WO2019196590A1 - 一种高模量玻璃纤维组合物以及玻璃纤维 - Google Patents

一种高模量玻璃纤维组合物以及玻璃纤维 Download PDF

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WO2019196590A1
WO2019196590A1 PCT/CN2019/078061 CN2019078061W WO2019196590A1 WO 2019196590 A1 WO2019196590 A1 WO 2019196590A1 CN 2019078061 W CN2019078061 W CN 2019078061W WO 2019196590 A1 WO2019196590 A1 WO 2019196590A1
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weight
glass
glass fiber
content
mgo
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PCT/CN2019/078061
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English (en)
French (fr)
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韩利雄
刘奇
何建明
郝名扬
张聪
赵世斌
樊正华
张亮
张燕
刘也
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重庆国际复合材料股份有限公司
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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
    • 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

Definitions

  • the invention relates to the technical field of inorganic non-metal materials, in particular to a high modulus glass fiber composition and a glass fiber.
  • Glass fiber is an inorganic non-metallic material. It has many advantages such as high mechanical strength, good electrical insulation, strong heat resistance, and stable physical and chemical properties. It is widely used in aerospace, automotive, marine, petrochemical, energy, electric power, construction, etc. In many fields, it is currently the most widely used inorganic fiber reinforced material. Because it is mainly used as a reinforcing substrate, the mechanical properties of glass fiber are particularly important, and with the increasing trend of glass fiber composites becoming larger and lighter, the mechanical properties of glass fibers, especially specific strength and specific modulus. Modulus puts higher and higher requirements.
  • S glass and R glass The basic composition of the S glass is: 65 wt% of SiO 2 , 25 wt% of Al 2 O 3 , and 10 wt% of MgO.
  • S glass fiber theoretical monofilament strength of up to 4500 MPa, elastic modulus of more than 85 GPa, excellent mechanical properties.
  • its molding temperature exceeds 1470 ° C, and it is easy to devitrify, which is very difficult to produce and cannot be widely applied.
  • R glass is also a high-strength modulus fiberglass, which is generally composed of SiO 2 , Al 2 O 3 , CaO, MgO, and is generally considered to be a compromise between production difficulty and mechanical properties, and thus compared to S glass. More productive.
  • Chinese patent CN200480015986.4 discloses a glass fiber composition comprising 50 to 65 wt% of SiO 2 , 12 to 20 wt% of Al 2 O 3 , 13 to 16 wt% of CaO, and 6 to 12 wt% of MgO, 0 to 3 wt% of B 2 O 3 , 0 to 3 wt% of TiO 2, 0 to 2 wt% of K 2 O+Na 2 O.
  • the glass fiber belongs to R-grade glass. By controlling the content of Al 2 O 3 and CaO, good mechanical properties and melting properties are obtained, but the specific modulus is only 35-36 MPa.kg -1 .m 3 , which is difficult to meet higher performance. demand.
  • Chinese patent CN200680041114.4 discloses a high performance glass fiber composition containing 60.5 to 70.5 wt% of SiO 2 , 10 to 24.5 wt% of Al 2 O 3 , 6 to 20 wt% of RO, and 0 to 3 wt%. R 2 O.
  • the patented glass fiber composition is also in the category of R-grade glass, but its published scope of rights is too broad, and it is difficult for people in the industry to easily achieve its technical goals through its technical solutions.
  • Japanese Patent JP2003171143 also describes a high-strength high-modulus glass fiber containing 55 to 65 wt% of SiO 2 , 17 to 23 wt% of Al 2 O 3 , 7 to 15 wt% of MgO, and 2 to 6 wt% of CaO. 1 to 7 wt% of TiO 2 .
  • the mechanical properties of the glass fiber are sacrificed, the molding properties are obviously improved, and the molding temperature is about 1340 to 1380 °C.
  • the glass fiber has a high content of TiO 2 , which makes the glass darker, which limits its application in some fields.
  • U.S. Patent Publication No. US 2010/0160139 discloses a high strength glass fiber composition comprising: 64 to 75 wt% SiO 2 , 16 to 24 wt% Al 2 O 3 , 8 to 12 wt% MgO, 0.25 to 3 wt. % Li 2 O+Na 2 O. Compared with S glass fiber, this glass fiber adds a certain amount of Li 2 O and Na 2 O, thereby improving the high temperature melting of the glass and reducing the difficulty of glass fiber formation.
