TWI392658B - Glass fiber composition - Google Patents
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本發明是有關於一種玻璃纖維組合物,尤其是有關於一種具有低鎂低硼含量之玻璃纖維組合物。 This invention relates to a glass fiber composition, and more particularly to a glass fiber composition having a low magnesium and low boron content.
E玻璃即無鹹玻璃,是用於生產連續玻璃纖維最常用的玻璃成分。無鹹玻璃成分的基礎是SiO2-Al2O3-CaO三元系統,它在三元相圖中是鈣長石、假矽灰石和a-鱗石英與液相平衡組成的一個低共熔點,其組分及重量百分比含量為:62% SiO2、14.7% Al2O3和22.3% CaO。 E glass, ie, no salty glass, is the most commonly used glass component for the production of continuous glass fibers. The basis of the non-salty glass component is the SiO 2 -Al 2 O 3 -CaO ternary system, which is a eutectic of the anemite, pseudo-ashite and a-scalar quartz and liquid phase equilibrium in the ternary phase diagram. Its composition and weight percentage are: 62% SiO 2 , 14.7% Al 2 O 3 and 22.3% CaO.
在此基礎上,玻璃組合物中添加B2O3替代部分SiO2,MgO替代部分CaO,形成了現在通用的無鹹玻璃成分。專利US2334981和US2571074中描述了其典型特徵,它一般以SiO2-Al2O3-CaO-B2O3四元系統為基礎。專利US2571074的玻璃組合物中引入重量百分比含量為5~13%的B2O3替代部分SiO2,目的在於降低玻璃的成型溫度和液相線溫度,且有利於玻璃的熔化及玻璃纖維的拉制成型。但是B2O3的大量引入導致傳統無鹹玻璃存在原料成本高、對環境污染大等缺點。 On this basis, B 2 O 3 is added to the glass composition to replace part of SiO 2 , and MgO replaces part of CaO to form a common non-salty glass component. Typical features are described in the patents US Pat. No. 2,343,981 and US Pat. No. 2,571,074, which are generally based on the SiO 2 -Al 2 O 3 -CaO-B 2 O 3 quaternary system. The glass composition of the patent US2571074 incorporates B 2 O 3 in a weight percentage of 5-13% to replace part of SiO 2 , in order to lower the molding temperature and liquidus temperature of the glass, and to facilitate the melting of the glass and the pulling of the glass fiber. Finished. However, the large introduction of B 2 O 3 leads to the disadvantages of high raw material cost and large environmental pollution.
在玻璃纖維行業中,成型溫度是指玻璃熔體達到易於拉絲成型時的溫度,實際上它是一個區域,溫度範圍相當於黏度為102.5~103泊時的溫度,本發明中取黏度為103泊時的溫度為成型溫度。液相線溫度是指玻璃熔體冷卻時晶核開始形成的溫度。為了避免在玻璃纖維拉制過程中出現任何失透危險,用△T值表示成型溫度與液相線溫度之差,它應該是正的,優選的大於50 ℃。較大的△T值表明玻璃熔體有較高的穩定性,有利於玻璃拉絲成型。 In the glass fiber industry, the molding temperature refers to the temperature at which the glass melt reaches the ease of wire drawing. In fact, it is a region whose temperature range corresponds to a temperature at a viscosity of 10 2.5 to 10 3 poise. In the present invention, the viscosity is The temperature at 10 3 poise is the molding temperature. The liquidus temperature refers to the temperature at which the nucleus begins to form as the glass melt cools. In order to avoid any risk of devitrification during the glass fiber drawing process, the difference between the forming temperature and the liquidus temperature is indicated by the ΔT value, which should be positive, preferably greater than 50 °C. A larger ΔT value indicates a higher stability of the glass melt, which is advantageous for glass drawing.
此外,本發明中提及的組成物含量均以“%”來表示,應該理解為“重量百分比”或“wt%”。 Further, the content of the composition mentioned in the present invention is expressed by "%" and should be understood as "% by weight" or "wt%".
