CN118290033A - Preparation method of T-shaped glass fiber and high-strength transparent composite material thereof - Google Patents

Preparation method of T-shaped glass fiber and high-strength transparent composite material thereof Download PDF

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CN118290033A
CN118290033A CN202410725217.2A CN202410725217A CN118290033A CN 118290033 A CN118290033 A CN 118290033A CN 202410725217 A CN202410725217 A CN 202410725217A CN 118290033 A CN118290033 A CN 118290033A
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glass fiber
glass
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汪庆卫
李云鹏
雷文燕
石艳洁
罗理达
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
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    • C03B37/00Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
    • C03B37/01Manufacture of glass fibres or filaments
    • C03B37/02Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
    • C03B37/022Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
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    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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    • D06N3/0002Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
    • D06N3/0022Glass fibres
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/10Transparent films; Clear coatings; Transparent materials

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Abstract

本发明涉及一种T型玻璃纤维及其高强度透明复合材料的制备方法,以所述T型玻璃纤维中所有玻璃原料总量为基准,按质量百分数计,T型玻璃纤维包括如下的玻璃原料组分:SiO266~72%,Al2O30~7%,K2O和Na2O总量10~12%,CaO和MgO总量10~14%,La2O30~3%,B2O30~3%;将混合均匀的玻璃原料熔化后,通过铂铑合金漏板拉丝,制得T型玻璃纤维;将T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,再络纱成锭织成玻璃纤维织物后,与环氧树脂复合制得高强度透明复合材料。本发明的T型玻璃纤维具有较低的折射率;制法简单;高强度透明复合材料的制法可以确保拉伸强度高的同时透过率高。

The invention relates to a method for preparing a T-glass fiber and a high-strength transparent composite material thereof. Based on the total amount of all glass raw materials in the T-glass fiber, the T-glass fiber includes the following glass raw material components by mass percentage: SiO2 66-72%, Al2O3 0-7 %, K2O and Na2O total 10-12%, CaO and MgO total 10-14%, La2O3 0-3%, B2O3 0-3 %; after the uniformly mixed glass raw materials are melted, they are drawn through a platinum-rhodium alloy plate to obtain the T-glass fiber; after the T-glass fiber is coated with a wetting agent to prepare glass fiber yarn, the yarn is wound into spindles and woven into glass fiber fabric, and then compounded with epoxy resin to obtain the high-strength transparent composite material. The T-glass fiber of the invention has a lower refractive index; the preparation method is simple; and the preparation method of the high-strength transparent composite material can ensure high tensile strength and high transmittance.

Description

一种T型玻璃纤维及其高强度透明复合材料的制备方法A method for preparing T-shaped glass fiber and high-strength transparent composite material thereof

技术领域Technical Field

本发明属于树脂基复合材料技术领域,涉及一种T型玻璃纤维及其高强度透明复合材料的制备方法。The invention belongs to the technical field of resin-based composite materials and relates to a preparation method of a T-shaped glass fiber and a high-strength transparent composite material thereof.

背景技术Background technique

树脂基玻璃纤维增强复合材料(GFRP),俗称玻璃钢,具有良好的力学、化学及耐热性能,广泛应用于各种结构增强材料,如汽车、飞机和高铁等交通工具框架结构,手机、电视等电子器件的外壳、光伏,风电等。然而目前已知的玻璃纤维复合材料都是白色,或在树脂里加入着色剂形成各种色彩。如果树脂基复合材料能做成有机玻璃一样的高透明,同时兼具复合材料的力学和化学性能,将在各种结构上具有广泛的用途。Resin-based glass fiber reinforced composites (GFRP), commonly known as glass fiber reinforced plastics, have good mechanical, chemical and heat resistance properties and are widely used in various structural reinforcement materials, such as the frame structure of vehicles such as automobiles, aircraft and high-speed railways, the shell of electronic devices such as mobile phones and televisions, photovoltaics, wind power, etc. However, the currently known glass fiber composite materials are all white, or colorants are added to the resin to form various colors. If the resin-based composite material can be made as highly transparent as organic glass and have both the mechanical and chemical properties of the composite material, it will have a wide range of uses in various structures.

现有技术中,玻璃纤维增强树脂透明度差,主要原因如下:玻璃纤维的折射率与树脂基不匹配;当光线从一个介质(如玻璃纤维)进入另一个介质(如树脂)时,如果两种介质的折射率不匹配,光线会在界面上发生反射和折射,而不能顺畅地通过。如光线从空气进入玻璃中,其表面反射率计算公式如式(1);In the prior art, glass fiber reinforced resin has poor transparency. The main reasons are as follows: the refractive index of glass fiber does not match that of the resin base; when light enters from one medium (such as glass fiber) into another medium (such as resin), if the refractive index of the two media does not match, the light will be reflected and refracted at the interface and cannot pass smoothly. For example, if light enters glass from air, the surface reflectivity calculation formula is as shown in formula (1);

R=(n玻璃-n空气)2/(n玻璃和n空气)2 (1);R = (n glass - n air ) 2 / (n glass and n air ) 2 (1);

普通平板玻璃的折射率n玻璃为1.50,n空气为1,则一个表面反射率达到4%;玻璃透过率测试为玻璃片前后两个玻璃面,因此总的反射率为8%,国家标准GB 11614-2022《平板玻璃》中引入公式(2)来计算不同厚度的玻璃透过率;The refractive index of ordinary flat glass, nglass , is 1.50, and nair is 1, so the reflectivity of one surface reaches 4%; the glass transmittance test is for the front and back glass surfaces of the glass sheet, so the total reflectivity is 8%. The national standard GB 11614-2022 "Flat Glass" introduces formula (2) to calculate the transmittance of glass of different thicknesses;

T2=92(T1/92)(D 2 /D 1 (2);T 2 =92(T 1 /92) (D 2 /D 1 ) (2);

其中,T1为试样的透过率,单位:%;T2为换算成D2厚度的透过率,单位:%;D1为试样厚度,单位:mm;Wherein, T1 is the transmittance of the sample, unit: %; T2 is the transmittance converted to D2 thickness, unit: %; D1 is the sample thickness, unit: mm;

如果是普通E玻璃纤维,其折射率为1.56,其单一表面反射率R将达到4.79%,则玻璃片双面总透过率仅为90.43%。If it is ordinary E glass fiber, its refractive index is 1.56, and its single surface reflectivity R will reach 4.79%, then the total transmittance of the double-sided glass sheet is only 90.43%.