  • Patent No. CN201080070857.0 discloses a high strength glass fiber comprising a composition comprising: 56 to 61 wt% SiO 2 , 16 to 23 wt% Al 2 O 3 , 8 to 12 wt% MgO, 6 to 10 wt. % CaO, 0 to 2 wt% Na 2 O, less than 1 wt% Li 2 O, and less than 2 wt% transition metal oxide.
  • the glass fiber does obtain good mechanical properties, but it can be seen from its actual embodiment that it has added more than 1% of Na 2 O due to the reduced amount of Li 2 O, in order to balance its production difficulty. May bring more side effects.
  • the technical problem to be solved by the present invention is to provide a high modulus glass fiber composition and glass fiber having high modulus, excellent mechanical properties and low viscosity molding properties.
  • the present invention provides a high modulus glass fiber composition comprising the following components:
  • the SiO 2 content is 50 wt% to 54.8 wt%; the Al 2 O 3 content is 23.1 wt% to 27.8 wt%; and the total content of the SiO 2 and Al 2 O 3 is 74.5 wt% to 80.6. Wt%.
  • the TiO 2 content is from 0.2% by weight to 1.0% by weight.
  • the CaO content is 6.2 wt% to 8.0 wt%; the MgO content is 10 wt% to 12 wt%; the total content of CaO and MgO is 16.8 wt% to 19.8 wt%; the MgO/CaO mass
  • the score ratio is 1.25 to 1.95.
  • the ZrO 2 content is from 0.2 wt% to 0.9 wt%.
  • the ZnO content is from 0.2% by weight to 0.9% by weight.
  • the Fe 2 O 3 content is from 0.2 wt% to 0.5 wt%.
  • the B 2 O 3 content is from 1.0 wt% to 3.0 wt%.
  • the total content of the Na 2 O, K 2 O and Li 2 O is 0.2% by weight to 0.8% by weight.
  • the present invention provides a high modulus glass fiber prepared by the composition described in the above technical solution.
  • the present invention provides a high modulus glass fiber composition
  • a high modulus glass fiber composition comprising the following components: SiO 2 50 wt% to 55.9 wt%; Al 2 O 3 20.5 wt% to 28.5 wt%; SiO 2 and The total content of Al 2 O 3 is 72.5 wt% to 82.5 wt%; the mass ratio of Al 2 O 3 /SiO 2 is 0.38 to 0.56; B 2 O 3 0 to 3.0 wt%; TiO 2 is 0.2 wt% to 1.5 wt%; 0 to 2.0 wt%; ZrO 2 0 to 2.0 wt%; Fe 2 O 3 0.1 wt% to 0.6 wt%; CaO 6 wt% to 8.1 wt%; MgO 9 wt% to 12 wt%; total content of CaO and MgO 15.8 wt% 20 wt%; MgO/CaO mass fraction ratio 1.2 to 2.0; total content of Na 2 O
  • the present invention provides high modulus glass fiber compositions as well as glass fibers, which can be implemented by those skilled in the art with appropriate modifications to the process parameters. It is to be noted that all such alternatives and modifications are obvious to those skilled in the art and are intended to be within the scope of the invention.
  • the method and the application of the present invention have been described by the preferred embodiments, and it is obvious that the method and application of the present invention may be modified or combined and modified to achieve and apply the present invention without departing from the scope of the present invention. Invention technology.
  • the present invention provides a high modulus glass fiber composition comprising the following components:
  • the silicon dioxide (SiO 2 ) is one of the main oxides forming a glass network, and mainly serves to improve the mechanical strength, chemical stability and thermal stability of the glass, but excessively high content increases the viscosity of the glass. And the melting temperature, resulting in glass fiber forming difficulty and production costs are high.
  • the SiO 2 content in the high composition of the present invention is from 50% by weight to 55.9% by weight, preferably from 50% by weight to 54.8% by weight; more preferably from 50.2% by weight to 54.8% by weight; most preferably from 50.4% by weight to 54.8% by weight.
  • Alumina is also one of the main oxides forming a glass network. It has a positive effect on improving the chemical stability and mechanical strength of the glass, especially the glass elastic modulus. However, if the Al 2 O 3 content is too high, In addition, the viscosity of the glass is too large, the glass is difficult to form fibers, and the problem of crystallization is prone to occur.
  • the Al 2 O 3 content in the composition of the present invention is from 20.5 wt% to 28.5 wt%, preferably from 23.1 wt% to 27.8 wt%; more preferably from 24.1 wt% to 27.8 wt%.
  • the ratio of total content and mass fraction of Al 2 O 3 and SiO 2 is important for the elastic modulus of aluminosilicate glass.