現在主流的低硼玻璃纖維組合物基本由SiO2-Al2O3-CaO-MgO四元系統組成,其中MgO含量大多高於1%。專利WO96/39362中描述了一種無硼玻璃纖維組合物,它主要由SiO2、Al2O3、CaO和MgO組成,且不添加或少量添加TiO2、SrO、MnO和ZnO等昂貴氧化物,在優選的實施方案中,MgO含量範圍為2~3.5%,該玻璃纖維組合物具有較大的△T值,但成型溫度和液相線溫度相對較高。過高的成型溫度和液相線溫度會大大提高能耗,也會加速窯爐和鉑金漏板的高溫老化,從而提高生產成本。專利WO01/32576中描述了一種低硼玻璃纖維組合物,它的組分也主要包括SiO2、Al2O3、CaO和MgO,在優選的實施方案中,MgO含量範圍為1.5~4%,該玻璃纖維組合物具有較大的△T值,成型溫度和液相線溫度也不高,但其中SiO2含量較低(58%以下)一定程度上影響了玻璃的機械強度。 The mainstream low boron glass fiber composition now consists essentially of a SiO 2 -Al 2 O 3 -CaO-MgO quaternary system in which the MgO content is mostly above 1%. Patent WO 96/39362 describes a boron-free glass fiber composition mainly composed of SiO 2 , Al 2 O 3 , CaO and MgO, without adding or adding a small amount of expensive oxides such as TiO 2 , SrO, MnO and ZnO. In a preferred embodiment, the MgO content ranges from 2 to 3.5%, and the glass fiber composition has a large ΔT value, but the molding temperature and the liquidus temperature are relatively high. Excessive molding temperatures and liquidus temperatures will greatly increase energy consumption and will also accelerate the high temperature aging of kiln and platinum drain plates, thereby increasing production costs. Patent WO 01/32576 describes a low boron glass fiber composition whose components also mainly comprise SiO 2 , Al 2 O 3 , CaO and MgO. In a preferred embodiment, the MgO content ranges from 1.5 to 4%. The glass fiber composition has a large ΔT value, and the molding temperature and the liquidus temperature are not high, but the low SiO 2 content (below 58%) affects the mechanical strength of the glass to some extent.
MgO含量低於1%的玻璃纖維組合物很少見,已知的少數幾件專利都存在一定的問題,無法很好地滿足工業化生產的需要。例如,專利WO00/73232中使用MgO含量低於1%的玻璃纖維組合物,它主要由SiO2-Al2O3-CaO三元系統組成,還添加了一定量的B2O3、Li2O、ZnO、MnO或MnO2,達到了降低成型溫度和液相線溫度的目的,但從其實施例看,或者成型溫度仍然偏高,或者△T值遠小於50℃。而且該玻璃纖維組合物的原料成本太高。又如,專利WO03/050049中描述了一種適用於汽車排氣系統的玻璃纖維組合物,它通過引入低於1%的MgO和高於1.5%的TiO2達到了提高耐酸性和耐高溫性的目的,但由於使用了大量的TiO2,該玻璃纖維組合物缺乏成本上的優勢。 Glass fiber compositions having a MgO content of less than 1% are rare, and a few of the known patents have certain problems and are not well suited to the needs of industrial production. For example, patent WO 00/73232 uses a glass fiber composition having a MgO content of less than 1%, which is mainly composed of a SiO 2 -Al 2 O 3 -CaO ternary system, and a certain amount of B 2 O 3 , Li 2 is also added. O, ZnO, MnO or MnO 2 achieves the purpose of lowering the molding temperature and the liquidus temperature, but from the examples thereof, the molding temperature is still high, or the ΔT value is much less than 50 °C. Moreover, the raw material cost of the glass fiber composition is too high. As another example, the patent WO 03/050049 describes a glass fiber composition suitable for use in an automotive exhaust system which achieves improved acid and high temperature resistance by introducing less than 1% MgO and more than 1.5% TiO 2 . Purpose, but due to the large amount of TiO 2 used , the glass fiber composition lacks cost advantages.
