WO2016165506A2 - 一种高模量玻璃纤维组合物及其玻璃纤维和复合材料 - Google Patents

一种高模量玻璃纤维组合物及其玻璃纤维和复合材料 Download PDF

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WO2016165506A2
WO2016165506A2 PCT/CN2016/075780 CN2016075780W WO2016165506A2 WO 2016165506 A2 WO2016165506 A2 WO 2016165506A2 CN 2016075780 W CN2016075780 W CN 2016075780W WO 2016165506 A2 WO2016165506 A2 WO 2016165506A2
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Prior art keywords
glass fiber
weight percentage
glass
content
fiber composition
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PCT/CN2016/075780
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English (en)
French (fr)
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WO2016165506A3 (zh
Inventor
章林
曹国荣
张毓强
邢文忠
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巨石集团有限公司
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Priority to PL16779481.7T priority Critical patent/PL3406575T3/pl
Priority to CA2989224A priority patent/CA2989224C/en
Application filed by 巨石集团有限公司 filed Critical 巨石集团有限公司
Priority to JP2017564678A priority patent/JP6662915B2/ja
Priority to MX2017016243A priority patent/MX2017016243A/es
Priority to AU2016248179A priority patent/AU2016248179B2/en
Priority to KR1020177036413A priority patent/KR102001760B1/ko
Priority to US15/738,563 priority patent/US10239781B2/en
Priority to RU2018117536A priority patent/RU2728618C2/ru
Priority to MA42576A priority patent/MA42576B1/fr
Priority to BR112017027039-0A priority patent/BR112017027039B1/pt
Priority to MYPI2018703022A priority patent/MY192699A/en
Priority to ES16779481T priority patent/ES2979116T3/es
Priority to EP24167719.4A priority patent/EP4371954A2/en
Priority to HRP20240680TT priority patent/HRP20240680T1/hr
Priority to EP16779481.7A priority patent/EP3406575B1/en
Publication of WO2016165506A2 publication Critical patent/WO2016165506A2/zh
Publication of WO2016165506A3 publication Critical patent/WO2016165506A3/zh
Priority to ZA2018/03114A priority patent/ZA201803114B/en
Priority to SA518391620A priority patent/SA518391620B1/ar
Priority to US16/269,379 priority patent/US10696581B2/en

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Classifications

    • 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
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045—Silica-containing oxide glass compositions
    • C03C13/046—Multicomponent glass compositions
    • 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
    • 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
    • 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
    • C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
    • 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
    • C03C2213/00—Glass fibres or filaments

Definitions

  • the present invention relates to a high modulus glass fiber composition, and more particularly to a high modulus glass fiber composition capable of reinforcing a substrate as an advanced composite material, and glass fibers and composite materials thereof.
  • Glass fiber is an inorganic fiber material, and it can be used to reinforce a resin to obtain a composite material with excellent properties.
  • high modulus glass fiber was originally used in the fields of defense, military and other defense industries. With the advancement of technology and economic development, high modulus glass fiber has been widely used in civil industry such as wind blades, high pressure vessels, marine pipelines, and automobile manufacturing.
  • the earliest high-modulus glass component is mainly composed of MgO-Al 2 O 3 -SiO 2 system.
  • the typical scheme is S-2 glass developed by American OC Company.
  • the modulus is 89-90 GPa, but its production is too difficult.
  • the glass fiber molding temperature is as high as 1571 ° C, and the liquidus temperature is as high as 1470 ° C. It is difficult to achieve large-scale pool kiln production. Therefore, OC Company voluntarily gave up the production of S-2 fiberglass and transferred its patent rights to AGY Company of the United States.
  • OC also developed HiPer-tex glass with a modulus of 87-89 GPa, which is a compromise strategy at the expense of some glass properties to reduce production difficulty, but since the design is only a simple improvement of S-2 glass, The glass fiber forming temperature and liquidus temperature are still high, and the production difficulty is still very large, and it is difficult to realize large-scale pool kiln production. Therefore, OC also abandoned the production of HiPer-tex fiberglass and transferred its patent to European 3B.
  • France Saint-Gobain has developed an R glass based on the MgO-CaO-Al 2 O 3 -SiO 2 system with a modulus of 86-89 GPa.
  • the traditional R glass has a high total content of silicon and aluminum, and lacks an effective solution to improve the crystallization performance of the glass.
  • the ratio of calcium to magnesium is also unreasonable, resulting in difficulty in forming glass and high risk of crystallization, and the surface tension of the glass is large and difficult to clarify.
  • High, its glass fiber molding temperature reaches 1410 ° C, and the liquidus temperature reaches 1350 ° C, which all cause difficulties in the efficient drawing of glass fiber, and it is also difficult to achieve large-scale pool kiln production.
  • Nanjing Glass Fiber Research and Design Institute has developed a kind of HS2 glass with a modulus of 84-87GPa. Its main components also include SiO 2 , Al 2 O 3 and MgO, and also introduce some Li 2 O and B 2 O 3 .
  • an object of the present invention is to provide a high modulus glass fiber composition which can significantly increase the modulus of elasticity of a glass, thereby overcoming the high liquidus temperature of a conventional high modulus glass.
  • the crystallization rate is fast, the molding temperature is high, the surface tension is large, and it is difficult to clarify. It is difficult to carry out the problem of high-efficiency pool kiln production, which can significantly reduce the liquidus temperature and molding temperature of high modulus glass, and is beneficial to lower under the same conditions.
  • the crystallization rate and bubble ratio of the glass while obtaining an ideal ⁇ T value, are particularly suitable for the production of high modulus glass fibers by kiln kiln.
  • a high modulus glass fiber composition comprising the following components, the content of each component being expressed by weight percentage as follows:
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / (Y 2 O 3 + La 2 O 3 ) is more than 0.26.