  • the higher the relative ratio of Al 2 O 3 the larger the elastic modulus of glass, but the difficulty in production and the crystallization.
  • the tendency is also significantly increased, and the present invention defines a total content of SiO 2 and Al 2 O 3 of from 72.5 wt% to 82.5 wt%, preferably from 74.5 wt% to 80.6 wt%; more preferably from 74.5 wt% to 79.4 wt%.
  • the Al 2 O 3 /SiO 2 mass fraction ratio is 0.38 to 0.56.
  • the Al 2 O 3 /SiO 2 mass fraction ratio is 0.40 to 0.54; more preferably 0.40 to 0.50; the ratio range can ensure that the glass fiber has Optimum modulus of elasticity and melt drawing performance, crystallization temperature.
  • TiO 2 titanium dioxide
  • the addition of titanium dioxide helps to improve the high temperature fluidity and crystallization tendency of the glass, and improves the mechanical properties and corrosion resistance of the glass fiber.
  • the content of titanium dioxide should not exceed 1.5% by weight, otherwise it will affect the color of the glass.
  • the content of TiO 2 of the present invention is from 0.2% by weight to 1.5% by weight, preferably from 0.2% by weight to 1.0% by weight; more preferably from 0.2% by weight to 0.9% by weight; most preferably from 0.2% by weight to 0.8% by weight.
  • Zinc oxide (ZnO) and zirconia (ZrO 2 ) may be added to the glass fiber of the present invention, and such an oxide having a small ionic radius and a large electric field strength has an effect of improving glass crystallization property, improving elastic modulus and glass chemical stability. effect.
  • the ZnO content is 0 to 2.0% by weight, preferably, the ZnO content is not 0, more preferably 0.2% by weight to 0.9% by weight; most preferably 0.3% by weight to 0.8% by weight; and the ZrO 2 content is 0%.
  • the small amount of Fe 2 O 3 contained therein is favorable for heat transfer in the kiln, but if the content is too high, it has an adverse effect on the color and heat transfer performance of the glass fiber.
  • the iron oxide content of the present invention is limited to 0.1% by weight to 0.6% by weight.
  • Calcium oxide (CaO) and magnesium oxide (MgO) have the effect of lowering the viscosity of the glass at a high temperature and improving the tendency of the glass to devitrify.
  • the MgO ion radius is smaller than CaO, so the higher MgO ratio helps to form a denser glass network structure and increase the glass elastic modulus.
  • the MgO content is too high, the production difficulty will become unacceptable.
  • the CaO content of the present invention is 6 wt% to 8.1 wt%, preferably, the CaO content is 6.2 wt% to 8.0 wt%, and most preferably, the CaO content is 6.4 wt% to 8.0 wt%, and the MgO content is 9 wt% to 12 wt%. %, preferably from 10% by weight to 12% by weight; more preferably from 10.2% by weight to 11.8% by weight; the total content of CaO and MgO is from 15.8% by weight to 20% by weight, preferably from 16.8% by weight to 19.8% by weight.
  • the MgO/CaO mass fraction ratio is 1.2 to 2.0.
  • the MgO/CaO mass fraction ratio is 1.25 to 1.95.
  • the glass fiber composition of the present invention further contains one or more of Li 2 O, Na 2 O and K 2 O, which contribute to lowering the viscosity of the glass and improving the tendency of the glass to devitrify.
  • the Li 2 O, Na 2 O and K 2 O contents are not too high, otherwise the chemical stability and mechanical properties of the glass may be impaired.
  • the total content of Na 2 O, K 2 O and Li 2 O in the glass composition of the present invention is from 0.2% by weight to 1.0% by weight.
  • boron oxide B 2 O 3
  • a certain amount of B 2 O 3 can enter the glass network to strengthen the network strength, thereby improving the mechanical properties of the glass, and it also helps to lower the high temperature viscosity of the glass, accelerate the clarification, and improve the crystallization tendency of the glass.
  • the glass composition of the present invention has a B 2 O 3 content of 0 to 3 wt%, preferably 1.0 wt% to 3.0 wt%, more preferably 1.2 wt% to 2.5 wt%.
  • the glass fiber composition of the present invention may further contain not more than 3 wt% of F 2 , Y 2 O 3 , BaO, in order to improve the glass fiber forming property without affecting the mechanical properties of the glass fiber.
  • F 2 , Y 2 O 3 , BaO a glass fiber composition of the present invention
  • the glass fiber composition of the present invention may further contain not more than 3 wt% of F 2 , Y 2 O 3 , BaO, in order to improve the glass fiber forming property without affecting the mechanical properties of the glass fiber.