为了提高树脂基体的折射率,需要引入额外基团,因此耐老化性能较差;在玻璃纤维的制作过程中,为了改善纤维与树脂之间的润湿性和粘附性,通常会涂覆一层浸润剂。然而,这层浸润剂在制备GFRP时很难完全去除,会在纤维和树脂之间形成一层界面,这层界面不仅会影响纤维和树脂之间的粘附力,还会对光线的透过率产生负面影响。光线在通过这层界面时可能会发生散射或反射,从而降低GFRP的透明度。In order to increase the refractive index of the resin matrix, additional groups need to be introduced, so the aging resistance is poor; in the production process of glass fiber, in order to improve the wettability and adhesion between the fiber and the resin, a layer of sizing agent is usually applied. However, this layer of sizing agent is difficult to completely remove when preparing GFRP, and an interface will be formed between the fiber and the resin. This interface will not only affect the adhesion between the fiber and the resin, but also have a negative impact on the transmittance of light. Light may be scattered or reflected when passing through this interface, thereby reducing the transparency of GFRP.

针对玻璃纤维增强树脂透明度不好的问题,已有一些研究尝试解决。例如,CN201310566036.1公开了一种透明玻纤增强聚丙烯复合材料及其制备方法,通过添加5~25%的玻璃纤维来制备透明复合材料,但其透过率均不超过80%,而且当玻璃纤维含量达到25%时,拉伸强度为70 MPa,透过率仅为65%,不能在高拉伸强度的同时具有较高的透过率。Some studies have attempted to solve the problem of poor transparency of glass fiber reinforced resin. For example, CN201310566036.1 discloses a transparent glass fiber reinforced polypropylene composite material and a preparation method thereof, wherein the transparent composite material is prepared by adding 5-25% glass fiber, but the transmittance thereof does not exceed 80%, and when the glass fiber content reaches 25%, the tensile strength is 70 MPa and the transmittance is only 65%, which means that the tensile strength cannot be high while having a high transmittance.

CN201810057510.0公开了架空导线用纤维增强树脂基复合材料透明芯棒及其制备工艺,该专利利用碳纤维和玻璃纤维复合,与热固性树脂制备成透明芯棒,专利中未明确提及透明度,但碳纤维为黑色,其透明度有限。CN201810057510.0 discloses a transparent core rod of a fiber-reinforced resin-based composite material for overhead conductors and its preparation process. The patent utilizes carbon fiber and glass fiber to composite and prepare a transparent core rod with a thermosetting resin. The patent does not explicitly mention transparency, but the carbon fiber is black and its transparency is limited.

CN202311726012.8公开了一种高透光玻璃纤维增强环氧树脂复合材料及其制备方法,其利用E玻璃纤维或S玻璃纤维来实现高透光玻璃纤维增强,利用环氧树脂作为基体,通过商业纤维束处理浸润剂后再涂覆,并加入质量分数为30~70%的玻璃纤维,其制备的透明复合材料厚度仅为0.40mm,根据其88.9%的透过率,换算成2mm的透过率仅为77.5%。CN202311726012.8 discloses a high-transmittance glass fiber reinforced epoxy resin composite material and a preparation method thereof, which utilizes E glass fiber or S glass fiber to achieve high-transmittance glass fiber reinforcement, uses epoxy resin as a matrix, and is coated with a commercial fiber bundle after being treated with a wetting agent, and a glass fiber with a mass fraction of 30 to 70% is added. The thickness of the prepared transparent composite material is only 0.40 mm. Based on its transmittance of 88.9%, the transmittance converted to 2 mm is only 77.5%.

因此,设法解决现有技术中玻璃纤维树脂复合材料不能在高拉伸强度的同时具有较高的透过率的问题,具有十分重要的意义。Therefore, it is of great significance to try to solve the problem in the prior art that glass fiber resin composite materials cannot have high tensile strength and high transmittance at the same time.

发明内容Summary of the invention

本发明的目的是解决现有技术中存在的问题,提供一种T型玻璃纤维及其高强度透明复合材料的制备方法。The purpose of the present invention is to solve the problems existing in the prior art and provide a method for preparing a T-shaped glass fiber and a high-strength transparent composite material thereof.

为达到上述目的,本发明采用的技术方案如下:To achieve the above object, the technical solution adopted by the present invention is as follows:

一种T型玻璃纤维,以所述T型玻璃纤维中所有玻璃原料总量为基准,按质量百分数计,所述T型玻璃纤维包括如下的玻璃原料组分:A T-glass fiber, based on the total amount of all glass raw materials in the T-glass fiber, the T-glass fiber comprises the following glass raw material components in terms of mass percentage:

SiO2 66~72%;SiO 2 66~72%;

Al2O3 0~7%;Al 2 O 3 0~7%;

K2O和Na2O总量 10~12%;Total amount of K 2 O and Na 2 O 10~12%;

CaO和MgO总量 10~14%;Total amount of CaO and MgO 10~14%;

La2O3 0~3%;La 2 O 3 0~3%;

B2O3 1~4%;B 2 O 3 1~4%;

所述玻璃原料中Fe2O3杂质的总含量(质量百分数)≤0.01%;The total content (mass percentage) of Fe 2 O 3 impurities in the glass raw material is ≤0.01%;

SiO2 66~72%,主要提供T型玻璃纤维的玻璃的四面体网络结构,确保玻璃具有良好的耐热性和稳定性,已及较低的熔化温度和成型操作性。SiO 2 66~72%, mainly provides the tetrahedral network structure of T-type glass fiber, ensuring that the glass has good heat resistance and stability, as well as lower melting temperature and molding operability.

Al2O3 0~7%,主要提供T型玻璃纤维的化学稳定性,与SiO2配合使用,降低玻璃的析晶趋势,提高成纤的拉丝窗口,提高合格率,在提高强度方面作用显著。Al 2 O 3 0~7%, mainly provides chemical stability for T-type glass fiber, and is used in conjunction with SiO 2 to reduce the crystallization tendency of glass, increase the fiber drawing window, improve the pass rate, and play a significant role in improving strength.

K2O和Na2O总量 10~12%,T型玻璃纤维的助熔剂,在降低熔化温度的同时,也能提高T型玻璃纤维的电导率,为了降低介电常数,K2O和Na2O的总含量不宜超过12%,其中K2O可以改善透过率和折射率。The total amount of K 2 O and Na 2 O is 10~12%. They are flux for T-glass fibers. While lowering the melting temperature, they can also increase the conductivity of T-glass fibers. In order to lower the dielectric constant, the total content of K 2 O and Na 2 O should not exceed 12%. K 2 O can improve the transmittance and refractive index.