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / Y 2 O 3 is more than 0.26.
  • the content of Li 2 O is further limited to be 0.1% to 1.5% by weight.
  • the content of SrO is further limited, and is represented by 0.1% to 2.5% by weight.
  • the content of CaO is further limited, and is represented by a percentage by weight of 6 to 10.3%.
  • the content of MgO is further limited, expressed as 8.6-13% by weight.
  • the content of Y 2 O 3 is further limited, and is 0.5 to 5% by weight.
  • the content of Y 2 O 3 is further limited, expressed as 1.5-5% by weight.
  • the content of SrO is further limited, and is 0.1 to 2% by weight.
  • the content of La 2 O 3 is further limited, and is 0.1 to 1% by weight.
  • the content of Y 2 O 3 is further limited, and is 2-4% by weight.
  • the content of CaO is further limited, expressed as 6.5 to 10% by weight.
  • the content of MgO is further limited to be more than 12% by weight and 13% or less.
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / (Y 2 O 3 + La 2 O 3 ) is more than 0.26.
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / (Y 2 O 3 + La 2 O 3 ) is more than 0.26.
  • CeO 2 may also be contained, and its content is 0-1% by weight.
  • a glass fiber made of the above glass fiber composition.
  • the glass fiber has a modulus of elasticity ranging from 90 to 103 GPa.
  • a composite material comprising the glass fibers described above.
  • the main innovation is the introduction of rare earth oxide Y 2 O 3 , which utilizes a special replenishment effect of ruthenium in the glass structure and controls (Li 2 O+Na 2 O+K 2 O) / (Y 2 O 3 + La 2 O 3 ) and MgO / (CaO + SrO) ratio, reasonable configuration of Y 2 O 3 , La 2 O 3 , Li 2 O, SrO, CaO, MgO and CaO + MgO
  • the content range of +SrO, and the synergistic effect between cerium and an alkali metal oxide and the mixed alkaline earth effect between SrO, CaO, and MgO, and optionally, an appropriate amount of CeO 2 or the like can be selectively introduced.
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / (Y 2 O 3 + La 2 O 3 ) is more than 0.26.
  • the functions and contents of the components in the glass fiber composition are as follows:
  • SiO 2 is the main oxide forming the glass skeleton and functions to stabilize the components.
  • the weight percentage of SiO 2 is limited to range from 55 to 64%.
  • the present invention specifically controls the silicon oxide content to a low level.
  • the content by weight of SiO 2 may be limited to 56-60.4%, and more preferably, the content by weight of SiO 2 may be limited to 57-60.4%.
  • Al 2 O 3 is also an oxide forming a glass skeleton. When combined with SiO 2 , it can play a substantial role in the mechanical properties of the glass and plays an important role in preventing phase separation and water resistance of the glass.
  • the content of Al 2 O 3 is limited to a range of 13 to 24% by weight, and if it is low in content, sufficient mechanical properties, especially modulus, cannot be obtained; if the content is too high It is easy to greatly increase the risk of glass phase separation.
  • the content by weight of Al 2 O 3 may be limited to 14-24%, and more preferably, the content by weight of Al 2 O 3 may be limited to 14-23%.
  • the inventors have unexpectedly found that when the content of controlled Al 2 O 3 is more than 19% by weight and 21% or less, the content of MgO is less than or equal to 10.5% by weight, Li 2 O+Na 2 O+ When the weight percentage of K 2 O is 1% or less, the glass can obtain excellent modulus performance, anti-crystallization ability, and molding range ⁇ T value.
  • Both K 2 O and Na 2 O reduce the viscosity of the glass and are good fluxing agents.
  • the inventors have found that replacing K 2 O with Na 2 O in the case where the total amount of alkali metal oxide is constant can lower the crystallization tendency of the glass and improve the fiber forming property.
  • Li 2 O not only can significantly reduce the viscosity of the glass, thereby improving the glass melting performance, and is obviously helpful for improving the mechanical properties of the glass.
  • a small amount of Li 2 O can provide considerable free oxygen, which is beneficial to the formation of tetrahedral coordination of more aluminum ions, enhance the network structure of the glass system, and further reduce the crystallization ability of the glass.
  • the weight percentage of Li 2 O+Na 2 O+K 2 O is limited to less than 2%. Further, the weight percentage content of Li 2 O may be limited to 0.1 to 1.5%, and preferably, the weight percentage of Li 2 O may be limited to 0.1 to 1%.
  • Y 2 O 3 is an important rare earth oxide, and the inventors have found that it is particularly effective in increasing the glass modulus and suppressing glass crystallization.
  • Y 3+ is difficult to enter the glass network. It is generally used as an external ion in the network space. It has high coordination number, high field strength, high charge and strong accumulation ability. It can improve the stability of the glass structure and increase the glass modulus. At the same time, it can effectively prevent the movement of other ions, and achieve the purpose of reducing the crystallization tendency of the glass.
  • the content of Y 2 O 3 is limited to a content ranging from 0.1 to 6% by weight.
  • the content by weight of Y 2 O 3 may be limited to 0.5-5%; preferably, the content by weight of Y 2 O 3 may be limited to 1.5-5%; preferably, the weight percentage of Y 2 O 3
  • the content range can be limited to 2-4%.
  • La 2 O 3 is also an important rare earth oxide.
  • the inventors have found that when it is used alone, the effect in increasing the glass modulus and inhibiting crystallization is significantly weaker than that of Y 2 O 3 , but its clarifying effect is better than Y. 2 O 3 .
  • the molar mass and ionic radius of bismuth are both large, if the amount of introduction is too large, not only the effect of improving the glass performance is weakened, but also the stability of the glass structure is broken, and the glass density is also significantly increased, so La 2 O 3 The introduction amount should not be much.