本發明要解決的技術問題在於提供一種低鎂低硼的玻璃纖維組合物,以獲得滿足成本上和環境上的要求且具有優良拉制性能和使用性能的玻璃纖維。 The technical problem to be solved by the present invention is to provide a low-magnesium and low-boron glass fiber composition to obtain a glass fiber which satisfies cost and environmental requirements and has excellent drawing properties and use properties.
為解決上述技術問題,本發明採用的技術方案如下:一種玻璃纖維組合物,其包含SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3,以SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3的總含量為100%計,各組分的重量百分比含量表示如下: In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: a glass fiber composition comprising SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O 3 and SO 3 with SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O 3 and SO 3 The total content is 100%, and the weight percentage of each component is expressed as follows:
其中,CaO和MgO的重量百分比含量之和RO=CaO+MgO的範圍在21~27%。 Among them, the sum of the weight percentages of CaO and MgO, RO=CaO+MgO, ranges from 21 to 27%.
在本發明的玻璃纖維組合物中,鹼土金屬氧化物組分CaO、MgO遵循如下的規定:定義比值Z1=RO/MgO,即Z1=(CaO+MgO)/MgO,代表CaO和MgO的重量百分比含量之和與MgO的重量百分比含量之比,比值Z1的範圍為21~43。此比值可以體現MgO與CaO的比例關係。因此,可以將其作為控制玻璃析晶和液相線溫度的參數。優選的Z1的範圍為25~35。 In the glass fiber composition of the present invention, the alkaline earth metal oxide components CaO, MgO are as follows: a defined ratio Z1 = RO / MgO, that is, Z1 = (CaO + MgO) / MgO, representing the weight percentage of CaO and MgO The ratio of the sum of the contents to the weight percentage of MgO, the ratio Z1 ranges from 21 to 43. This ratio can reflect the proportional relationship between MgO and CaO. Therefore, it can be used as a parameter for controlling the crystallization of the glass and the temperature of the liquidus. A preferred range of Z1 is 25 to 35.
本發明所述玻璃纖維組合物的成型溫度為1200~1300℃,液相線溫度一般比成型溫度低55℃以上。 The glass fiber composition of the present invention has a molding temperature of 1200 to 1300 ° C, and the liquidus temperature is generally 55 ° C lower than the molding temperature.
需要說明的是,本發明所述玻璃纖維組合物除了上述組分外,可能不可避免地存在一些由於原料帶來的微量雜質,這些微量雜質不會對玻璃纖維的性能帶來實質性的影響。此外,在不對本發明的玻璃纖維組成物構成限制的情況下,可將不超過1%的SrO加入到玻璃纖維組成物中以降低成型溫度和/或液相線溫度;也可將不超過1%的CeO2加入到玻璃纖維組成物中,不僅可以起到良好的澄清作用,還可以將部分二價鐵離子氧化成三價鐵離子,使玻璃纖維的綠色變淺。上述SrO和CeO2組分的重量百分比含量也是以所述的SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3的總含量為100%計。 It should be noted that, in addition to the above components, the glass fiber composition of the present invention may inevitably have some trace impurities due to the raw materials, and these trace impurities do not have a substantial influence on the performance of the glass fibers. Further, in the case where the glass fiber composition of the present invention is not limited, not more than 1% of SrO may be added to the glass fiber composition to lower the molding temperature and/or the liquidus temperature; or may not exceed 1 The addition of % CeO 2 to the glass fiber composition not only serves as a good clarifying effect, but also oxidizes some of the divalent iron ions to ferric ions to lighten the green color of the glass fibers. The content of the above SrO and CeO 2 components is also SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O. The total content of 3 and SO 3 is 100%.