CaO和MgO总量 10~14%,由于碱金属含量受限,为了进一步降低熔化温度,因此加入碱土金属氧化物来助熔,同时MgO也可以提高玻璃网络体强度,提高玻璃纤维力学性能,MgO对提高T玻璃纤维的强度具有较好的调节作用。The total amount of CaO and MgO is 10~14%. Due to the limited alkali metal content, in order to further reduce the melting temperature, alkaline earth metal oxides are added to assist melting. At the same time, MgO can also increase the strength of the glass network and improve the mechanical properties of the glass fiber. MgO has a good regulating effect on improving the strength of T-glass fiber.

La2O3 0~3%,该氧化物主要用于调节T型玻璃纤维的折射率,由于折射率的匹配直接影响了高强度透明复合材料的透过率,因此通过La2O3含量的微调,来实现折射率的精准调配。La 2 O 3 0~3%. This oxide is mainly used to adjust the refractive index of T-type glass fiber. Since the matching of the refractive index directly affects the transmittance of the high-strength transparent composite material, the precise adjustment of the refractive index is achieved by fine-tuning the La 2 O 3 content.

B2O3 1~4%,氧化硼具有进一步降低熔化温度、提高玻璃纤维耐热性能的作用,并起到降低玻璃折射率的作用,在调配折射率方面和熔化温度方面作用显著。B 2 O 3 1~4%, boron oxide has the effect of further reducing the melting temperature, improving the heat resistance of glass fiber, and reducing the refractive index of glass. It plays a significant role in adjusting the refractive index and melting temperature.

玻璃原料中Fe2O3杂质的总含量≤0.01%,严格控制Fe2O3的含量,是为了降低玻璃对可见光及紫外线的吸收系数。The total content of Fe 2 O 3 impurities in glass raw materials is ≤ 0.01%. The content of Fe 2 O 3 is strictly controlled in order to reduce the absorption coefficient of glass to visible light and ultraviolet light.

所述T型玻璃纤维的折射率为1.502~1.512。The refractive index of the T-type glass fiber is 1.502-1.512.

作为优选的技术方案:As the preferred technical solution:

如上所述的一种T型玻璃纤维,以所述T型玻璃纤维中所有玻璃原料总量为基准,按质量百分数计,所述T型玻璃纤维包括如下的玻璃原料组分:The T-glass fiber as described above, based on the total amount of all glass raw materials in the T-glass fiber, the T-glass fiber includes the following glass raw material components in terms of mass percentage:

SiO2 68%;SiO 2 68%;

Al2O3 6%;Al 2 O 3 6%;

K2O和Na2O总量 11%;Total amount of K 2 O and Na 2 O 11%;

CaO和MgO总量 13%;Total amount of CaO and MgO 13%;

La2O3 1%;La 2 O 3 1%;

B2O3 1%;B 2 O 3 1%;

玻璃原料中Fe2O3杂质的总含量为0.006%。The total content of Fe 2 O 3 impurities in the glass raw materials is 0.006%.

如上所述的一种T型玻璃纤维,以所述T型玻璃纤维中所有玻璃原料总量为基准,按质量百分数计,所述T型玻璃纤维包括如下的玻璃原料组分:The T-glass fiber as described above, based on the total amount of all glass raw materials in the T-glass fiber, the T-glass fiber includes the following glass raw material components in terms of mass percentage:

SiO2 72%;SiO 2 72%;

Al2O3 1%Al 2 O 3 1%

K2O和Na2O总量 11%;Total amount of K 2 O and Na 2 O 11%;

CaO和MgO总量 13%;Total amount of CaO and MgO 13%;

B2O3 3%;B 2 O 3 3%;

玻璃原料中Fe2O3杂质的总含量为0.08%。The total content of Fe 2 O 3 impurities in the glass raw materials is 0.08%.

本发明还提供如上任一项所述的一种T型玻璃纤维的制备方法,将混合均匀的玻璃原料在1450~1550℃下熔化3~4小时后,通过铂铑合金漏板拉丝,制得T型玻璃纤维。The present invention also provides a method for preparing a T-shaped glass fiber as described in any of the above items, wherein the uniformly mixed glass raw materials are melted at 1450-1550° C. for 3-4 hours and then drawn through a platinum-rhodium alloy bushing to obtain the T-shaped glass fiber.

本发明还提供一种高强度透明复合材料的制备方法,将如上任一项所述的T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,玻璃纤维纱线络纱成锭织成20~50微米厚的玻璃纤维织物后,与环氧树脂进行复合制得高强度透明复合材料;The present invention also provides a method for preparing a high-strength transparent composite material, comprising coating the T-shaped glass fiber as described in any one of the above items with a sizing agent to prepare a glass fiber yarn, winding the glass fiber yarn into spindles and weaving it into a glass fiber fabric with a thickness of 20 to 50 microns, and then compounding it with an epoxy resin to obtain a high-strength transparent composite material;

浸润剂为折射率1.502~1.512的环氧树脂;The impregnating agent is an epoxy resin with a refractive index of 1.502 to 1.512;

高强度透明复合材料的厚度为2mm,拉伸强度为250MPa以上,透过率为85%以上。The high-strength transparent composite material has a thickness of 2 mm, a tensile strength of more than 250 MPa, and a transmittance of more than 85%.

作为优选的技术方案:As the preferred technical solution:

如上所述的一种高强度透明复合材料的制备方法,浸润剂的涂覆量为0.1~0.5wt%。In the method for preparing a high-strength transparent composite material as described above, the coating amount of the wetting agent is 0.1-0.5wt%.

如上所述的一种高强度透明复合材料的制备方法,高强度透明复合材料中玻璃纤维织物的占比为10~50wt%。In the method for preparing a high-strength transparent composite material as described above, the proportion of glass fiber fabric in the high-strength transparent composite material is 10-50wt%.

发明原理:Principle of the invention:

传统玻璃纤维中的铁元素影响透过率,本发明通过降低铁杂质含量来提高玻璃纤维的透过率。根据超白浮法玻璃行业标准JC/T 2128-2012中定义的:成分中Fe2O3含量不大于0.015%。本发明为了制备高透过率T型玻璃纤维,更需要严格控制原料中Fe2O3含量来实现,因此控制玻璃原料中Fe2O3杂质的总含量≤0.01%。The iron element in traditional glass fiber affects the transmittance. The present invention improves the transmittance of glass fiber by reducing the content of iron impurities. According to the definition in the ultra-white float glass industry standard JC/T 2128-2012: the content of Fe2O3 in the composition is not more than 0.015%. In order to prepare high-transmittance T-type glass fiber, the present invention needs to strictly control the content of Fe2O3 in the raw materials, so the total content of Fe2O3 impurities in the glass raw materials is controlled to be ≤0.01 %.