  • a small amount of La 2 O 3 may be selectively introduced, and the weight percentage of La 2 O 3 is defined to be in the range of 0 to 1.2%. Further, the weight percentage of La 2 O 3 may be defined to range from 0.1 to 1%.
  • Y 2 O 3 has vacancy defects in the crystalline state. When Y 2 O 3 is added to the glass, these vacancy defects can be filled with free oxygen provided by other oxides, especially alkali metal oxides, and different filling levels affect Y.
  • the coordination state of 2 O 3 and its bulk density have a significant effect on the glass properties.
  • La 2 O 3 also requires a certain amount of oxygen to fill the vacancies. In order to obtain sufficient free oxygen, the structure is more densely packed and the anti-crystallization is more remarkable.
  • the range of the ratio C1 can be defined to be greater than 0.28. More preferably, the range of the ratio C1 may be defined to be greater than 0.29.
  • CaO, MgO and SrO mainly control the crystallization of glass and adjust the viscosity and material properties of the glass. Especially in controlling the crystallization of glass, the inventors obtained unexpected effects by controlling their introduction amount and proportional relationship.
  • high-performance glass mainly composed of MgO-CaO-Al 2 O 3 -SiO 2 system
  • the crystal phase contained in the glass after crystallization is mainly composed of diopside (CaMgSi 2 O 6 ) and anorthite ( CaAl 2 Si 2 O 8 ).
  • the content of CaO+MgO+SrO is limited to a content of less than 22% by weight.
  • the weight percentage content of CaO+MgO+SrO may be limited to less than 21%.
  • the range of the ratio C2 can be defined as 0.9-1.8. More preferably, the range of the ratio C2 can be defined as 0.9-1.7.
  • the content of CaO is limited to a range of from 3.4 to 10.9% by weight.
  • the content of the content of CaO may be limited to 5-10.6%; preferably, the content of the content of CaO may be limited to 6-10.3%; preferably, the content of the content of CaO may be limited to 6.5-10%.
  • the weight percentage of MgO is defined to range from 8 to 14%. Further, in an embodiment, preferably, the weight percentage content of MgO may be limited to 8.6-13%. In another embodiment, preferably, the weight percentage content of MgO may be defined to be greater than 12 and less than or equal to 13%. Further, the weight percentage of the defined SrO ranges from less than 3%. Preferably, the weight percentage content of SrO may be limited to 0.1 to 2.5%. More preferably, the weight percentage content of SrO may be limited to 0.1 to 2%.
  • TiO 2 not only reduces the viscosity of the glass at high temperatures, but also has a certain fluxing effect. However, since the titanium ion has a certain coloring effect, especially when the TiO 2 content exceeds 2%, the coloring effect becomes particularly remarkable, and the appearance of the glass fiber product is affected to some extent. Accordingly, in the glass fiber composition of the present invention, the content of TiO 2 is limited to a content of less than 2% by weight.
  • Fe 2 O 3 is advantageous for the melting of glass and also for improving the crystallization properties of glass. However, since iron ions and ferrous ions have a coloring effect, the amount of introduction is not preferable. Accordingly, in the glass fiber composition of the present invention, the weight percentage of Fe 2 O 3 is limited to less than 1.5%.
  • an appropriate amount of CeO 2 may be selectively introduced to further improve the crystallization tendency and the clarifying effect of the glass.
  • the content of CeO 2 is limited to a range of from 0 to 1% by weight.
  • the glass fiber composition of the present invention is also allowed to contain a small amount of other components, and the total content by weight is generally not more than 2%.
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percent as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the composition has a liquidus temperature of not more than 1,320 ° C, preferably not more than 1,300 ° C, more preferably not more than 1,250 ° C; the glass fiber formed from the composition has an elastic modulus of from 90 to 103 GPa.
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / (Y 2 O 3 + La 2 O 3 ) is more than 0.26.
  • the glass fiber formed from the composition has an elastic modulus of more than 95 GPa.
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the ratio of the weight percentage C1 (Li 2 O + Na 2 O + K 2 O) / (Y 2 O 3 + La 2 O 3 ) is more than 0.26.
  • the high modulus glass fiber composition according to the present invention contains the following components, and the content of each component is expressed by weight percentage as follows:
  • the basic idea of the present invention is that the content of each component of the glass fiber composition is expressed by weight percentage: SiO 2 is 55-64%, Al 2 O 3 is 13-24%, and Y 2 O 3 is 0.1-6%.
  • CaO is 3.4-10.9%
  • MgO is 8-14%
  • CaO+MgO+SrO is less than 22%
  • Li 2 O+Na 2 O+K 2 O is less than 2%
  • TiO 2 is less than 2%
  • Fe 2 O 3 is less than 1.5%
  • La 2 O 3 is 0-1.2%
  • the composition can significantly improve the elastic modulus of the glass, and can effectively inhibit the crystallization tendency of the glass, lower the liquidus temperature of the glass, obtain an ideal ⁇ T value, and improve the clarification effect of the high modulus glass, especially Suitable for use in pool kiln production of high modulus glass fibers.
  • the molding temperature corresponds to the temperature at which the glass melt has a viscosity of 10 3 poise.
  • the liquidus temperature corresponds to the temperature at which the crystal nucleus begins to form when the glass melt is cooled, that is, the upper limit temperature of the glass crystallization.
  • the temperature of the crystallization peak which corresponds to the temperature of the strongest peak of glass crystallization during the DTA test.
  • the higher the temperature the more energy is required to grow the crystal nucleus, and the crystallization tendency of the glass is smaller.
  • the modulus of elasticity which is the modulus of elasticity along the machine direction, characterizes the ability of the glass fiber to resist elastic deformation and is tested in accordance with ASTM 2343.
