO is added in mass percent 2 The amount of addition of (B) was changed to 57.7wt%, and Al was added 2 O 3 The amount of CaO added was changed to 14wt%, and the amount of CaO added was changed to 21.5wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1196 ℃ and the upper limit of the crystallization temperature T of the molten glass Liquid for treating urinary tract infection 1130 ℃ C., the refractive index nD/20 ℃ C. Of the chopped glass fiber yarn was 1.580, and the tensile modulus was 88.3GPa.
Example 7
The difference from example 3 is that SiO is added in mass percent 2 Is added in an amount ofChanged to 56.8wt% and Al 2 O 3 The amount of CaO added was changed to 13.2wt%, and the amount of CaO added was changed to 23.3wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1191 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection 1128 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn was 1.586, and the tensile modulus was 88.2GPa.
Example 8
The difference from example 3 is that SiO is added in mass percent 2 The amount of Al added was changed to 56.4wt%, based on the total weight of Al 2 O 3 The amount of CaO added was changed to 12.9wt%, and the amount of CaO added was changed to 24wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1188 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection 1128 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn is 1.587, and the tensile modulus is 87.9GPa.
Examples 5 to 8 were conducted based on example 3, and the influence of the preferable CaO content range on the refractive index was examined, and the refractive index of the high-refractive-index, high-performance glass fiber was improved with the increase of the CaO content, and the refractive index of the high-refractive-index, high-performance glass fiber was also improved with the increase of SiO content 2 And Al 2 O 3 Reduced total amount, high refractive index and high performance glass fiber forming temperature T logη＝3 And the tensile modulus decreases.
Example 9
The difference from example 3 is that SiO is added in mass percent 2 The amount of MgO added was changed to 57.5wt%, and the amount of MgO added was changed to 0.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1194 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection 1125 ℃ and the refractive index nD/20 ℃ of the chopped glass fiber yarn was 1.585, and the tensile modulus was 88.1GPa.
Example 10
The difference from example 3 is that SiO is added in mass percent 2 The amount of MgO added was changed to 56.6wt%, and the amount of MgO added was changed to 0.9wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1190 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection At 1130 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn was 1.585, and the tensile modulus was 88.0GPa.
Example 11
The difference from example 3 is that SiO is added in mass percent 2 The amount of MgO added was changed to 56.0wt%, and the amount of MgO added was changed to 1.5wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1187 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The glass fiber yarn had a refractive index nD/20 ℃ of 1.585 and a tensile modulus of 87.9GPa at 1132 ℃.
Examples 9 to 11 were conducted based on example 3 to verify the variation range of MgO content, and it was not possible to replace CaO with MgO, which replaced part of SiO in this experiment, since it was necessary to ensure the refractive index of high-refractive index high-performance glass fiber 2 . In general, small amounts of MgO do not have a significant effect on the properties, but too high a content can lead to SiO 2 The content is low, so that the molding temperature is reduced, and the molding interval (T) is logη＝3 -T Liquid for treating urinary tract infection ) And the size is reduced, which is not beneficial to the stable drawing of the high-refractivity high-performance glass fiber.
Example 12
The difference from example 3 is that Li is added in mass percent 2 The addition of O is changed to 0wt%, and the corresponding SiO 2 In an amount of 57.6wt%, na 2 O+K 2 The amount of O added was 0.7wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 At 1201 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The melt index nD/20 ℃ of the chopped glass fiber yarn was 1.556, and the tensile modulus was 87.9GPa, at 1126 ℃.
Example 13
The difference from example 3 is that Li is added in mass percent 2 The addition of O was changed to 1.0wt%, corresponding to SiO 2 In an amount of 56.8wt%, na 2 O+K 2 Addition amount of OIs 0.5wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1185 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection 1125 ℃ and 1.584 for the refractive index nD/20 ℃ of the chopped glass fiber yarn, and 87.9GPa for the tensile modulus.
Example 14
The difference from example 3 is that Li is added in mass percent 2 The addition of O was changed to 1.5wt% corresponding to SiO 2 In an amount of 56.3wt%, na 2 O+K 2 The amount of O added was 0.5wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1179 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The melt index nD/20 ℃ of the chopped glass fiber yarn was 1.583, and the tensile modulus was 87.5GPa, at 1126 ℃.
Examples 12 to 14 were conducted on the basis of example 3 to verify Li 2 The content of O varies within a range where a small amount of Li is observed 2 O pairs for lowering glass forming temperature T logη＝3 The effect is obvious, and the influence on other properties is not great. However, if the content is too high, the molding temperature may be lowered too low, resulting in a molding interval (T) logη＝3 -T Liquid for treating urinary tract infection ) Too small, is not favorable for the stable wire drawing of the glass fiber.