  • La 2 O 3 and CeO 2 One or more of La 2 O 3 and CeO 2 .
  • the glass fiber not only has an extremely high elastic modulus, but also has a melt drawing property and a crystallization temperature within an acceptable range; Adding a suitable ratio of Na 2 O, K 2 O and Li 2 O content helps to lower the glass melting temperature and production difficulty.
  • the high modulus glass fiber composition comprises the following components:
  • the high modulus glass fiber composition comprises the following components:
  • the present invention also provides a high modulus glass fiber prepared from the above composition.
  • the method for preparing the glass fiber of the present invention is not particularly limited, and may be a method well known to those skilled in the art, preferably produced by a pool kiln method, and specifically prepared according to the following method:
  • the glass liquid is subjected to cooling, effluent and wire drawing treatment to obtain glass fibers.
  • the invention firstly mixes various raw materials in a mixing tank, mixes them uniformly, and then transports them to the kiln silo; then the pool kiln silo puts the mixture into the kiln and melts at 1400-1800 ° C, Clarification and homogenization to obtain a glass liquid;
  • the glass filaments are spray cooled and sizing coated to obtain glass fibers.
  • the glass fibers were obtained, the glass fibers were subjected to performance tests.
  • the experimental results show that the molding temperature of the glass fiber of the invention does not exceed 1350 ° C, the upper limit temperature of crystallization is lower than 1300 ° C, and the elastic modulus of the glass fiber is greater than 95 GPa or even greater than 97 GPa.
  • the raw materials are conveyed to the mixing tank, and after being uniformly mixed, the mixed materials are sent to the kiln silo, and the contents of the raw materials are as shown in Table 1;
  • the mixture in the silo silo is put into the tank kiln.
  • the mixture In the tank kiln, the mixture is gradually melted into a glass liquid at a high temperature of 1400 ° C or higher. After clarification and homogenization, the stable and high-quality glass liquid enters the drawing operation channel. ;
  • the glass liquid in the drawing working channel After cooling the glass liquid in the drawing working channel to a suitable temperature, it flows out through the platinum leakage plate, and is quickly drawn into a glass wire with a diameter of 3 to 25 ⁇ m by a wire drawing machine.
  • the glass wire is spray-cooled, sizing coated, bundled, and wound on a wire drawing machine.
  • Table 1 shows the formulation and properties of the glass fiber provided by the examples and comparative examples of the present invention.
  • the preparation method was the same as that of the examples except that the contents of various raw materials were changed, as shown in Table 1.
  • Table 1 shows the formulation and performance data sheets of the glass fibers provided in the examples and comparative examples of the present invention.
  • the various raw materials were transported to the mixing tank, and after being uniformly mixed, the mixed materials were transferred to the kiln silo, and the contents of the raw materials were as shown in Table 1;
  • the mixture in the silo silo is put into the tank kiln.
  • the mixture In the tank kiln, the mixture is gradually melted into a glass liquid at a high temperature of 1400 ° C or higher. After clarification and homogenization, the stable and high-quality glass liquid enters the drawing operation channel. ;
  • the glass liquid in the drawing working channel After cooling the glass liquid in the drawing working channel to a suitable temperature, it flows out through the platinum leakage plate, and is quickly drawn into a glass wire with a diameter of 3 to 25 ⁇ m by a wire drawing machine.
  • the glass wire is spray-cooled, sizing coated, bundled, and wound on a wire drawing machine.
  • Table 1 is a table of the formulation and performance data of the glass fiber provided in the examples and the comparative examples of the present invention.
  • the present invention improves the overall performance of glass fibers by precisely adjusting various components and their specific contents.