  • the number of bubbles wherein the approximate method of measuring the number of bubbles is: using a special mold to press each sample batch into a sample of the same shape, placed in a sample platform of a high temperature microscope, and then programmed to a set space temperature. At 1500 ° C, the glass samples were cooled to room temperature with the furnace; then, the number of bubbles of each glass sample was observed from a microscopic angle by a polarizing microscope. Among them, the number of bubbles is based on the imaging range of the microscope.
  • each component can be obtained from a suitable raw material, and various raw materials are mixed in proportion to achieve the final expected weight percentage of each component, and the mixed batch material is melted and clarified, and then the glass liquid
  • the glass fiber is formed by the leaking nozzle on the drain plate being pulled out, and the glass fiber is drawn around the rotating head of the wire drawing machine to form a raw silk cake or a yarn group.
  • these glass fibers can be further processed in a conventional manner to meet the expected requirements.
  • the content of the glass fiber composition is expressed by weight percentage. It should be noted that the total content of the components of the examples is slightly less than 100%, and it can be understood that the residual amount is a trace impurity or a small component which cannot be analyzed.
  • the glass fiber composition of the present invention has the following advantages as compared with S glass and conventional R glass: (1) having a much higher modulus of elasticity; (b) having a much lower The liquidus temperature, which is beneficial to reduce the crystallization risk of the glass and improve the drawing efficiency of the fiber; has a higher crystallization peak temperature, which indicates that the nucleation and growth of the glass requires more energy during crystallization. That is to say, under the same conditions, the crystallization rate of the glass of the invention is smaller; (3) having a smaller number of bubbles, which indicates that the clarification effect of the glass is better.
  • both S glass and conventional R glass cannot achieve pool kiln production.
  • Improved R glass reduces the liquidus temperature and molding temperature by sacrificing part of the performance to reduce the production difficulty and realize the kiln kiln production.
  • the composition of the present invention not only has a sufficiently low liquidus temperature and molding temperature, but can also be used for kiln kiln production, while also achieving a glass modulus. The substantial increase has broken the technical bottleneck that the modulus levels of S- and R-grade glass fibers cannot be increased simultaneously with the production scale.
  • Glass fibers having the above-described excellent properties can be produced from the glass fiber composition according to the present invention.
  • the glass fiber composition according to the present invention can be combined with one or more organic and/or inorganic materials to produce a composite material having excellent properties, for example, a glass fiber reinforced substrate.
  • the composition of the invention not only has a sufficiently low liquidus temperature and molding temperature, but also can perform the kiln kiln production, and at the same time, the glass modulus is greatly improved, and the modulus level of the S-class and R-grade glass fibers cannot be broken.
  • the technical bottleneck of the simultaneous increase in production scale, compared with the current mainstream high modulus glass, the glass fiber composition of the present invention has made a breakthrough in elastic modulus, crystallization performance and glass clarification, under the same conditions of glass