Example 15
The difference from example 3 is that the amount of BaO added was changed to 0.1wt% in terms of mass%, corresponding to SiO 2 The amount of (B) was 58.1wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 The upper limit T of the crystallization temperature of the molten glass is 1200 DEG C Liquid for treating urinary tract infection 1128 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn was 1.580, and the tensile modulus was 88.2GPa.
Example 16
The difference from example 3 is that the amount of BaO added was changed to 1.5wt% in terms of mass%, corresponding to SiO 2 The amount of (B) was 56.4wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1188 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection 1129 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn is 1.587, and the tensile modulus is 88.1GPa.
Examples 15 to 16 were conducted by examining the range of variation of the BaO content on the basis of example 3, and it can be seen that the crystallization temperature T can be lowered by adding a small amount of BaO Liquid for treating urinary tract infection Increasing the molding interval (T) logη＝3 -T Liquid for treating urinary tract infection ) And has certain positive effect on the refractive index and the elastic modulus of the glass.
Example 17
The difference from example 3 is that Bi is added in mass percent 2 O 3 The addition amount of (A) was changed to 0.6wt%, corresponding to SiO 2 The amount of (B) was 56.9wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1192 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for medical purpose 1125 ℃ and the refractive index nD/20 ℃ of the chopped glass fiber yarn was 1.585, and the tensile modulus was 88.2GPa.
Example 18
The difference from example 3 is that Bi is added in mass percent 2 O 3 The addition amount of (b) is changed to 0.9wt%, corresponding to SiO 2 The amount of (B) was 56.6wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1190 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The glass fiber yarn had a refractive index nD/20 ℃ of 1.586 and a tensile modulus of 88.2GPa at 1124 ℃.
Examples 17 to 18 were conducted to verify Bi based on example 3 2 O 3 In the content range of (B), it can be seen that a small amount of Bi acts similarly to BaO 2 O 3 It also has the functions of reducing crystallization temperature and enlarging forming interval. However, baO and Bi 2 O 3 If the amount is too high, not only the cost is increased, but also adverse effects may occur.
Example 19
The difference from example 3 is that Y is calculated by mass percentage 2 O 3 The addition amount of (B) was changed to 4.9wt%,corresponding SiO 2 The amount of (B) was 56.3wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1191 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The glass fiber was 1132 ℃ C., the refractive index nD/20 ℃ C. Of the chopped glass fiber yarn was 1.590, and the tensile modulus was 88.9GPa.
Example 20
The difference from example 3 is that Y is calculated by mass percentage 2 O 3 The addition amount of (b) was changed to 4.5wt%, corresponding to SiO 2 The amount of (B) added was 56.7wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1192 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection The resultant was 1129 ℃, and the chopped glass fiber yarn had a refractive index nD/20 ℃ of 1.588 and a tensile modulus of 88.7GPa.
Example 21
The difference from example 3 is that Y is calculated by mass percentage 2 O 3 The addition amount of (b) was changed to 3.5wt%, corresponding to SiO 2 The amount of (B) was 57.7wt%.
The test shows that the forming temperature T of the glass fiber with high refractive index and high performance logη＝3 1198 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for treating urinary tract infection 1125 ℃ and the refractive index nD/20 ℃ of the chopped glass fiber yarn was 1.580, and the tensile modulus was 87.7GPa.
Examples 19 to 21 were carried out to verify Y on the basis of example 3 2 O 3 The content of (3) is within the range, and analysis shows that Y is increased 2 O 3 The content, the refractive index and the elastic modulus of the glass fiber are obviously increased, and the crystallization temperature is increased along with the increase of the content, the refractive index and the elastic modulus of the glass fiber, because of SiO 2 The content is relatively reduced, and the forming temperature is also reduced. So if Y continues to be increased 2 O 3 Content, on the one hand, increased cost, over-standard refractive index, and on the other hand, the molding window (T) logη＝3 -T Liquid for treating urinary tract infection ) Too small, which is not conducive to wire drawing production.
Comparative example 1
54.4 percent by weight of SiO 2 14.9 wt.% Al 2 O 3 16.6wt% CaO,4.6wt% MgO, trace TiO 2 ，<0.5wt% of Na 2 O+K 2 O，<0.5wt% Fe 2 O 3 8.5wt% of B and 0.3wt% of F, calculating the addition proportion of the required raw materials according to the formula, quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain qualified batch; conveying the batch to a kiln head bin of the tank furnace, and delivering the batch to the tank furnace by a feeder at a constant speed; heating the batch materials at 1300-1500 ℃ in a tank furnace, melting, clarifying and homogenizing to form qualified molten glass; cooling the molten glass to the molding temperature through the operation channel, and then flowing out through a platinum bushing to form glass filaments; rapidly drawing the glass fiber into glass fiber with a set diameter (13 +/-1 um) under the high-speed traction of a wire drawing machine, and winding the glass fiber into a spinning cake by the wire drawing machine after spray cooling, impregnating compound coating and bundling; and then on a short cutting production line, cutting the silk cake into short strands with required length, and drying, granulating, sieving and the like to obtain the common short glass fiber yarn.