玻璃纤维纱线之间由于折射率不同会产生折射,本发明采用与T型玻璃纤维具有几乎相同折射率的浸润剂,使得制备的玻璃纤维纱线之间的折射率相同,减少折射;Glass fiber yarns will refraction due to different refractive indices. The present invention uses a sizing agent with almost the same refractive index as the T-type glass fiber, so that the refractive indices of the prepared glass fiber yarns are the same, thereby reducing refraction.

玻璃纤维纱线与树脂基体之间由于折射率不同也会产生反射和折射,本发明通过确保它们之间的折射率基本相同,消除了反射和折射,进一步提高了透明度;Due to the different refractive indices between the glass fiber yarn and the resin matrix, reflection and refraction will also occur. The present invention eliminates reflection and refraction by ensuring that the refractive indices between them are substantially the same, thereby further improving transparency.

传统透明复合材料中的纤维纱线中的浸润剂去除不干净或无法去除,导致光线反射和损耗,本发明由于不需要去除浸润剂,通过使用具有相同折射率的浸润剂,避免了这一问题。The wetting agent in the fiber yarn in the traditional transparent composite material is not removed cleanly or cannot be removed, resulting in light reflection and loss. The present invention avoids this problem by using a wetting agent with the same refractive index because the wetting agent does not need to be removed.

本发明T型玻璃纤维的折射率为1.502~1.512,较普通玻璃纤维的1.54~1.57低,这使得与相同折射率的树脂更容易匹配,提高了复合材料的稳定性,减少了黄变现象。The refractive index of the T-shaped glass fiber of the present invention is 1.502-1.512, which is lower than 1.54-1.57 of common glass fiber, so it is easier to match with resins with the same refractive index, improves the stability of the composite material, and reduces the yellowing phenomenon.

综上所述,本发明制得的高强度透明复合材料在确保拉伸强度为250MPa以上的同时透过率达到85%以上。In summary, the high-strength transparent composite material prepared in the present invention has a transmittance of more than 85% while ensuring a tensile strength of more than 250 MPa.

有益效果:Beneficial effects:

(1)本发明的一种T型玻璃纤维,玻璃原料中Fe2O3杂质的总含量≤0.01%,使T型玻璃纤维具有较低的折射率和较高的透过率;(1) A T-type glass fiber of the present invention, wherein the total content of Fe 2 O 3 impurities in the glass raw material is ≤0.01%, so that the T-type glass fiber has a lower refractive index and a higher transmittance;

(2)本发明的一种T型玻璃纤维的制备方法,过程简单,便于操作;(2) The method for preparing T-shaped glass fiber of the present invention has a simple process and is easy to operate;

(3)本发明的一种高强度透明复合材料的制备方法,采用与T型玻璃纤维具有相同折射率的浸润剂,使得玻璃纤维纱线之间的折射率相同,减少折射,无需去除浸润剂,简化了制备工艺,并使得高强度透明复合材料具有良好的稳定性和耐黄变性能;(3) A method for preparing a high-strength transparent composite material of the present invention uses a sizing agent having the same refractive index as the T-glass fiber, so that the refractive index between the glass fiber yarns is the same, reducing refraction, and there is no need to remove the sizing agent, thereby simplifying the preparation process and making the high-strength transparent composite material have good stability and yellowing resistance;

(4)本发明的一种高强度透明复合材料的制备方法,在保证力学性能的前提下,显著提高光学性能,制得的高强度透明复合材料可以确保拉伸强度为250MPa以上的同时透过率达到85%以上。(4) The method for preparing a high-strength transparent composite material of the present invention significantly improves the optical properties while ensuring the mechanical properties. The prepared high-strength transparent composite material can ensure that the tensile strength is above 250 MPa and the transmittance reaches above 85%.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1为实施例6~10的高强度透明复合材料透过率曲线;其中,T1为实施例6,T2为实施例7,T3为实施例8,T4为实施例9,T5为实施例10。FIG1 is a transmittance curve of high-strength transparent composite materials of Examples 6 to 10; wherein T1 is Example 6, T2 is Example 7, T3 is Example 8, T4 is Example 9, and T5 is Example 10.

具体实施方式Detailed ways

下面结合具体实施方式,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

本发明实施例和对比例中性能指标涉及的测试方法如下:The test methods involved in the performance indicators in the embodiments and comparative examples of the present invention are as follows:

玻璃纤维密度:参考GB/T 5432-2008《玻璃密度测定浮力法》。Glass fiber density: refer to GB/T 5432-2008 "Determination of glass density by buoyancy method".

玻璃纤维折射率:参考GB/T 7962.1-2010 无色光学玻璃测试方法 第1部分:折射率和色散系数。Glass fiber refractive index: refer to GB/T 7962.1-2010 Test method for colorless optical glass Part 1: Refractive index and dispersion coefficient.

玻璃纤维透过率:参考GB/T 7962.12-2010 无色光学玻璃测试方法 第12部分:光谱内透射比,测量GB/T 2680-2021标准中可见光波段透过率的平均值。Glass fiber transmittance: Refer to GB/T 7962.12-2010 Test method for colorless optical glass Part 12: Spectral transmittance, and measure the average transmittance in the visible light band in the GB/T 2680-2021 standard.

玻璃纤维拉伸强度:参考GB/T 31290-2022碳纤维 单丝拉伸性能的测定。Glass fiber tensile strength: refer to GB/T 31290-2022 Determination of tensile properties of carbon fiber monofilament.

玻璃纤维弹性模量:参考GB/T 31290-2022碳纤维 单丝拉伸性能的测定。Glass fiber elastic modulus: refer to GB/T 31290-2022 Determination of tensile properties of carbon fiber monofilament.

复合材拉伸强度:参考GB/T 1447-2005纤维增强塑料拉伸性能试验方法。Composite material tensile strength: refer to GB/T 1447-2005 Test method for tensile properties of fiber reinforced plastics.

复合材料透过率:参考GB/T 2410-2008 透明塑料透光率和雾度的测定,测量GB/T2680-2021标准中可见光波段透过率的平均值。Composite material transmittance: Refer to GB/T 2410-2008 Determination of light transmittance and haze of transparent plastics, and measure the average transmittance in the visible light band in GB/T2680-2021 standard.