  • the elastic modulus is greatly improved, the risk of crystallization is greatly reduced, and the number of bubbles is small.
  • the overall technical solution is easy to realize large-scale pool kiln production.

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Abstract

本发明提供一种高模量玻璃纤维组合物及其玻璃纤维和复合材料。其中，玻璃纤维组合物各组分的含量以重量百分比表示如下：SiO2为55-64%，Al2O3为13-24%，Y2O3为0.1-6%，CaO为3.4-10.9%，MgO为8-14%，CaO+MgO+SrO为小于22%，Li2O+Na2O+K2O为小于2%，TiO2为小于2%，Fe2O3为小于1.5%，La2O3为0-1.2%，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。该组合物能显著提高玻璃的弹性模量，并能有效抑制玻璃的析晶倾向、降低玻璃的液相线温度，获得较理想的△T值，还有利于改善高模量玻璃的澄清效果，特别适合用于池窑化生产高模量玻璃纤维。

Description

一种高模量玻璃纤维组合物及其玻璃纤维和复合材料
本申请要求在2016年2月29日提交中国专利局、申请号为201610113362.0、发明名称为“一种高模量玻璃纤维组合物及其玻璃纤维和复合材料”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种高模量玻璃纤维组合物，尤其涉及一种能作为先进复合材料增强基材的高模量玻璃纤维组合物及其玻璃纤维和复合材料。
背景技术
玻璃纤维属于无机纤维材料，用它增强树脂可制得性能优良的复合材料。高模量玻璃纤维作为先进复合材料的增强基材，最初主要应用于航空、航天、兵器等国防军工领域。随着科技的进步及经济的发展，高模量玻璃纤维在风力叶片、高压容器、海洋管道、汽车制造等民用工业领域得到了广泛应用。
最早的高模量玻璃成分以MgO-Al2O3-SiO2系统为主体，典型方案如美国OC公司开发的S-2玻璃，模量在89-90GPa，但是它的生产难度过大，其玻纤成型温度高达1571℃，液相线温度高达1470℃，难于实现大规模池窑化生产。因此，OC公司主动放弃了生产S-2玻璃纤维，将其专利权转让给了美国AGY公司。
随后，OC公司还开发了HiPer-tex玻璃，模量在87-89GPa，这是一种以牺牲部分玻璃性能以降低生产难度的折衷策略，不过由于设计方案只是对S-2玻璃的简单改进，造成玻纤成型温度和液相线温度依然很高，生产难度还是很大，难于实现大规模池窑化生产。因此，OC公司也放弃了生产HiPer-tex玻璃纤维，将其专利权转让给了欧洲3B公司。
法国圣戈班公司开发过一种以MgO-CaO-Al2O3-SiO2系统为主体的R玻璃，模量在86-89GPa。但是传统R玻璃的硅铝总含量较高，又缺乏改善玻璃析晶性能的有效方案，钙镁比例也不合理，造成玻璃成型困难、析晶风险高，同时玻璃液的表面张力大、澄清难度高，其玻纤成型温度达到1410℃，液相线温度达到1350℃，这都造成玻璃纤维高效拉制上的困难，同样难于实现大规模池窑化生产。
在国内，南京玻璃纤维研究设计院开发过一种HS2玻璃，模量在84-87GPa，其主要成分 也包括SiO2、Al2O3、MgO，同时还引入部分Li2O、B2O3、CeO2和Fe2O3，它的成型温度只有1245℃，液相线温度为1320℃，两者的温度均比S玻璃低得多，但其成型温度比液相线温度低△T值为负，极不利于玻璃纤维的高效拉制，必须提高拉丝温度，采用特殊形式的漏嘴，以防止拉丝过程中发生玻璃失透现象，这造成温度控制上的困难，也难于实现大规模池窑化生产。
综上所述，我们发现，现阶段的各类高模量玻璃纤维在实际生产中均存在池窑化生产难度大的普遍问题，具体表现为玻璃的液相线温度偏高、析晶速率快，成型温度偏高、表面张力大、澄清难度大，△T值小甚至为负。为此，大部分公司往往以牺牲部分玻璃性能的方式来降低生产难度，这造成上述玻璃纤维的模量水平无法与生产规模同步提升，也一直无法突破S玻璃的模量瓶颈。
发明内容
针对上述问题，本发明的目的是提供一种高模量玻璃纤维组合物，该组合物能显著提高玻璃的弹性模量，在此基础上，克服了传统高模量玻璃液相线温度偏高、析晶速率快，成型温度偏高、表面张力大、不易澄清，难于进行高效率池窑生产的问题，能显著降低高模量玻璃的液相线温度和成型温度，同等条件下有利于降低玻璃的析晶速率和气泡率，同时获得较理想的△T值，特别适合用于池窑化生产高模量玻璃纤维。
根据本发明的一个方面，提供一种高模量玻璃纤维组合物，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000001
Figure PCTCN2016075780-appb-000002
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
其中，进一步限定重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000003
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3的范围为大于0.26。
其中，进一步限定Li2O的含量，以重量百分比表示为0.1-1.5％。
其中，进一步限定SrO的含量，以重量百分比表示为0.1-2.5％。
其中，进一步限定CaO的含量，以重量百分比表示为6-10.3％。
其中，进一步限定MgO的含量，以重量百分比表示为8.6-13％。
其中，进一步限定Y2O3的含量，以重量百分比表示为0.5-5％。
其中，进一步限定Y2O3的含量，以重量百分比表示为1.5-5％。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000004
Figure PCTCN2016075780-appb-000005
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3的范围为大于0.26，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000006
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000007
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000008
Figure PCTCN2016075780-appb-000009
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.8。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000010
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.7。
其中，进一步限定SrO的含量，以重量百分比表示为0.1-2％。
其中，进一步限定La2O3的含量，以重量百分比表示为0.1-1％。
其中，进一步限定Y2O3的含量，以重量百分比表示为2-4％。
其中，进一步限定CaO的含量，以重量百分比表示为6.5-10％。
其中，进一步限定MgO的含量，以重量百分比表示为大于12％且小于等于13％。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000011
Figure PCTCN2016075780-appb-000012
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
其中，各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000013
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