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Abstract

一种高模量玻璃纤维组合物，包括：SiO 250wt％～55.9wt％；Al 2O 320.5wt％～28.5wt％；SiO 2与Al 2O 3的总含量72.5wt％～82.5wt％；Al 2O 3/SiO 2质量分数比值0.38～0.56；B 2O 3 0～3.0wt％；TiO 2 0.2wt％～1.5wt％；ZnO 0～2.0wt；ZrO 2 0～2.0wt；Fe 2O 3 0.1wt％～0.6wt％；CaO6wt％～8.1wt％；MgO 9wt％～12wt％；CaO与MgO的总含量15.8wt％～20wt％；MgO/CaO质量分数比值1.2～2.0；Na 2O、K 2O与Li 2O的总含量0.2wt％～1.0wt％；上述组分总计100％。

Description

一种高模量玻璃纤维组合物以及玻璃纤维 技术领域
本发明涉及无机非金属材料技术领域，尤其涉及一种高模量玻璃纤维组合物以及玻璃纤维。
背景技术
玻璃纤维属于无机非金属材料，它具有机械强度高、电绝缘性好、耐热性强、物理化学性质稳定等诸多优点，广泛应用于航空航天、汽车、船舶、石化、能源、电力、建筑等诸多领域，是目前应用量最大的无机纤维增强材料。由于主要用作增强基材，玻璃纤维的力学性能就显得尤为重要，而且随着玻璃纤维复合材料日益大型化、轻量化的发展趋势，人们对玻璃纤维的力学性能尤其是比强度、比模量模量提出越来越高的要求。
对于提升玻璃纤维强度和模量的方法，目前已有许多的相关研究。最典型的就是S玻璃和R玻璃。S玻璃的基本组成为：65wt％的SiO 2，25wt％的Al 2O 3，10wt％的MgO。S玻璃纤维理论单丝强度高达4500MPa，弹性模量超过85GPa，力学性能非常优异。但它的成型温度超过了1470℃，且极易析晶，生产难度很大，无法实现大规模推广应用。R玻璃也是一种高强度搞模量玻璃纤维，它一般是由SiO 2、Al 2O 3、CaO、MgO组成，一般被认为是生产难度和力学性能的一种折衷，从而比起S玻璃，更具有生产可行性。
中国专利CN200480015986.4公开了一种玻璃纤维组合物，它含有50～65wt％的SiO 2，12～20wt％的Al 2O 3，13～16wt％的CaO，6～12wt％的MgO，0～3wt％的B 2O 3，0～3wt％的TiO 2，0～2wt％的K 2O+Na 2O。该玻璃纤维属于R级玻璃，通过控制Al 2O 3和CaO含量获得了较好的力学性能和熔化性能，但比模量只有35-36MPa.kg -1.m 3，难以满足更高性能的需求。
中国专利CN200680041114.4公开了一种高性能玻璃纤维组合物，它含有60.5～70.5wt％的SiO 2，10～24.5wt％的Al 2O 3，6～20wt％的RO，0～3wt％的R 2O。该专利玻璃纤维组合物其实也属于R级玻璃范畴，但其公布的权利范围过于宽泛，一般行业内人员难以通过其技术方案轻易的实现其技术目标。
日本专利JP2003171143也描述了一种高强度高模量玻璃纤维，它含有55～65wt％的SiO 2，17～23wt％的Al 2O 3，7～15wt％的MgO，2～6wt％的CaO，1～7wt％的 TiO 2。比起S玻璃，该玻璃纤维虽然力学性能有所牺牲，但成型性能有了明显改善，成型温度约为1340～1380℃。但该玻纤中TiO 2含量很高，使得玻璃颜色偏深，这限制了其在某些领域的应用。
公开号为US2010/0160139的美国专利公开了一种高强度玻璃纤维组合物，包括：64～75wt％的SiO 2，16～24wt％的Al 2O 3，8～12wt％的MgO，0.25～3wt％的Li 2O+Na 2O。相对于S玻纤，这种玻璃纤维加入了一定量的Li 2O与Na 2O，从而改善玻璃的高温熔化情况，降低玻纤成型难度。
申请号为CN201080070857.0的专利公开了一种高强度玻璃纤维，其组合物包含：56～61wt％的SiO 2，16～23wt％的Al 2O 3，8～12wt％的MgO，6～10wt％的CaO，0～2wt％的Na 2O，小于1wt％的Li 2O，以及小于2wt％的过渡金属氧化物。该玻璃纤维确实获得了良好的机械性能，但从其实际实施例中可看到，由于减少了Li 2O用量，为了平衡其生产难度，它又加入了超过1％的Na 2O，而这可能带来更多副作用。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种高模量玻璃纤维组合物以及玻璃纤维，具有高模量、优异的力学性能和较低粘度的成型性能。