实施例1Example 1

一种T型玻璃纤维的制备方法,具体步骤如下:A method for preparing T-shaped glass fiber, the specific steps are as follows:

(1)以T型玻璃纤维中所有玻璃原料的总量为基准,按质量百分数计,T型玻璃纤维包括如下的玻璃原料组分:(1) Based on the total amount of all glass raw materials in T-glass fiber, calculated by mass percentage, T-glass fiber includes the following glass raw material components:

SiO2 68%;SiO 2 68%;

Al2O3 6%;Al 2 O 3 6%;

K2O 1%; K2O 1%;

Na2O 10%; Na2O 10%;

CaO 10%;CaO 10%;

MgO 3%;MgO 3%;

La2O3 1%;La 2 O 3 1%;

B2O3 1%;B 2 O 3 1%;

玻璃原料中Fe2O3杂质的总含量为0.006%;The total content of Fe 2 O 3 impurities in the glass raw materials is 0.006%;

(2)将混合均匀的玻璃原料在1480℃下熔化4小时后,通过铂铑合金漏板拉丝,制得T型玻璃纤维。(2) After the uniformly mixed glass raw materials are melted at 1480°C for 4 hours, they are drawn through a platinum-rhodium alloy wire drawing plate to produce T-shaped glass fibers.

制得的T型玻璃纤维的折射率为1.508。The refractive index of the prepared T-glass fiber is 1.508.

实施例2Example 2

一种T型玻璃纤维的制备方法,具体步骤如下:A method for preparing T-shaped glass fiber, the specific steps are as follows:

(1)以T型玻璃纤维中所有玻璃原料的总量为基准,按质量百分数计,T型玻璃纤维包括如下的玻璃原料组分:(1) Based on the total amount of all glass raw materials in T-glass fiber, calculated by mass percentage, T-glass fiber includes the following glass raw material components:

SiO2 68%;SiO 2 68%;

Al2O3 5%;Al 2 O 3 5%;

Na2O 10%; Na2O 10%;

CaO 12%;CaO 12%;

La2O3 3%;La 2 O 3 3%;

B2O3 2%;B 2 O 3 2%;

玻璃原料中Fe2O3杂质的总含量为0.008%;The total content of Fe 2 O 3 impurities in the glass raw materials is 0.008%;

(2)将混合均匀的玻璃原料在1530℃下熔化3.5小时后,通过铂铑合金漏板拉丝,制得T型玻璃纤维。(2) After the uniformly mixed glass raw materials are melted at 1530°C for 3.5 hours, they are drawn through a platinum-rhodium alloy filter plate to produce T-shaped glass fibers.

制得的T型玻璃纤维的折射率为1.511。The refractive index of the prepared T-glass fiber is 1.511.

实施例3Example 3

一种T型玻璃纤维的制备方法,具体步骤如下:A method for preparing T-shaped glass fiber, the specific steps are as follows:

(1)以T型玻璃纤维中所有玻璃原料的总量为基准,按质量百分数计,T型玻璃纤维包括如下的玻璃原料组分:(1) Based on the total amount of all glass raw materials in T-glass fiber, calculated by mass percentage, T-glass fiber includes the following glass raw material components:

SiO2 72%;SiO 2 72%;

Al2O3 1%;Al 2 O 3 1%;

K2O 1%; K2O 1%;

Na2O 10%; Na2O 10%;

CaO 8%;CaO 8%;

MgO 5%;MgO 5%;

B2O3 3%;B 2 O 3 3%;

玻璃原料中Fe2O3杂质的总含量为0.008%;The total content of Fe 2 O 3 impurities in the glass raw materials is 0.008%;

(2)将混合均匀的玻璃原料在1520℃下熔化3小时后,通过铂铑合金漏板拉丝,制得T型玻璃纤维。(2) After the uniformly mixed glass raw materials are melted at 1520°C for 3 hours, they are drawn through a platinum-rhodium alloy wire drawing plate to produce T-shaped glass fibers.

制得的T型玻璃纤维的折射率为1.502。The refractive index of the prepared T-glass fiber is 1.502.

对比例1Comparative Example 1

一种E型玻璃纤维的制备方法,基本同实施例3,不同之处在于以E型玻璃纤维中所有玻璃原料的总量为基准,按质量百分数计,E型玻璃纤维包括如下的玻璃原料组分:A method for preparing an E-glass fiber is basically the same as that of Example 3, except that the E-glass fiber includes the following glass raw material components, calculated by mass percentage, based on the total amount of all glass raw materials in the E-glass fiber:

SiO2 54%;SiO 2 54%;

Al2O3 16%;Al 2 O 3 16%;

Na2O 0.5%; Na2O 0.5%;

CaO 17%;CaO 17%;

MgO 4.4%;MgO 4.4%;

B2O3 8%;B 2 O 3 8%;

Fe2O3 0.1%。Fe 2 O 3 0.1%.

制得的E型玻璃纤维的折射率为1.560,内透过率仅为92%。The refractive index of the prepared E-type glass fiber is 1.560, and the internal transmittance is only 92%.

将对比例1和实施例3进行对比,可以发现该E型玻璃纤维折射率高、内透过率低,这是因为E型玻璃纤维中原料含有少量Fe2O3,做成玻璃纤维后由于直径变小的原因光线散射,因此呈现灰白色,内透过率低。Comparing Comparative Example 1 with Example 3, it can be found that the E-type glass fiber has a high refractive index and a low internal transmittance. This is because the raw material of the E-type glass fiber contains a small amount of Fe 2 O 3 . After being made into glass fiber, the light is scattered due to the reduced diameter, so it appears grayish white and has a low internal transmittance.

实施例4Example 4

一种T型玻璃纤维的制备方法,具体步骤如下:A method for preparing T-shaped glass fiber, the specific steps are as follows:

(1)以T型玻璃纤维中所有玻璃原料的总量为基准,按质量百分数计,T型玻璃纤维包括如下的玻璃原料组分:(1) Based on the total amount of all glass raw materials in T-glass fiber, calculated by mass percentage, T-glass fiber includes the following glass raw material components:

SiO2 70%;SiO 2 70%;

Al2O3 1%;Al 2 O 3 1%;

Na2O 12%; Na2O 12%;

CaO 10%;CaO 10%;

MgO 2%;MgO 2%;

La2O3 1%;La 2 O 3 1%;

B2O3 4%;B 2 O 3 4%;

玻璃原料中Fe2O3杂质的总含量为0.008%;The total content of Fe 2 O 3 impurities in the glass raw materials is 0.008%;

(2)将混合均匀的玻璃原料在1550℃下熔化3小时后,通过铂铑合金漏板拉丝,制得T型玻璃纤维。(2) After the uniformly mixed glass raw materials are melted at 1550°C for 3 hours, they are drawn through a platinum-rhodium alloy wire drawing plate to produce T-shaped glass fibers.