其中，还可以含有CeO2，其含量以重量百分比表示为0-1％。
根据本发明的另一个方面，提供一种玻璃纤维，所述玻璃纤维由上述的玻璃纤维组合物制成。
其中，所述玻璃纤维的弹性模量范围为90-103GPa。
根据本发明的第三方面，提供一种复合材料，所述复合材料包括上述的玻璃纤维。
根据本发明的高模量玻璃纤维组合物，主要创新点是引入稀土氧化物Y2O3，利用钇在玻璃结构中特殊的补位作用，并控制(Li2O+Na2O+K2O)/(Y2O3+La2O3)和MgO/(CaO+SrO)的比值，合理配置Y2O3、La2O3、Li2O、SrO、CaO、MgO和CaO+MgO+SrO的含量范围，以及利用钇与碱金属氧化物之间的协同效应及SrO、CaO、MgO之间的混合碱土效应，此外还可以选择性地引入适量CeO2等。
具体来说，根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000014
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
该玻璃纤维组合物中各组分的作用及含量说明如下：
SiO2是形成玻璃骨架的主要氧化物，并且起稳定各组分的作用。在本发明的玻璃纤维组合物中，限定SiO2的重量百分比含量范围为55-64％。在保证机械性能的基础上，为了不增加玻璃的澄清难度，本发明中特意将氧化硅含量控制在不高的水平。优选地，SiO2的重量百分比含量范围可以限定为56-60.4％，更优选地，SiO2的重量百分比含量范围可以限定为57-60.4％。
Al2O3也是形成玻璃骨架的氧化物，与SiO2结合时可对玻璃的机械性能起到实质性的作用，并且在阻止玻璃分相和抗水性方面起着重要作用。在本发明的玻璃纤维组合物中，限定Al2O3的重量百分比含量范围为13-24％，若其含量较低会无法获得足够高的机械性能，尤其 是模量；若其含量太高容易大幅增加玻璃分相的风险。优选地，Al2O3的重量百分比含量范围可以限定为14-24％，更优选地，Al2O3的重量百分比含量范围可以限定为14-23％。另外，在一实施方案中，发明人意外发现，当控制Al2O3的重量百分比含量大于19％且小于等于21％，MgO的重量百分比含量小于等于10.5％，Li2O+Na2O+K2O的重量百分比含量小于等于1％时，玻璃能获得优异的模量性能、抗析晶能力及成型范围△T值。
K2O和Na2O均能降低玻璃粘度，是良好的助熔剂。发明人发现，在碱金属氧化物总量不变的情况下，用K2O替代Na2O，能降低玻璃的析晶倾向，改善纤维成型性能。同Na2O和K2O相比，Li2O不仅能显著地降低玻璃粘度，从而改善玻璃熔制性能，并且对提高玻璃的力学性能有明显帮助。同时，少量Li2O就能提供可观的游离氧，有利于更多的铝离子形成四面体配位，增强玻璃体系的网络结构，可进一步降低玻璃的析晶能力。但由于碱金属离子过多会影响玻璃结构的稳定性，故引入量不宜多。因此，在本发明的玻璃纤维组合物中，限定Li2O+Na2O+K2O的重量百分比含量范围为小于2％。进一步地，Li2O的重量百分比含量范围可限定为0.1-1.5％，优选地，Li2O的重量百分比含量范围可限定为0.1-1％。
Y2O3是一种重要的稀土氧化物，发明人发现，它在提高玻璃模量、抑制玻璃析晶方面特别有效。Y3+很难进入玻璃网络，一般处于网络空隙间作为网络外离子，它的配位数高、场强高、电荷高，积聚能力强，能提高玻璃结构的稳定性，提高玻璃模量，同时还能有效阻止其他离子的移动排列，达到降低玻璃析晶倾向的目的。在本发明的玻璃纤维组合物中，限定Y2O3的重量百分比含量范围为0.1-6％。优选地，Y2O3的重量百分比含量范围可以限定为0.5-5％；优选地，Y2O3的重量百分比含量范围可以限定为1.5-5％；优选地，Y2O3的重量百分比含量范围可以限定为2-4％。
La2O3也是一种重要的稀土氧化物，发明人发现，当单独使用它时，在提高玻璃模量及抑制析晶方面的作用明显弱于Y2O3，但是其澄清效果优于Y2O3。同时，由于镧的摩尔质量和离子半径均较大，若引入量过多，不仅对提高玻璃性能作用减弱，甚至会破坏玻璃结构的稳定性，还会明显增大玻璃密度，因此La2O3的引入量不宜多。在本发明的玻璃纤维组合物中，可以选择性地引入少量La2O3，限定La2O3的重量百分比含量范围为0-1.2％。进一步地，可以限定La2O3的重量百分比含量范围为0.1-1％。
发明人还发现，Y2O3的配位状态与玻璃中游离氧的含量密切相关。Y2O3在晶体状态下存在空位缺陷，当Y2O3加入到玻璃中后，这些空位缺陷可以由其他氧化物特别是碱金属氧化物提供的游离氧填充，不同的填充程度会影响Y2O3的配位状态及其堆积密度，从而对玻璃性能产生显著的影响。与之类似，La2O3同样需要一定数量的氧来填补空位。为了获得足够的游离 氧，使结构堆积更紧密、抗析晶作用更显著，本发明中限定重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。优选地，比值C1的范围可以限定为大于0.28。更优选地，比值C1的范围可以限定为大于0.29。
CaO、MgO和SrO主要起控制玻璃析晶、调节玻璃粘度和料性的作用。尤其是在控制玻璃析晶方面，发明人通过控制它们的引入量和比例关系获得了意想不到的效果。一般来说，以MgO-CaO-Al2O3-SiO2系统为主体的高性能玻璃，其玻璃析晶后所包含的晶相主要包括透辉石(CaMgSi2O6)和钙长石(CaAl2Si2O8)。为了有效抑制两种晶相的析晶倾向，降低玻璃的液相线温度和析晶速率，本发明中通过合理控制CaO+MgO+SrO的含量范围及各组分间的比例关系C2＝MgO/(CaO+SrO)，利用混合碱土效应形成更紧密的堆积结构，使其晶核形成和长大时需要更多的能量；此外，Sr2+的离子半径大，不仅自身很难移动，而且同等条件下还可以有效阻碍Mg2+和Ca2+离子的移动重组，从而达到抑制玻璃析晶倾向的目的。同时，还能有效改善玻璃的料性。在本发明的玻璃纤维组合物中，限定CaO+MgO+SrO的重量百分比含量范围为小于22％。优选地，CaO+MgO+SrO的重量百分比含量范围可以限定为小于21％。进一步地，在一实施方案中，可以限定重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。优选地，比值C2的范围可以限定为0.9-1.8。更优选地，比值C2的范围可以限定为0.9-1.7。在另一实施方案中，当MgO的含量大于12％时，可以不受上述比值C2范围的限制。
在本发明的玻璃纤维组合物中，限定CaO的重量百分比含量范围为3.4-10.9％。优选地，CaO的重量百分比含量范围可以限定为5-10.6％；优选地，CaO的重量百分比含量范围可以限定为6-10.3％；优选地，CaO的重量百分比含量范围可以限定为6.5-10％。在本发明的玻璃纤维组合物中，限定MgO的重量百分比含量范围为8-14％。进一步地，在一实施方案中，优选地，MgO的重量百分比含量范围可以限定为8.6-13％。在另一实施方案中，优选地，MgO的重量百分比含量范围可以限定为大于12且小于等于13％。进一步地，限定SrO的重量百分比含量范围为小于3％。优选地，SrO的重量百分比含量范围可以限定为0.1-2.5％。更优选地，SrO的重量百分比含量范围可以限定为0.1-2％。
TiO2不仅可以降低高温时的玻璃粘度，还具有一定的助熔作用。但由于钛离子具有一定的着色作用，尤其是当TiO2含量超过2％后，这种着色作用变得特别显著，一定程度上会影响玻纤制品的外观。因此，本发明的玻璃纤维组合物中，限定TiO2的重量百分比含量范围为小于2％。
Fe2O3有利于玻璃的熔制，也能改善玻璃的析晶性能。但由于铁离子和亚铁离子具有着色作用，故引入量不宜多。因此，在本发明的玻璃纤维组合物中，限定Fe2O3的重量百分比含 量范围为小于1.5％。
本发明的玻璃纤维组合物中，还可以选择性地引入适量CeO2，以进一步改善玻璃的析晶倾向和澄清效果。在本发明的玻璃纤维组合物中，限定CeO2的重量百分比含量范围为0-1％。
此外，本发明的玻璃纤维组合物中还允许含有少量其他组分，重量百分比总含量一般不超过2％。
本发明的玻璃纤维组合物中，选择各组分含量的上述范围的有益效果将通过实施例给出具体实验数据进行说明。
下面是根据本发明的玻璃纤维组合物中所包括的各组分的优选取值范围示例。
优选示例一
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000015
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
优选示例二
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示 如下：