本發明具體推薦一種玻璃纖維組合物,其基本上由SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3所組成,各組分的含量以重量百分比表示如下: RO=CaO+MgO 21~27% The present invention specifically recommends a glass fiber composition substantially consisting of SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O 3 and The composition of SO 3 , the content of each component is expressed by weight percentage as follows: RO=CaO+MgO 21~27%
所謂“基本上由…所組成(基本含有)”表示除了上述組分,玻璃纖維組合物中不含其他起實質性作用的組分,但是本發明允許生產過程中不可避免帶入的微量雜質。 The phrase "consisting essentially of (consistently contained)" means that the glass fiber composition contains no other substantially effective components in addition to the above components, but the present invention allows a trace amount of impurities which are inevitably brought in during production.
在本發明的玻璃纖維組合物中,各組分含量還遵循如下的規定:定義比值Z2=(SiO2+Al2O3)/(RO+R2O+B2O3+F2),比值Z2的範圍為2.55~2.95。此比值可以理解為形成玻璃網路的組分總量與改善玻璃網路的組分總量之比。因此,可以將其作為調節玻璃強度和黏度的參數。 In the glass fiber composition of the present invention, the content of each component also follows the following definition: the definition ratio Z2 = (SiO 2 + Al 2 O 3 ) / (RO + R 2 O + B 2 O 3 + F 2 ), The ratio Z2 ranges from 2.55 to 2.95. This ratio can be understood as the ratio of the total amount of components forming the glass network to the total amount of components of the glass network. Therefore, it can be used as a parameter for adjusting the strength and viscosity of the glass.
在本發明的玻璃纖維組合物中,SiO2是形成玻璃骨架的主要氧化物,並且起穩定各組分的作用。本發明所限定的SiO2含量範圍為58~65%,若其含量太低會影響玻璃的結構穩定;若其含量太高則會使玻璃的黏度升高導致澄清困難。優選的SiO2含量範圍為58~61%。 In the glass fiber composition of the present invention, SiO 2 is a main oxide forming a glass skeleton and functions to stabilize the components. The SiO 2 content defined by the present invention ranges from 58 to 65%. If the content is too low, the structural stability of the glass is affected; if the content is too high, the viscosity of the glass is increased to cause difficulty in clarification. A preferred SiO 2 content ranges from 58 to 61%.
在本發明的玻璃纖維組合物中,Al2O3也是形成玻璃骨架的氧化物,與SiO2結合時可對玻璃模量起到實質性的作用,並且在阻止玻璃分相和抗水性方面起著重要作用。本發明所限定的Al2O3含量範圍為9~17%,若其含量太低會使液相線溫度升高,同時使得玻璃的抗水性變差;若其含量太高則會導致出現玻璃失透的危險及增加玻璃的黏度。優選的Al2O3含量範圍為12~15%。 In the glass fiber composition of the present invention, Al 2 O 3 is also an oxide forming a glass skeleton, which has a substantial effect on the glass modulus when combined with SiO 2 and plays a role in preventing phase separation and water resistance of the glass. Play an important role. The Al 2 O 3 content defined by the present invention ranges from 9 to 17%. If the content is too low, the liquidus temperature will increase, and at the same time, the water resistance of the glass will be deteriorated; if the content is too high, the glass will be formed. The danger of devitrification and increasing the viscosity of the glass. The preferred Al 2 O 3 content ranges from 12 to 15%.
在本發明的玻璃纖維組合物中,CaO是玻璃的網路外體氧化物,適當的加入可提高玻璃的化學穩定性和機械強度,還能使玻璃料性變短,提高成型速度。本發明所限定的CaO含量範圍為20~26%,若其含量太低起不到上述作用;若其含量太高則會增大玻璃的結晶傾向。優選的CaO含量範圍為22~25%。 In the glass fiber composition of the present invention, CaO is a network outer oxide of glass. Appropriate addition can improve the chemical stability and mechanical strength of the glass, and can shorten the glass frit and increase the molding speed. The CaO content defined by the present invention ranges from 20 to 26%, and if the content is too low, the above effect is not obtained; if the content is too high, the crystallization tendency of the glass is increased. The preferred CaO content ranges from 22 to 25%.