制得的T型玻璃纤维的折射率为1.506。The refractive index of the prepared T-glass fiber is 1.506.

实施例5Example 5

一种T型玻璃纤维的制备方法,具体步骤如下:A method for preparing T-shaped glass fiber, the specific steps are as follows:

(1)以T型玻璃纤维中所有玻璃原料的总量为基准,按质量百分数计,T型玻璃纤维包括如下的玻璃原料组分:(1) Based on the total amount of all glass raw materials in T-glass fiber, calculated by mass percentage, T-glass fiber includes the following glass raw material components:

SiO2 66%;SiO 2 66%;

Al2O3 7%;Al 2 O 3 7%;

Na2O 10%; Na2O 10%;

CaO 11%;CaO 11%;

MgO 2%;MgO 2%;

La2O3 1.0 %;La 2 O 3 1.0 % ;

B2O3 3%;B 2 O 3 3%;

玻璃原料中Fe2O3杂质的总含量为0.009%;The total content of Fe 2 O 3 impurities in the glass raw materials is 0.009%;

(2)将混合均匀的玻璃原料在1450℃下熔化4小时后,通过铂铑合金漏板拉丝,制得T型玻璃纤维。(2) After the uniformly mixed glass raw materials are melted at 1450°C for 4 hours, they are drawn through a platinum-rhodium alloy wire drawing plate to produce T-shaped glass fibers.

制得的T型玻璃纤维的折射率为1.504。The refractive index of the prepared T-glass fiber is 1.504.

实施例1~5的详细性能数据见表1:The detailed performance data of Examples 1 to 5 are shown in Table 1:

表1Table 1

实施例1Example 1 实施例2Example 2 实施例3Example 3 实施例4Example 4 实施例5Example 5 玻璃纤维密度/ g.cm-3 Glass fiber density/g.cm -3 2.5122.512 2.5212.521 2.5062.506 2.5162.516 2.5182.518 玻璃纤维折射率/ %Glass fiber refractive index/% 1.5081.508 1.5111.511 1.5021.502 1.5061.506 1.5041.504 玻璃纤维内透过率/ %Transmission rate in glass fiber/% 99%99% 99%99% 99%99% 99%99% 99%99% 玻璃纤维拉伸强度/ MPaGlass fiber tensile strength/MPa 12681268 15241524 13661366 13801380 12571257 玻璃纤维弹性模量/ GPaGlass fiber elastic modulus/GPa 7272 7676 7171 7272 7575

实施例6Example 6

一种高强度透明复合材料的制备方法,具体步骤如下:A method for preparing a high-strength transparent composite material, the specific steps are as follows:

(1)原料的准备:(1) Preparation of raw materials:

实施例1的T型玻璃纤维;The T-glass fiber of Example 1;

浸润剂:通过质量比为45:55的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.508的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS:80-04-6;Sizing agent: A composite epoxy resin with a refractive index of 1.508 is prepared by mixing two hydrogenated bisphenol A epoxy resins I102215 and P464946 in a mass ratio of 45:55. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS: 80-04-6;

环氧树脂:通过质量比为45:55的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.508的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS:80-04-6;Epoxy resin: A composite epoxy resin with a refractive index of 1.508 was prepared by mixing two hydrogenated bisphenol A epoxy resins, I102215 and P464946, in a mass ratio of 45:55. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS: 80-04-6;

(2)将T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,玻璃纤维纱线络纱成锭织成35微米厚的玻璃纤维织物后,与环氧树脂进行复合制得高强度透明复合材料;(2) coating T-shaped glass fibers with a sizing agent to prepare glass fiber yarns, winding the glass fiber yarns into spindles to weave glass fiber fabrics with a thickness of 35 μm, and then compounding with epoxy resin to obtain a high-strength transparent composite material;

浸润剂的涂覆量为0.15wt%;高强度透明复合材料中玻璃纤维织物的占比为20wt%。The coating amount of the wetting agent is 0.15wt%; the proportion of the glass fiber fabric in the high-strength transparent composite material is 20wt%.

最终制得的高强度透明复合材料的厚度为2mm,拉伸强度为286MPa,透过率为86.6%。The final high-strength transparent composite material has a thickness of 2 mm, a tensile strength of 286 MPa, and a transmittance of 86.6%.

实施例7Example 7

一种高强度透明复合材料的制备方法,具体步骤如下:A method for preparing a high-strength transparent composite material, the specific steps are as follows:

(1)原料的准备:(1) Preparation of raw materials:

实施例2的T型玻璃纤维;The T-glass fiber of Example 2;

浸润剂:通过质量比为24:76的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.511的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS号:80-04-6;Sizing agent: A composite epoxy resin with a refractive index of 1.511 is prepared by mixing two hydrogenated bisphenol A epoxy resins I102215 and P464946 in a mass ratio of 24:76. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 80-04-6;

环氧树脂:通过质量比为24:76的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.511的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS号:80-04-6;Epoxy resin: A composite epoxy resin with a refractive index of 1.511 was prepared by mixing two hydrogenated bisphenol A epoxy resins, I102215 and P464946, in a mass ratio of 24:76. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 80-04-6;

(2)将T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,玻璃纤维纱线络纱成锭织成50微米厚的玻璃纤维织物后,与环氧树脂进行复合制得高强度透明复合材料;(2) coating T-shaped glass fibers with a sizing agent to prepare glass fiber yarns, winding the glass fiber yarns into spindles to weave glass fiber fabrics with a thickness of 50 μm, and then compounding with epoxy resin to obtain a high-strength transparent composite material;

浸润剂的涂覆量为0.1wt%;高强度透明复合材料中玻璃纤维织物的占比为25wt%。The coating amount of the wetting agent is 0.1wt%; the proportion of the glass fiber fabric in the high-strength transparent composite material is 25wt%.

最终制得的高强度透明复合材料的厚度为2mm,拉伸强度为269MPa,如图1所示,透过率为87.4%。The high-strength transparent composite material finally obtained has a thickness of 2 mm, a tensile strength of 269 MPa, as shown in FIG1 , and a transmittance of 87.4%.