Figure PCTCN2016075780-appb-000016
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
优选示例三
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000017
Figure PCTCN2016075780-appb-000018
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
优选示例四
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000019
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.8。
优选示例五
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000020
Figure PCTCN2016075780-appb-000021
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.7。
根据优选示例五，该组合物的液相线温度不大于1320℃，优选地不大于1300℃，更优选地不大于1250℃；由该组合物形成的玻璃纤维的弹性模量为90-103GPa。
优选示例六
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000022
Figure PCTCN2016075780-appb-000023
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.7。
优选示例七
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000024
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
优选示例八
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000025
Figure PCTCN2016075780-appb-000026
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
优选示例九
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000027
Figure PCTCN2016075780-appb-000028
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
优选示例十
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000029
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
根据优选示例十，由该组合物形成的玻璃纤维的弹性模量为大于95GPa。
优选示例十一
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000030
Figure PCTCN2016075780-appb-000031
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
优选示例十二
根据本发明的高模量玻璃纤维组合物含有下述组分，且各组分的含量以重量百分比表示如下：
Figure PCTCN2016075780-appb-000032
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明的一部分实施例，而不是全部 的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互任意组合。
本发明的基本思想是，玻璃纤维组合物的各组分含量以重量百分比表示为：SiO2为55-64％，Al2O3为13-24％，Y2O3为0.1-6％，CaO为3.4-10.9％，MgO为8-14％，CaO+MgO+SrO为小于22％，Li2O+Na2O+K2O为小于2％，TiO2为小于2％，Fe2O3为小于1.5％，La2O3为0-1.2％，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。该组合物能显著提高玻璃的弹性模量，并能有效抑制玻璃的析晶倾向、降低玻璃的液相线温度，获得较理想的△T值，还能改善高模量玻璃的澄清效果，特别适合用于池窑化生产高模量玻璃纤维。
选取本发明的玻璃纤维组合物中SiO2、Al2O3、Y2O3、CaO、MgO、Li2O、Na2O、K2O、Fe2O3、TiO2、SrO和La2O3的具体含量值作为实施例，与S玻璃、传统R玻璃和改良R玻璃的性能参数进行对比。在性能对比时，选用六个性能参数：
(1)成型温度，对应于玻璃熔体在粘度为103泊时的温度。
(2)液相线温度，对应于玻璃熔体冷却时晶核开始形成的温度，即玻璃析晶的上限温度。
(3)△T值，成型温度与液相线温度之差，表示拉丝成型的温度范围。
(4)析晶峰温度，DTA测试过程中对应于玻璃析晶最强峰的温度。一般情况下，该温度越高，表明晶核长大所需能量越多，玻璃的析晶倾向越小。
(5)弹性模量，是沿纵向的弹性模量，表征玻璃纤维抵抗弹性变形的能力，按ASTM2343测试。
(6)气泡数量，其中测定气泡数量的大致方法为：利用专用的模具将每个实施例配合料压制成一样形状的样品，放置于高温显微镜的样品平台，然后按程序升温至设定空间温度1500℃，不保温，玻璃样品随炉冷却至常温；然后，通过偏光显微镜从微观角度观察各个玻璃样品的气泡数量。其中，气泡数量按显微镜成像范围为准。
上述六个参数及其测定方法是本领域技术人员所熟知的，因此采用上述参数能够有力地说明本发明的玻璃纤维组合物的性能。
实验的具体过程为：各组分可从适当的原料中获取，按比例将各种原料进行混合，使各组分达到最终的预期重量百分比，混合后的配合料进行熔化并澄清，然后玻璃液通过漏板上的漏嘴被拉出从而形成玻璃纤维，玻璃纤维被牵引绕到拉丝机旋转机头上形成原丝饼或纱团。当然，这些玻璃纤维可用常规方法进行深加工以符合预期要求。
下面给出根据本发明的玻璃纤维组合物的具体实施例。
实施例一
Figure PCTCN2016075780-appb-000033
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3为0.74，重量百分比的比值C2＝MgO/(CaO+SrO)为0.96。
在实施例一中测定的六个参数的数值分别是：
Figure PCTCN2016075780-appb-000034
实施例二
Figure PCTCN2016075780-appb-000035
Figure PCTCN2016075780-appb-000036
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3为0.41，重量百分比的比值C2＝MgO/(CaO+SrO)为1.18。
在实施例二中测定的六个参数的数值分别是：
Figure PCTCN2016075780-appb-000037
实施例三
Figure PCTCN2016075780-appb-000038
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3为0.29，重量百分比的比值C2＝MgO/(CaO+SrO)为1.49。
在实施例三中测定的六个参数的数值分别是：
Figure PCTCN2016075780-appb-000039
实施例四
Figure PCTCN2016075780-appb-000040
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3为0.31，重量百分比的比值C2＝MgO/(CaO+SrO)为1.79。
在实施例四中测定的六个参数的数值分别是：
Figure PCTCN2016075780-appb-000041
实施例五
Figure PCTCN2016075780-appb-000042
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3为0.32，重量百分比的比值C2＝MgO/(CaO+SrO)为1.37。
在实施例五中测定的六个参数的数值分别是：