在本發明的玻璃纖維組合物中,MgO具有與CaO類似的作用,主要起到調節玻璃黏度和控制玻璃析晶的作用,還對比楊氏模量產生有利的作用。本發明所限定的MgO含量範圍為0.5~1%。本發明中將少量MgO與CaO混合使用,MgO含量與CaO含量相關,兩者的總含量在特定範圍內能夠得到液相線溫度很低的玻璃。加入少量的MgO能夠引入矽灰石(CaSiO3)與透輝石(CaMgSi2O6)晶體之間的競爭生長,從而延緩這兩種晶體的生長,達到降低玻璃失透危險的目的。若MgO含量太高,尤其高於或等於3.5%時,透輝石晶體的生長速度特別快,反而使得液相線溫度升高,不利於玻璃的良好拉制。在本發明的含量範圍內,當CaO和MgO的含量分別大於22%和0.5%,且保持鹼土金屬氧化物總含量大於23%時,可獲得良好的拉制性能。但其總含量不應超過26%,因為這時CaO的含量過高可導致玻璃失透生成矽灰石的速度增加,從而有損於玻璃的良好拉制。同時,由於Mg2+的離子場強大於Ca2+,所以適量引入MgO可提高玻璃的機械強度和化學穩定性。優選的MgO含量範圍為0.7~1%。優選的CaO和MgO的總含量為23~26%。 In the glass fiber composition of the present invention, MgO has a similar effect as CaO, mainly serves to adjust the viscosity of the glass and control the crystallization of the glass, and also has an advantageous effect in comparison with the Young's modulus. The MgO content defined by the present invention ranges from 0.5 to 1%. In the present invention, a small amount of MgO is mixed with CaO, and the MgO content is related to the CaO content, and the total content of the two can obtain a glass having a very low liquidus temperature within a specific range. The addition of a small amount of MgO can introduce competitive growth between the dolomite (CaSiO 3 ) and the diopside (CaMgSi 2 O 6 ) crystals, thereby delaying the growth of the two crystals and achieving the purpose of reducing the risk of devitrification of the glass. If the MgO content is too high, especially higher than or equal to 3.5%, the growth rate of the diopside crystals is particularly fast, which in turn causes the liquidus temperature to rise, which is not conducive to good drawing of the glass. In the content range of the present invention, when the contents of CaO and MgO are more than 22% and 0.5%, respectively, and the total content of the alkaline earth metal oxide is maintained at more than 23%, good drawing properties can be obtained. However, the total content should not exceed 26%, because the excessive content of CaO at this time can lead to an increase in the rate of devitrification of the glass to form the asbestos, thereby detracting from the good drawing of the glass. At the same time, since the ion field of Mg 2+ is stronger than Ca 2+ , the proper introduction of MgO can improve the mechanical strength and chemical stability of the glass. A preferred MgO content ranges from 0.7 to 1%. The preferred total content of CaO and MgO is 23 to 26%.
在本發明的玻璃纖維組合物中,B2O3是玻璃的網路形成體,起著較好的助熔作用,也是一種可以降低玻璃成型溫度和液相線溫度的組分。本發明所限定的B2O3含量範圍為0~5%,實際上希望把B2O3的含量限制在很小的值,因為含硼的原料價格很高,同時硼是易揮發的污染物質,需將其在排放的廢氣中除去,B2O3含量過高不僅增加生產成本,而且容易造成廢棄物的二次污染。因此,降低B2O3含量是有利的。優選的B2O3含量範圍為0~2%,更優選的B2O3含量範圍為0~1%。 In the glass fiber composition of the present invention, B 2 O 3 is a network forming body of glass, which functions as a better fluxing and is a component which can lower the glass forming temperature and the liquidus temperature. The B 2 O 3 content defined by the present invention ranges from 0 to 5%, and it is actually desirable to limit the B 2 O 3 content to a small value because the boron-containing raw material is expensive and boron is a volatile contamination. The substance needs to be removed from the exhaust gas. The high B 2 O 3 content not only increases the production cost, but also easily causes secondary pollution of the waste. Therefore, it is advantageous to lower the B 2 O 3 content. A preferred B 2 O 3 content ranges from 0 to 2%, and a more preferred B 2 O 3 content ranges from 0 to 1%.