本发明提供了一种高模量玻璃纤维组合物，包括如下组分：
Figure PCTCN2019078061-appb-000001
上述组分总计100％。
优选的，所述SiO 2含量为50wt％～54.8wt％；所述Al 2O 3含量为23.1wt％～27.8wt％；所述SiO 2与Al 2O 3的总含量为74.5wt％～80.6wt％。
优选的，所述TiO 2含量为0.2wt％～1.0wt％。
优选的，所述CaO含量为6.2wt％～8.0wt％；所述MgO含量为10wt％～12wt％；所述CaO与MgO的总含量为16.8wt％～19.8wt％；所述MgO/CaO质量分数比值为1.25～1.95。
优选的，所述ZrO 2含量为0.2wt％～0.9wt％。
优选的，所述ZnO含量为0.2wt％～0.9wt％。
优选的，所述Fe 2O 3含量为0.2wt％～0.5wt％。
优选的，所述B 2O 3含量为1.0wt％～3.0wt％。
优选的，所述Na 2O、K 2O与Li 2O的总含量0.2wt％～0.8wt％。
本发明提供了一种高模量玻璃纤维，由上述技术方案所述的组合物制备得到。
与现有技术相比，本发明提供了一种高模量玻璃纤维组合物，包括如下组分：SiO 250wt％～55.9wt％；Al 2O 3 20.5wt％～28.5wt％；SiO 2与Al 2O 3的总含量72.5wt％～82.5wt％；Al 2O 3/SiO 2质量分数比值0.38～0.56；B 2O 3 0～3.0wt％；TiO 20.2wt％～1.5wt％；ZnO 0～2.0wt％；ZrO 2 0～2.0wt％；Fe 2O 30.1wt％～0.6wt％；CaO6wt％～8.1wt％；MgO 9wt％～12wt％；CaO与MgO的总含量15.8wt％～20wt％；MgO/CaO质量分数比值1.2～2.0；Na 2O、K 2O与Li 2O的总含量0.2wt％～1.0wt％；上述组分总计100％。本发明通过控制上述各组分的特定百分比含量，使得最终得到的高模量玻璃纤维组合物具有高模量、优异的力学性能和较低粘度的成型性能。
具体实施方式
本发明提供了高模量玻璃纤维组合物以及玻璃纤维，本领域技术人员可以借鉴本文内容，适当改进工艺参数实现。特别需要指出的是，所有类似的替换和改动对本领域技术人员来说是显而易见的，它们都属于本发明保护的范围。本发明的方法及应用已经通过较佳实施例进行了描述，相关人员明显能在不脱离本发明内容、精神和范围内对本文的方法和应用进行改动或适当变更与组合，来实现和应用本发明技术。
本发明提供了一种高模量玻璃纤维组合物，包括如下组分：
Figure PCTCN2019078061-appb-000002
上述组分总计100％。
其中，所述二氧化硅(SiO 2)是形成玻璃网络的主要氧化物之一，它主要起提高玻璃的机械强度、化学稳定性和热稳定性的作用，但含量过高会增加玻璃的粘度和熔化温度，导致玻璃纤维成型难度和生产成本偏高。本发明高组合物中SiO 2含量为50wt％～55.9wt％，优选为50wt％～54.8wt％；更优选为50.2wt％～54.8wt％；最优选为50.4wt％～54.8wt％。
氧化铝(Al 2O 3)也是形成玻璃网络的主要氧化物之一，它对提高玻璃化学稳定性和机械强度、尤其是玻璃弹性模量有积极作用，但若Al 2O 3含量过高，又会使得玻璃粘度过大，玻璃成纤困难，还容易出现析晶问题。本发明组合物中Al 2O 3含量为20.5wt％～28.5wt％，优选为23.1wt％～27.8wt％；更优选为24.1wt％～27.8wt％。
所述Al 2O 3和SiO 2总含量和质量分数比值对铝硅酸盐玻璃弹性模量有重要意义，Al 2O 3相对比例越高，玻璃弹性模量大，但同时生产难度和析晶倾向也会显著增加，本发明限定SiO 2与Al 2O 3的总含量为72.5wt％～82.5wt％，优选为74.5wt％～80.6wt％；更优选为74.5wt％～79.4wt％。Al 2O 3/SiO 2质量分数比值为0.38～0.56，优选的，所述Al 2O 3/SiO 2质量分数比值为0.40～0.54；更优选为0.40～0.50；该比例范围能够保证玻璃纤维具有最佳的弹性模量和熔融拉丝性 能、析晶温度。