实施例8Example 8

一种高强度透明复合材料的制备方法,具体步骤如下:A method for preparing a high-strength transparent composite material, the specific steps are as follows:

(1)原料的准备:(1) Preparation of raw materials:

实施例3的T型玻璃纤维;The T-glass fiber of Example 3;

浸润剂:通过质量比为76:24的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.502的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS号:80-04-6;Sizing agent: A composite epoxy resin with a refractive index of 1.502 is prepared by mixing two hydrogenated bisphenol A epoxy resins I102215 and P464946 in a mass ratio of 76:24. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 80-04-6;

环氧树脂:通过质量比为76:24的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.502的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS号:80-04-6;Epoxy resin: A composite epoxy resin with a refractive index of 1.502 was prepared by mixing two hydrogenated bisphenol A epoxy resins, I102215 and P464946, in a mass ratio of 76:24. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 80-04-6;

(2)将T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,玻璃纤维纱线络纱成锭织成30微米厚的玻璃纤维织物后,与环氧树脂进行复合制得高强度透明复合材料;(2) coating T-shaped glass fibers with a sizing agent to prepare glass fiber yarns, winding the glass fiber yarns into spindles to weave glass fiber fabrics with a thickness of 30 μm, and then compounding with epoxy resin to obtain high-strength transparent composite materials;

浸润剂的涂覆量为0.3wt%;高强度透明复合材料中玻璃纤维织物的占比为30wt%。The coating amount of the wetting agent is 0.3wt%; the proportion of the glass fiber fabric in the high-strength transparent composite material is 30wt%.

最终制得的高强度透明复合材料的厚度为2mm,拉伸强度为275MPa,如图1所示,透过率为86.2%。The high-strength transparent composite material finally obtained has a thickness of 2 mm, a tensile strength of 275 MPa, as shown in FIG1 , and a transmittance of 86.2%.

对比例2Comparative Example 2

一种透明复合材料的制备方法,基本同实施例8,不同之处仅在于将T型玻璃纤维替换为对比例1的E型玻璃纤维。A method for preparing a transparent composite material is basically the same as that of Example 8, except that the T-type glass fiber is replaced by the E-type glass fiber of Comparative Example 1.

制得的透明复合材料的厚度为2mm,拉伸强度为234MPa,透过率为58.4%。The prepared transparent composite material has a thickness of 2 mm, a tensile strength of 234 MPa, and a transmittance of 58.4%.

将对比例2和实施例8进行对比,可以发现对比例2光学透过率显著降低,从86.2%降低到58.4%,这是因为对比例2中的玻璃纤维中含有的较多的Fe2O3吸收了可见光,同时由于组分不同导致玻璃纤维的折射率不同,对比例2中玻璃纤维与树脂折射率差别较大,玻璃纤维与树脂间的界面反射损失较多,而且还导致光线散射,散射的光线进一步降低了玻璃透过率。Comparing Comparative Example 2 with Example 8, it can be found that the optical transmittance of Comparative Example 2 is significantly reduced, from 86.2% to 58.4%. This is because the glass fiber in Comparative Example 2 contains more Fe2O3 , which absorbs visible light. At the same time, due to the different components, the refractive index of the glass fiber is different. The refractive index of the glass fiber and the resin in Comparative Example 2 is quite different, and the interface reflection loss between the glass fiber and the resin is relatively large. It also causes light scattering, and the scattered light further reduces the glass transmittance.

对比例3Comparative Example 3

一种透明复合材料的制备方法,基本同实施例8,不同之处仅在于浸润剂为通过质量比30:70的氢化双酚A环氧树脂(P464946,厂商:上海阿拉丁生化科技股份有限公司,CAS号:80-04-6)和双酚A型环氧树脂(E-03型,厂商:湖北信康医药化工有限公司,CAS号:25085-99-8)复配的折射率为1.544的复合环氧树脂。A method for preparing a transparent composite material is basically the same as Example 8, except that the wetting agent is a composite epoxy resin with a refractive index of 1.544 compounded by hydrogenated bisphenol A epoxy resin (P464946, manufacturer: Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 80-04-6) and bisphenol A type epoxy resin (E-03 type, manufacturer: Hubei Xinkang Pharmaceutical Chemical Co., Ltd., CAS No.: 25085-99-8) in a mass ratio of 30:70.

制得的透明复合材料的厚度为2mm,拉伸强度为215MPa,透过率为63.6%。The thickness of the prepared transparent composite material is 2 mm, the tensile strength is 215 MPa, and the transmittance is 63.6%.

将对比例3和实施例8进行对比,可以发现对比例3复合材料的拉伸强度降低、光学透过率显著减低,还能看到显著的玻璃纤维织物的纹路,这是因为三个方面的因素:1 由于玻璃纤维涂敷的浸润剂与基体树脂折射率不一致,导致光线的扭曲,因此能清楚看到复合材料的表面织物的纹路;2 由于两种树脂差别,导致基体树脂与纤维织物结合不紧密,因此拉伸性能降低;3 由于玻璃纤维与基体树脂折射率不同,因此产生多个界面,一方面每个界面都有反射,同时每个界面也会产生折射、散射,因此会显著降低复合材料的透过率。By comparing Comparative Example 3 with Example 8, it can be found that the tensile strength of the composite material of Comparative Example 3 is reduced, the optical transmittance is significantly reduced, and the obvious texture of the glass fiber fabric can still be seen. This is due to three factors: 1. Since the refractive index of the impregnating agent coated on the glass fiber is inconsistent with that of the matrix resin, the light is distorted, so the texture of the surface fabric of the composite material can be clearly seen; 2. Due to the difference between the two resins, the matrix resin and the fiber fabric are not tightly combined, so the tensile performance is reduced; 3. Since the refractive index of the glass fiber and the matrix resin is different, multiple interfaces are generated. On the one hand, each interface has reflection, and on the other hand, each interface will also produce refraction and scattering, which will significantly reduce the transmittance of the composite material.

实施例9Example 9

一种高强度透明复合材料的制备方法,具体步骤如下:A method for preparing a high-strength transparent composite material, the specific steps are as follows:

(1)原料的准备:(1) Preparation of raw materials:

实施例4的T型玻璃纤维;The T-glass fiber of Example 4;

浸润剂:通过质量比为40:60的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.506的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS:80-04-6;Sizing agent: A composite epoxy resin with a refractive index of 1.506 is prepared by mixing two hydrogenated bisphenol A epoxy resins I102215 and P464946 in a mass ratio of 40:60. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS: 80-04-6;

环氧树脂:通过质量比为40:60的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.506的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS:80-04-6;Epoxy resin: A composite epoxy resin with a refractive index of 1.506 was prepared by mixing two hydrogenated bisphenol A epoxy resins, I102215 and P464946, in a mass ratio of 40:60. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS: 80-04-6;

(2)将T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,玻璃纤维纱线络纱成锭织成25微米厚的玻璃纤维织物后,与环氧树脂进行复合制得高强度透明复合材料;(2) coating T-shaped glass fibers with a sizing agent to prepare glass fiber yarns, winding the glass fiber yarns into spindles to weave glass fiber fabrics with a thickness of 25 μm, and then compounding with epoxy resin to obtain a high-strength transparent composite material;

浸润剂的涂覆量为0.2wt%;高强度透明复合材料中玻璃纤维织物的占比为10 wt%。The coating amount of the wetting agent is 0.2wt%; the proportion of the glass fiber fabric in the high-strength transparent composite material is 10 wt%.