本發明的玻璃纖維組合物中還存在少量的TiO2,基本上由礦物原料以雜質形式帶入,它不僅可以降低高溫時的玻璃黏度,還具有一定的助熔作用。本發明的玻璃纖維組合物中還加入少量的氟來改善玻璃的熔融性。我國規 定E玻璃的鹼金屬含量必須小於0.8%,所以本發明的玻璃纖維組合物中鹼金屬的總量控制在0.8%以內。 A small amount of TiO 2 is also present in the glass fiber composition of the present invention, which is substantially carried by the mineral raw material in the form of impurities, which not only reduces the glass viscosity at high temperatures, but also has a certain fluxing effect. A small amount of fluorine is also added to the glass fiber composition of the present invention to improve the meltability of the glass. In China, the alkali metal content of E glass must be less than 0.8%, so the total amount of alkali metal in the glass fiber composition of the present invention is controlled within 0.8%.
優選的方案:所述玻璃纖維組合物基本上由SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3所組成,各組分的含量以重量百分比表示如下: Preferred solution: the glass fiber composition consists essentially of SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O 3 and SO 3 composition, the content of each component is expressed in weight percent as follows:
其中,組分含量遵循如下比例關係:25<Z1<35。 Among them, the component content follows the following proportional relationship: 25 < Z1 < 35.
更優選的方案:所述玻璃纖維組合物基本上由SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3,各組分的含量以重量百分比表示如下: More preferably, the glass fiber composition consists essentially of SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O 3 and SO 3 , the content of each component is expressed as a percentage by weight as follows:
具體的,所述的玻璃纖維組合物可由下列組分所組成,基於所述的SiO2、Al2O3、CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3,各組分的重量百分比含量表示如下: Specifically, the glass fiber composition may be composed of the following components, based on the SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 O 3 and SO 3 , the weight percentage content of each component is expressed as follows:
需要特別指出的是,上述玻璃纖維組合物的組分含量是以SiO2、Al2O3、 CaO、MgO、B2O3、F2、TiO2、K2O、Na2O、Fe2O3和SO3的總含量為100%計,得到的玻璃纖維組合物的總含量有可能大於100%。 It should be particularly noted that the component content of the above glass fiber composition is SiO 2 , Al 2 O 3 , CaO, MgO, B 2 O 3 , F 2 , TiO 2 , K 2 O, Na 2 O, Fe 2 . The total content of O 3 and SO 3 is 100%, and the total content of the obtained glass fiber composition may be more than 100%.