二氧化钛(TiO 2)的添加有助于改善玻璃高温流动性和析晶倾向，提高玻璃纤维机械性能和耐腐蚀性能。但二氧化钛的含量不宜超过1.5wt％，否则会影响玻璃颜色。本发明TiO 2的含量为0.2wt％～1.5wt％，优选为0.2wt％～1.0wt％；更优选为0.2wt％～0.9wt％；最优选为0.2wt％～0.8wt％。
本发明玻璃纤维中可以添加氧化锌(ZnO)和氧化锆(ZrO 2)，这类离子半径小、电场强度大的氧化物，具有改善玻璃析晶性能、提高弹性模量和玻璃化学稳定性的作用。本发明中，ZnO含量为0～2.0wt％，优选的，ZnO含量不为0，更优选为0.2wt％～0.9wt％；最优选为0.3wt％～0.8wt％；ZrO 2含量为0～2.0wt％，优选的，ZrO 2含量不为0，更优选为0.2wt％～0.9wt％；最优选为0.2wt％～0.7wt％。
其中所含的少量的Fe 2O 3有利于池窑热量传递，但如果含量过高，对玻璃纤维的颜色和传热性能都有不利影响。本发明氧化铁含量限定为0.1wt％～0.6wt％。
氧化钙(CaO)和氧化镁(MgO)具有降低玻璃高温粘度、改善玻璃析晶倾向的作用。其中MgO离子半径小于CaO，因而较高的MgO比例，有助于形成更致密的玻璃网络结构，提升玻璃弹性模量。但如果MgO含量过高，生产难度会变得难以接受。本发明所述CaO含量为6wt％～8.1wt％，优选的，CaO含量为6.2wt％～8.0wt％，最优选的，CaO含量为6.4wt％～8.0wt％，MgO含量为9wt％～12wt％，优选为10wt％～12wt％；更优选为10.2wt％～11.8wt％；CaO与MgO的总含量为15.8wt％～20wt％，优选为16.8wt％～19.8wt％。MgO/CaO质量分数比值为1.2～2.0，优选的，所述MgO/CaO质量分数比值为1.25～1.95。
本发明所述玻璃纤维组合物中还含有Li 2O、Na 2O和K 2O中的一种或多种，它们有助于降低玻璃粘度，改善玻璃析晶倾向。但Li 2O、Na 2O和K 2O含量也不可太高，否则会损害玻璃的化学稳定性和力学性能。本发明玻璃组合物中Na 2O、K 2O与Li 2O总含量为0.2wt％～1.0wt％。
本发明特别的，还在所述玻璃纤维组合物中添加了一定量的氧化硼(B 2O 3)。少量的B 2O 3可以进入玻璃网络中加强网络强度，从而提高玻璃力学性能，同时它还有助于降低玻璃高温粘度、加速澄清、改善玻璃析晶倾向作用。本发明玻璃组合物B 2O 3含量为0～3wt％，优选为1.0wt％～3.0wt％，更优选为1.2wt％～2.5wt％。
按照本发明，作为优选方案，在不影响玻璃纤维力学性能的前提下，为了改善玻璃纤维成型性能，本发明玻璃纤维组合物还可以含有不超过3wt％的F 2、Y 2O 3、BaO、La 2O 3、CeO 2中的一种或多种。
本发明通过精确控制Al 2O 3/SiO 2和MgO/CaO的比例和各自含量范围，使得玻璃纤维不仅具有极高的弹性模量，同时熔融拉丝性能和析晶温度均在可接受范围内；加入合适比例的Na 2O、K 2O与Li 2O含量，则有助于降低玻璃熔融温度和生产难度。而引入少量离子半径小、电场强度大的ZnO和ZrO 2，并限定ZnO和ZrO 2含量，又可以进一步抑制玻璃析晶倾向，并对玻璃弹性模量也有积极作用；因此，由于本发明玻璃纤维中含有上述组分，并精确控制各组分的含量和比例，从而使得玻璃纤维获得了优异的力学性能和较低粘度的成型性能。
在本发明一部分优选实施方案中，所述高模量玻璃纤维组合物，包括如下组分：
Figure PCTCN2019078061-appb-000003
上述组分总计100％。
在本发明一部分优选实施方案中，所述高模量玻璃纤维组合物，包括如下组分：
Figure PCTCN2019078061-appb-000004
Figure PCTCN2019078061-appb-000005
上述组分总计100％。
本发明还提供了一种高模量玻璃纤维，由上述组合物制备得到。
本发明对所述玻璃纤维的制备方法没有特别的限制，可以为本领域技术人员熟知的方法，优选为池窑法生产，具体可以按照下述方法制备：
将各种原料混合均匀后投入池窑，经熔化、澄清、均化后，得到玻璃液；
将所述玻璃液经冷却、流出和拉丝处理后得到玻璃纤维。
本发明首先将各种原料在混料罐中混合，混合均匀后，将其输送至池窑料仓；然后池窑料仓将混合料投入池窑，在1400～1800℃的条件下进行熔化、澄清和均化，得到玻璃液；