最终制得的高强度透明复合材料的厚度为2mm,拉伸强度为256MPa,如图1所示,透过率为88.2%。The high-strength transparent composite material finally obtained has a thickness of 2 mm, a tensile strength of 256 MPa, as shown in FIG1 , and a transmittance of 88.2%.

实施例10Example 10

一种高强度透明复合材料的制备方法,具体步骤如下:A method for preparing a high-strength transparent composite material, the specific steps are as follows:

(1)原料的准备:(1) Preparation of raw materials:

实施例5的T型玻璃纤维;The T-glass fiber of Example 5;

浸润剂:通过质量比为32:68的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.504的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS:80-04-6;Sizing agent: A composite epoxy resin with a refractive index of 1.504 was prepared by mixing two hydrogenated bisphenol A epoxy resins I102215 and P464946 in a mass ratio of 32:68. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS: 80-04-6;

环氧树脂:通过质量比为32:68的I102215与P464946两种氢化双酚A环氧树脂调配制得折射率1.504的复合环氧树脂,I102215与P464946的厂商:上海阿拉丁生化科技股份有限公司,CAS:80-04-6;Epoxy resin: A composite epoxy resin with a refractive index of 1.504 was prepared by mixing two hydrogenated bisphenol A epoxy resins, I102215 and P464946, in a mass ratio of 32:68. The manufacturer of I102215 and P464946 is Shanghai Aladdin Biochemical Technology Co., Ltd., CAS: 80-04-6;

(2)将T型玻璃纤维涂覆浸润剂后制备玻璃纤维纱线,玻璃纤维纱线络纱成锭织成50微米厚的玻璃纤维织物后,与环氧树脂进行复合制得高强度透明复合材料;(2) coating T-shaped glass fibers with a sizing agent to prepare glass fiber yarns, winding the glass fiber yarns into spindles to weave glass fiber fabrics with a thickness of 50 μm, and then compounding with epoxy resin to obtain a high-strength transparent composite material;

浸润剂的涂覆量为0.5wt%;高强度透明复合材料中玻璃纤维织物的占比为50 wt%。The coating amount of the wetting agent is 0.5wt%; the proportion of the glass fiber fabric in the high-strength transparent composite material is 50 wt%.

最终制得的高强度透明复合材料的厚度为2mm,拉伸强度为266MPa,如图1所示,透过率为85.8%。The high-strength transparent composite material finally obtained has a thickness of 2 mm, a tensile strength of 266 MPa, as shown in FIG1 , and a transmittance of 85.8%.

Claims (7)

1. A T-glass fiber, characterized in that: based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 66~72%;
Al2O3 0~7%;
10-12% of the total amount of K 2 O and Na 2 O;
10-14% of the total amount of CaO and MgO;
La2O3 0~3%;B2O3 1~4%;
The total content of Fe 2O3 impurities in the glass raw material is less than or equal to 0.01 percent;
The refractive index of the T-shaped glass fiber is 1.502-1.512.
2. A T-glass fiber according to claim 1, wherein the T-glass fiber comprises the following glass raw material components in mass percent based on the total amount of all glass raw materials in the T-glass fiber:
SiO2 68%;
Al2O3 6%
11% of the total amount of K 2 O and Na 2 O;
13% of the total amount of CaO and MgO;
La2O3 1%;
B2O3 1%;
the total content of Fe 2O3 impurities in the glass raw material is 0.006%.
3. A T-glass fiber according to claim 1, wherein the T-glass fiber comprises the following glass raw material components in mass percent based on the total amount of all glass raw materials in the T-glass fiber:
SiO2 72%;
Al2O3 1%;
11% of the total amount of K 2 O and Na 2 O;
13% of the total amount of CaO and MgO;
B2O3 3%;
the total content of Fe 2O3 impurities in the glass raw material is 0.008%.
4. A method for preparing a T-glass fiber according to any one of claims 1 to 3, wherein: and melting the uniformly mixed glass raw materials at 1450-1550 ℃ for 3-4 hours, and drawing wires through a platinum-rhodium alloy bushing plate to obtain the T-shaped glass fiber.
5. A preparation method of a high-strength transparent composite material is characterized by comprising the following steps: preparing glass fiber yarns after coating the impregnating compound on the T-shaped glass fibers according to any one of claims 1-3, and weaving the glass fiber yarns into glass fiber fabrics with the thickness of 20-50 microns by winding, and then compounding the glass fiber fabrics with epoxy resin to prepare a high-strength transparent composite material;
the impregnating compound is epoxy resin with the refractive index of 1.502-1.512;
the thickness of the high-strength transparent composite material is 2mm, the tensile strength is more than 250MPa, and the transmittance is more than 85%.
6. The method for preparing a high-strength transparent composite material according to claim 5, wherein the coating amount of the impregnating compound is 0.1-0.5wt%.
7. The method for preparing the high-strength transparent composite material according to claim 5, wherein the glass fiber fabric in the high-strength transparent composite material accounts for 10-50wt%.
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RU2036869C1 (en) * 1993-02-04 1995-06-09 Научно-производственное объединение "Стеклопластик" Glass for glass fiber
JP2006312706A (en) * 2005-04-08 2006-11-16 Asahi Fiber Glass Co Ltd Cyclic polyolefin resin composition and molded product
JP2012082297A (en) * 2010-10-08 2012-04-26 Sumitomo Bakelite Co Ltd Resin cured product, transparent composite substrate, and display element substrate
CN109790061A (en) * 2016-11-10 2019-05-21 日本板硝子株式会社 Glass filler and its manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1049834A (en) * 1989-08-11 1991-03-13 伊索福圣戈班公司 The glass fibre that can in Physiological Medium, decompose
RU2036869C1 (en) * 1993-02-04 1995-06-09 Научно-производственное объединение "Стеклопластик" Glass for glass fiber
JP2006312706A (en) * 2005-04-08 2006-11-16 Asahi Fiber Glass Co Ltd Cyclic polyolefin resin composition and molded product
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CN109790061A (en) * 2016-11-10 2019-05-21 日本板硝子株式会社 Glass filler and its manufacturing method

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