本發明的玻璃纖維組合物以SiO2-Al2O3-CaO三元系統為基礎,引入低含量的MgO和B2O3,並且合理設計鹼土金屬氧化物的總量及MgO與CaO的比例關係,具有以下優勢:a)由於Mg2+的離子場強大於Ca2+,故在玻璃纖維中適量引入MgO可提高玻璃的機械強度和化學穩定性。同時通過合理設計鹼土金屬氧化物的總量及MgO與CaO的比例關係,可以有效控制玻璃析晶和液相線溫度。本發明中當Z1在21~43範圍內時,玻璃纖維組合物具有相對較低的成型溫度和液相線溫度,減少了玻璃失透的危險,有利於玻璃纖維的良好拉制。所以,本發明的玻璃纖維組合物不僅有利於改善玻璃的機械強度、耐高溫性及化學穩定性,同時還具有良好的拉制性能;b)採用低硼配方,降低B2O3的使用量可以降低成本,同時也符合環保要求。 The glass fiber composition of the invention is based on the SiO 2 -Al 2 O 3 -CaO ternary system, introducing low content of MgO and B 2 O 3 , and rationally designing the total amount of alkaline earth metal oxides and the ratio of MgO to CaO. The relationship has the following advantages: a) Since the ion field of Mg 2+ is stronger than Ca 2+ , the proper introduction of MgO in the glass fiber can improve the mechanical strength and chemical stability of the glass. At the same time, by reasonably designing the total amount of alkaline earth metal oxides and the ratio of MgO to CaO, the glass crystallization and liquidus temperature can be effectively controlled. In the present invention, when Z1 is in the range of 21 to 43, the glass fiber composition has a relatively low molding temperature and liquidus temperature, which reduces the risk of devitrification of the glass and facilitates good drawing of the glass fiber. Therefore, the glass fiber composition of the present invention not only helps to improve the mechanical strength, high temperature resistance and chemical stability of the glass, but also has good drawing performance; b) uses a low boron formula to reduce the amount of B 2 O 3 used. It can reduce costs and meet environmental requirements.
以下藉由實施例對本發明的技術方案進行具體說明,但本發明內容並不受以下實施例的任何制約。 The technical solutions of the present invention are specifically described below by way of examples, but the present invention is not limited by the following examples.
本發明實施例中為操作方便,以玻璃纖維組合物的總含量為100%計,其中實施例組分總含量略微小於100%,可以理解為殘餘量是微量雜質或不能分析出的少量組分。 In the embodiment of the present invention, the operation is convenient, and the total content of the glass fiber composition is 100%, wherein the total content of the components in the embodiment is slightly less than 100%, which can be understood as the residual amount is a trace impurity or a small component which cannot be analyzed. .
本發明中生產玻璃纖維的主要原料為葉臘石、石英粉、生灰石、白雲石、 硼鈣石等。本發明實施例的具體過程如下:各組合物可從適當的原料中獲取(如石英粉中的SiO2,生石灰中的CaO),按適當比例將各種原料進行混合,使各組分達到最終的預期重量百分比,然後將混合後的配合料在池窯中熔化並澄清,形成的玻璃液通過通路流至位於通路底部的纖維成型漏板,玻璃液通過漏板上的漏嘴被拉出從而形成玻璃纖維,玻璃纖維被牽引繞到拉絲機旋轉機頭上形成原絲餅或紗團,這些玻璃纖維可用常規方法進行深加工以符合預期要求。 The main raw materials for producing glass fibers in the present invention are pyrophyllite, quartz powder, ash, dolomite, bauxite and the like. The specific process of the embodiments of the present invention is as follows: each composition can be obtained from a suitable raw material (such as SiO 2 in quartz powder, CaO in quicklime), and various raw materials are mixed in an appropriate ratio to make the components reach the final The weight percentage is expected, and then the mixed batch is melted and clarified in the kiln, and the formed glass flows through the passage to the fiber forming drain plate at the bottom of the passage, and the molten glass is pulled out through the leak nozzle on the drain plate to form the glass. The fibers, glass fibers are drawn around the rotating head of the wire drawing machine to form a raw silk cake or a group of yarns which can be further processed in a conventional manner to meet the desired requirements.
表1和表2中列出了本發明的六個實施例,其編號為C1-C6,另外還有兩個對比實施例,其編號為E1-E2,E1是傳統的E玻璃纖維組合物,E2是專利WO96/39362中的玻璃纖維組合物。玻璃纖維組合物各組分的含量以重量百分比表示。 Six examples of the invention are listed in Tables 1 and 2, numbered C1-C6, in addition to two comparative examples, numbered E1-E2, E1 being a conventional E-glass fiber composition, E2 is the glass fiber composition of patent WO 96/39362. The content of each component of the glass fiber composition is expressed in weight percent.