将所述玻璃液冷却至1250～1350℃，经铂金漏板流出，在拉丝机的牵引下，拉丝成直径为3～25μm的玻璃丝；
将所述玻璃丝经过喷雾冷却、浸润剂涂覆得到玻璃纤维。
在得到玻璃纤维后，对所述玻璃纤维进行性能测试。
实验结果表明，本发明玻璃纤维的成型温度不超过1350℃，析晶上限温度低于1300℃，玻璃纤维的弹性模量大于95GPa，甚至大于97GPa。
为了进一步说明本发明，下面结合实施例对本发明提供的高模量玻璃纤维组合物以及玻璃纤维进行详细描述。
实施例1
将各原料输送至混料罐，混合均匀后，将混合料输送至池窑料仓，所述各原料的含量按照表1所示；
将池窑料仓中的混合料投入池窑，在池窑中，混合料经1400℃以上的高温逐渐熔化成玻璃液，经澄清、均化后，稳定而高品质的玻璃液进入拉丝作业通 道；
将拉丝作业通道中的玻璃液冷却至合适温度后，经铂金漏板流出，被拉丝机快速牵引成直径3～25μm的玻璃丝，玻璃丝经喷雾冷却、浸润剂涂覆、集束后，在拉丝机上缠绕成丝饼；
所有丝饼经烘干、络纱或短切等工序后，得到各种类型的玻璃纤维产品。
对所述玻璃纤维进行性能测试，结果参见表1，表1为本发明实施例及比较例提供的玻璃纤维的配方及性能。
实施例2～6
制备方法与实施例相同，只是各种原料的含量发生了变化，具体如表1所示。
对所述玻璃纤维进行性能测试，结果参见表1，表1为本发明实施例及比较例提供的玻璃纤维的配方及性能数据表。
对比例1～2
按照表1所示的配方，将各种原料输送至混料罐，混合均匀后，将混合料输送至池窑料仓，所述各原料的含量按照表1所示；
将池窑料仓中的混合料投入池窑，在池窑中，混合料经1400℃以上的高温逐渐熔化成玻璃液，经澄清、均化后，稳定而高品质的玻璃液进入拉丝作业通道；
将拉丝作业通道中的玻璃液冷却至合适温度后，经铂金漏板流出，被拉丝机快速牵引成直径3～25μm的玻璃丝，玻璃丝经喷雾冷却、浸润剂涂覆、集束后，在拉丝机上缠绕成丝饼；
所有丝饼经烘干、络纱或短切等工序后，得到玻璃纤维。
对所述玻璃纤维进行性能测试，结果参见表1，表1为本发明实施例及对比例提供的玻璃纤维的配方及性能数据表。
表1实施例及对比例提供的玻璃纤维的配方及性能数据表
Figure PCTCN2019078061-appb-000006
Figure PCTCN2019078061-appb-000007
由上述实施例及比较例可知，本发明通过精确调节多种组分及其具体含量，提高了玻璃纤维的综合性能。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (10)

  1. 一种高模量玻璃纤维组合物，其特征在于，包括如下组分：
    Figure PCTCN2019078061-appb-100001
  2. 根据权利要求1所述的组合物，其特征在于，所述SiO 2含量为50wt％～54.8wt％；所述Al 2O 3含量为23.1wt％～27.8wt％；所述SiO 2与Al 2O 3的总含量为74.5wt％～80.6wt％。
  3. 根据权利要求1～2任意一项所述的组合物，其特征在于，所述TiO 2含量为0.2wt％～1.0wt％。
  4. 根据权利要求1～3任意一项所述的组合物，其特征在于，所述CaO含量为6.2wt％～8.0wt％；所述MgO含量为10wt％～12wt％；所述CaO与MgO的总含量为16.8wt％～19.8wt％；所述MgO/CaO质量分数比值为1.25～1.95。
  5. 根据权利要求1～4任意一项所述的组合物，其特征在于，所述ZrO 2含量为0.2wt％～0.9wt％。
  6. 根据权利要求1～5任意一项所述的组合物，其特征在于，所述ZnO含量为0.2wt％～0.9wt％。
  7. 根据权利要求1～6任意一项所述的组合物，其特征在于，所述Fe 2O 3含量为0.2wt％～0.5wt％。
  8. 根据权利要求1～7任意一项所述的组合物，其特征在于，所述B 2O 3含量 为1.0wt％～3.0wt％。
  9. 根据权利要求1～8任意一项所述的组合物，其特征在于，所述Na 2O、K 2O与Li 2O的总含量0.2wt％～0.8wt％。
  10. 一种高模量玻璃纤维，其特征在于，由权利要求1～9任一项所述的组合物制备得到。
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