Figure PCTCN2016075780-appb-000043
实施例六
Figure PCTCN2016075780-appb-000044
Figure PCTCN2016075780-appb-000045
并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/Y2O3为0.35，重量百分比的比值C2＝MgO/(CaO+SrO)为2。
在实施例六中测定的六个参数的数值分别是：
Figure PCTCN2016075780-appb-000046
下面进一步通过列表的方式，给出本发明玻璃纤维组合物的上述实施例以及其他实施例与S玻璃、传统R玻璃和改良R玻璃的性能参数的对比。其中，玻璃纤维组合物的含量以重量百分比表示。需要说明的是，实施例组分总含量略微小于100％，可以理解为残余量是微量杂质或不能分析出的少量组分。
表1A
Figure PCTCN2016075780-appb-000047
表1B
Figure PCTCN2016075780-appb-000048
表1C
Figure PCTCN2016075780-appb-000049
由上述表中的具体数值可知，与S玻璃和传统R玻璃相比，本发明的玻璃纤维组合物拥有以下优势：(一)具有高得多的弹性模量；(二)具有低得多的液相线温度，这有利于降低玻璃的析晶风险、提高纤维的拉丝效率；具有较高的析晶峰温度，这表明玻璃在析晶过程中晶核的形成和长大需要更多的能量，也就是说同等条件下本发明玻璃的析晶速率更小；(三)具有较少的气泡数量，这表明玻璃的澄清效果更优。
S玻璃和传统R玻璃均无法实现池窑化生产，改良R玻璃通过牺牲部分性能的方式来降低液相线温度和成型温度，以降低生产难度实现池窑化生产。与之不同的是，本发明组合物不仅拥有足够低的液相线温度和成型温度，可以进行池窑化生产，同时还实现了玻璃模量的 大幅提升，打破了S级和R级玻璃纤维的模量水平无法与生产规模同步提升的技术瓶颈。
由根据本发明的玻璃纤维组合物可制成具有上述优良性能的玻璃纤维。
根据本发明的玻璃纤维组合物与一种或多种有机和/或无机材料结合可制备得到性能优良的复合材料，例如，玻纤增强基材。
最后应说明的是：在本文中，术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包含一系列要素的过程、方法、物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程、方法、物品或者设备所固有的要素。在没有更多限制的情况下，由语句“包括一个…”限定的要素，并不排除在包括所述要素的过程、方法、物品或者设备中还存在另外的相同要素。
以上实施例仅用以说明本发明的技术方案，而非对其限制。尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。
工业实用性
本发明组合物不仅拥有足够低的液相线温度和成型温度，可以进行池窑化生产，同时还实现了玻璃模量的大幅提升，打破了S级和R级玻璃纤维的模量水平无法与生产规模同步提升的技术瓶颈，与目前主流的高模量玻璃相比，本发明的玻璃纤维组合物在弹性模量、析晶性能和玻璃澄清方面取得了突破性的进展，同等条件下玻璃的弹性模量大幅提升、析晶风险大幅下降、气泡数量较少，整体技术方案易于实现大规模池窑化生产。

Claims (24)

  1. 一种高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100001
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
  2. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
  3. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100002
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
  4. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，Li2O的含量以重量百分比表示为0.1-1.5％。
  5. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，SrO的含量以重量百分比表示为0.1-2.5％。
  6. 根据权利要求1或2所述的高模量玻璃纤维组合物，其特征在于，CaO的含量以重量百分比表示为6-10.3％。
  7. 根据权利要求1或2所述的高模量玻璃纤维组合物，其特征在于，MgO的含量以重量百分比表示为8.6-13％。
  8. 根据权利要求2或4所述的高模量玻璃纤维组合物，其特征在于，Y2O3的含量以重量百分比表示为0.5-5％。
  9. 根据权利要求2或4所述的高模量玻璃纤维组合物，其特征在于，Y2O3的含量以重量百分比表示为1.5-5％。
  10. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100003
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
  11. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100004
    Figure PCTCN2016075780-appb-100005
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
  12. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100006
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.28，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.8-2.1。
  13. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100007
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.8。
  14. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100008
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.29，重量百分比的比值C2＝MgO/(CaO+SrO)的范围为0.9-1.7。
  15. 根据权利要求1或14所述的高模量玻璃纤维组合物，其特征在于，SrO的含量以重 量百分比表示为0.1-2％。
  16. 根据权利要求1或12所述的高模量玻璃纤维组合物，其特征在于，La2O3的含量以重量百分比表示为0.1-1％。
  17. 根据权利要求1或12所述的高模量玻璃纤维组合物，其特征在于，Y2O3的含量以重量百分比表示为2-4％。
  18. 根据权利要求1或12所述的高模量玻璃纤维组合物，其特征在于，CaO的含量以重量百分比表示为6.5-10％。
  19. 根据权利要求1或5所述的高模量玻璃纤维组合物，其特征在于，MgO的含量以重量百分比表示为大于12％且小于等于13％。
  20. 根据权利要求1所述的高模量玻璃纤维组合物，其特征在于，所述玻璃纤维组合物含有下述组分，各组分的含量以重量百分比表示如下：
    Figure PCTCN2016075780-appb-100009
    并且，重量百分比的比值C1＝(Li2O+Na2O+K2O)/(Y2O3+La2O3)的范围为大于0.26。
  21. 根据权利要求1或12所述的高模量玻璃纤维组合物，其特征在于，所述高模量玻璃纤维组合物还含有CeO2，其含量以重量百分比表示为0-1％。
  22. 一种玻璃纤维，其特征在于，所述玻璃纤维由如权利要求1-21中任一项所述的玻璃纤维组合物制成。
  23. 根据权利要求22所述的玻璃纤维，其特征在于，所述玻璃纤维的弹性模量范围为90-103GPa。
  24. 一种复合材料，其特征在于，所述复合材料包括如权利要求22或23中所述的玻璃纤维。
PCT/CN2016/075780 2016-02-29 2016-03-07 一种高模量玻璃纤维组合物及其玻璃纤维和复合材料 WO2016165506A2 (zh)

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