為了說明本發明玻璃纖維組合物的優點,表中給出了四個基本參數: To illustrate the advantages of the glass fiber composition of the present invention, four basic parameters are given in the table:
1-成型溫度,對應於玻璃熔體在黏度為103泊時的溫度。 1-Molding temperature, corresponding to the temperature at which the glass melt has a viscosity of 10 3 poise.
2-液相線溫度,對應於玻璃熔體冷卻時晶核開始形成的溫度,即玻璃析晶的上限溫度。 The 2-liquidus temperature corresponds to the temperature at which the nucleus begins to form when the glass melt cools, that is, the upper limit temperature of the glass crystallization.
3-△T值,即成型溫度與液相線溫度之差,表示可能拉絲成型的溫度範圍。上述三個溫度值及其測定方法是本技術領域的技術人員所熟知的。 The 3-ΔT value, which is the difference between the molding temperature and the liquidus temperature, indicates the temperature range at which wire drawing can take place. The above three temperature values and methods for their determination are well known to those skilled in the art.
4-以環氧樹脂為基玻璃纖維增強的複合材料的拉伸強度,它以ASTM D2343為標準進行檢測。 4- Tensile strength of epoxy resin-based glass fiber reinforced composites, which is tested according to ASTM D2343.
表1
表2
由表1和表2可知,本發明的玻璃纖維在複合材料的拉伸強度方面明顯優於傳統E玻璃纖維(對比實施例E1)。與對比實施例E2相比,本發明的玻璃纖維則具有相對較低的成型溫度和液相線溫度,這有利於降低能耗,減緩窯爐和鉑金漏板的高溫老化。同時,本發明的玻璃纖維還具有與對比實施例E2足夠可比的拉伸強度,且拉制成型條件有所改進。 As is apparent from Tables 1 and 2, the glass fiber of the present invention is remarkably superior to the conventional E glass fiber in the tensile strength of the composite material (Comparative Example E1). Compared with Comparative Example E2, the glass fiber of the present invention has a relatively low molding temperature and liquidus temperature, which is advantageous for reducing energy consumption and slowing the high temperature aging of the kiln and the platinum leakage plate. Meanwhile, the glass fiber of the present invention also has a tensile strength sufficiently comparable to that of Comparative Example E2, and the stretch forming conditions are improved.
以上所述僅為舉例性,而非為限制性者。任何未脫離本發明之精神與範疇 ,而對其進行之等效修改或變更,均應包含於後附之申請專利範圍中。 The above is intended to be illustrative only and not limiting. Any spirit and scope without departing from the invention And equivalent modifications or changes to this shall be included in the scope of the patent application attached.
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FR2692248A1 (en) * | 1992-06-16 | 1993-12-17 | Vetrotex France Sa | Continuous silica-alumina-lime glass fibre of high acid resistance and low cost - contg. silica, alumina, calcia, magnesia, boria, sodium and potassium oxide(s) and iron oxide |
WO2000073232A1 (en) * | 1999-05-27 | 2000-12-07 | Ppg Industries Ohio, Inc. | Glass fiber composition |
US20010008864A1 (en) * | 1996-10-16 | 2001-07-19 | Shinichi Tamura | Glass fiber of low permittivity |
US20060166805A1 (en) * | 2002-08-27 | 2006-07-27 | Hong Li | Low-temperature, fluoride free fiber glass compositions and products made using same |
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FR2692248A1 (en) * | 1992-06-16 | 1993-12-17 | Vetrotex France Sa | Continuous silica-alumina-lime glass fibre of high acid resistance and low cost - contg. silica, alumina, calcia, magnesia, boria, sodium and potassium oxide(s) and iron oxide |
US20010008864A1 (en) * | 1996-10-16 | 2001-07-19 | Shinichi Tamura | Glass fiber of low permittivity |
WO2000073232A1 (en) * | 1999-05-27 | 2000-12-07 | Ppg Industries Ohio, Inc. | Glass fiber composition |
US20060166805A1 (en) * | 2002-08-27 | 2006-07-27 | Hong Li | Low-temperature, fluoride free fiber glass compositions and products made using same |
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