The test shows that the forming temperature T of the glass fiber logη＝3 1214 ℃ and the upper limit T of the crystallization temperature of the molten glass Liquid for medical purpose The glass fiber yarn had a refractive index nD/20 ℃ of 1.545 and a tensile modulus of 81.9GPa at 1135 ℃.
Comparative example 2
58.0wt% of SiO by mass percentage 2 11.2wt% of Al 2 O 3 22wt% CaO,2.7wt% MgO,<2.2wt% TiO 2 0.5wt% of Na 2 O+K 2 O,0.3wt% Fe 2 O 3 Calculating the adding proportion of the required raw materials according to the formula, quantitatively conveying various raw materials to a mixing bin according to the proportion, and fully and uniformly mixing to obtain qualified batch; conveying the batch to a kiln head bin of the tank furnace, and delivering the batch to the tank furnace by a feeder at a constant speed; heating the batch materials at 1300-1500 ℃ in a tank furnace, melting, clarifying and homogenizing to form qualified molten glass; cooling the molten glass to the molding temperature through the operation channel, and then flowing out through a platinum bushing to form glass filaments; the glass fiber is drawn into a set straight line rapidly under the high-speed traction of a wire drawing machineGlass fiber with diameter of 13 +/-1 um is sprayed, cooled, coated with impregnating compound and collected to be wound into a spinning cake by a wire drawing machine; and then on a short cutting production line, cutting the silk cake into short strands with required length, and drying, granulating, sieving and the like to obtain the common short glass fiber yarn.
The test shows that the forming temperature T of the glass fiber logη＝3 1261 deg.C, upper limit of crystallization temperature T of molten glass Liquid for treating urinary tract infection 1173 ℃, the refractive index nD/20 ℃ of the chopped glass fiber yarn is 1.579, and the tensile modulus is 83.1GPa.
Table 1 below is a summary of the ingredients and properties of examples 1-20 of the present invention and comparative examples 1-2.
The present invention can be used for reinforcing transparent PC resins, and also for reinforcing transparent Polyamide (PA) resins having a refractive index of about 1.57 to 1.59.
The glass fiber composition according to the present invention can be combined with one or more organic and/or inorganic materials, which may include thermosetting resins such as epoxy resins, unsaturated polyesters, vinyl resins, etc., and thermoplastic resins such as Polycarbonate (PC), polypropylene (PP), polyamide (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), etc., to produce a composite material having excellent properties.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The high-refractive-index high-performance glass fiber composition is characterized by comprising the following components in percentage by mass:
wherein, Y is 2 O 3 The mass percentage of the TiO is 3.5-4.9wt percent 2 、Na 2 O、K 2 O is introduced as an impurity, not separately added, and the Li 2 O、Na 2 O、K 2 The sum of the mass percent of O is not more than 1.5wt%; wherein said Bi 2 O 3 The content of (b) is 0.1-0.9wt%, wherein the content of BaO is 0.1-1.5wt%.
2. The high index high performance glass fiber composition of claim 1, wherein the TiO is introduced as an impurity 2 The mass percentage of the components is controlled to be 0-0.4wt%.
3. The high index, high performance glass fiber composition of claim 1, wherein the Fe is 2 O 3 The mass percentage of the components is controlled to be 0-0.3wt%.
4. The high index high performance glass fiber composition of claim 1, wherein the Li is Li 2 O、Na 2 O、K 2 The mass percentage of O should be controlled between 0.3 and 1.5wt percent.
5. The high index high performance glass fiber composition of claim 1, wherein the SiO 2 The mass percentage of the components is controlled to be 55.2-59.2wt%.
6. The high index, high performance glass fiber composition of claim 1, wherein said Al is 2 O 3 The mass percentage of the components is controlled to be 11.6-15.6wt%.
7. The composition of claim 1, wherein the CaO is present in an amount of 21.5 to 23.3wt%.
8. The composition of claim 1, wherein the MgO is contained in an amount of 0 to 0.5wt%.
9. A high refractive index high performance glass fiber made from the high refractive index high performance glass fiber composition of any one of claims 1 to 8, wherein the high refractive index high performance glass fiber has a refractive index of 1.580 to 1.590.
10. A high refractive index high performance glass fiber reinforced composite comprising the high refractive index high performance glass fiber of claim 9.
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