WO2020156374A1 - 一种低介电玻璃纤维组分及其制造方法 - Google Patents

一种低介电玻璃纤维组分及其制造方法 Download PDF

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WO2020156374A1
WO2020156374A1 PCT/CN2020/073474 CN2020073474W WO2020156374A1 WO 2020156374 A1 WO2020156374 A1 WO 2020156374A1 CN 2020073474 W CN2020073474 W CN 2020073474W WO 2020156374 A1 WO2020156374 A1 WO 2020156374A1
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glass
glass fiber
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zno
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黄建国
宁祥春
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Henan Guangyuan New Material Co Ltd
East China University of Science and Technology
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Henan Guangyuan New Material Co Ltd
East China University of Science and Technology
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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
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • 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

Definitions

  • the invention relates to the field of electronic information substrate materials, in particular to a low-dielectric glass fiber component and a manufacturing method thereof.
  • glass fiber is widely used in substrate materials such as reinforced copper clad laminate (CCL) and printed circuit board (PCB).
  • CCL reinforced copper clad laminate
  • PCB printed circuit board
  • electronic glass fibers are also increasingly important.
  • the lower the dielectric constant the faster the signal transmission speed in the circuit board, and the lower the energy loss during transmission. Therefore, it is required that the glass fiber constituting the substrate composite material also has a low dielectric constant and a low tangent loss.
  • SiO 2 and B 2 O 3 have relatively low dielectric constants, so glass with high silicon dioxide and high boron oxide content has relatively low dielectric constants.
  • D glass fiber has very excellent dielectric properties, and its composition in terms of mass percentage is: 72% to 76% SiO 2 , 0% to 5% Al 2 O 3 , 20% to 25% B 2 O 3 , 3% ⁇ 5% of Na 2 O+K 2 O.
  • the dielectric constant is 3.8-4.2, and the dielectric loss is about 8 ⁇ 10 -4 , but because the composition contains more SiO 2 (above 70%wt), its melting temperature is higher, and the drawing operation temperature is higher , It is easy to produce bubbles or streaks during the drawing process to cause wire breakage.
  • D glass has poor water resistance and poor adhesion with resin; while common E glass fiber has good performance indicators and is widely used in the market, but its relative dielectric constant at 1MHz is 6.8 , Does not meet the requirements of the modern electronic information industry for the dielectric constant of the substrate composite material.
  • the improved composition proposed by Japanese patent JP2009286686 is 45-65% SiO 2 , 10-20% Al 2 O 3 , 13-25% B 2 O 3 , 5.5-9% MgO, 0-10% CaO, 0- 1% Li 2 O+Na 2 O+K 2 O.
  • the improved composition proposed by Japan Textile Co., Ltd., JP 10-120437, in terms of mass percentage: 50-56% SiO 2 , 10-18% Al 2 O 3 , 18-25% B 2 O 3 , 0-4% MgO , 10-17% CaO, 0-1% Li 2 O+Na 2 O+K 2 O, 0-2% F.
  • AGY patent CN101594987B essentially contains 52-60% SiO 2 , 11-16% Al 2 O 3 , 20-30% B 2 O 3 and 4-8% CaO in terms of mass percentage, and basically does not contain MgO and basically Li 2 O, basically no Na 2 O, basically no K 2 O, and basically no TiO 2 .
  • the improved composition proposed by Chinese patent CN107298531(A) is: mass fraction 62-65% SiO 2 , 11-13% Al 2 O 3 , 13-15% B 2 O 3 , 5-8% CaO, 0.5-2% TiO 2 , 0.5-2% Li 2 O and 0.5-2% La 2 O 3 .
  • the dielectric constant of the glass composed of the above patent is about 4.5-5.5.
  • the technical problem to be solved by the present invention is to provide a low-dielectric glass fiber component, while ensuring that the glass has a good balance of water resistance, acid resistance, alkali resistance, etc., and controlling the phase separation and crystallization range of the glass to avoid Environmental pollution caused by F volatilization in production.
  • a low-dielectric glass fiber component in terms of mass fraction, includes the following components:
  • a manufacturing method of low-dielectric glass fiber includes the following steps:
  • step S2 Melt, homogenize and clarify the mixture obtained in step S1;
  • step S3 Pour the molten glass that has been clarified in step S2 into a preheated mold, annealed at 600°C for 3 hours and then cooled to room temperature in the furnace, and perform performance testing after processing.
  • the raw materials in the step S1 are quartz, boric acid, aluminum oxide, calcium carbonate, magnesium oxide, zinc oxide, titanium dioxide and bismuth oxide.
  • the melting and homogenization is to pour the evenly mixed batch material in step S1 into a platinum crucible, and melt in a high-temperature electric furnace, the melting temperature is controlled at 1600°C, and the temperature is kept at the highest temperature for 3 hours to obtain Uniform glass liquid.
  • the mold is pre-heated before the molten glass is poured.
  • the molten and clarified glass liquid in step 2 flows into the platinum drain plate to perform wire drawing, cooling by cooling gas and cooling water to obtain glass fiber, and adjusting the diameter parameter of the glass fiber by controlling the rotation speed of the wire drawing machine.
  • the present invention provides a low-dielectric glass fiber component, in terms of mass fraction, including the following components:
  • the bond energy of this bond is greater than the Si-O bond energy, which can stabilize the glass network structure and limit the polarization of oxygen ions in the glass; therefore Appropriate addition of B 2 O 3 can optimize the dielectric properties of the glass; at the same time, because B 3+ has a smaller electronic polarizability than Si 4+ and Al 3+ , increasing its content will help reduce the dielectric constant; Al 2 O 3 is also the oxide that forms the framework of the glass structure network.
  • Al 2 O 3 can reduce the phase separation and crystallization tendency of the glass, improve the chemical stability, and improve the thermal stability; but its content will increase the high temperature viscosity of the glass , Leading to difficulties in melting and clarification, so the present invention limits the content of Al 2 O 3 to 12-15%; and the addition of a small amount of ZrO 2 and TiO 2 can improve the water resistance, acid and alkali resistance of the glass.
  • the composition of the ternary mixed alkaline earth oxide and introducing a small amount of bismuth oxide a glass with higher melting quality is obtained.
  • the present invention provides a method for manufacturing low-dielectric glass fiber, which includes the following steps: weighing raw materials according to the composition of the formula, and then mixing them for use; melting, homogenizing and clarifying the mixture obtained in step S1; melting and clarifying step S2
  • the good molten glass is poured into the preheated mold, annealed at 600°C for 3 hours and then cooled to room temperature in the furnace, and then the performance is tested after processing.
  • the glass obtained by the present invention has a lower dielectric constant, a lower wire drawing temperature, and the difference between the wire drawing temperature and the glass liquidus temperature is far greater than 200°C, which is convenient for production control; compared with the prior art, the present invention Glass has a relatively low glass dielectric constant, while ensuring a good balance of water resistance, acid resistance, alkali resistance, etc., and achieving the key goals to be solved; the composition does not contain F, which is beneficial to environmental protection and is applicable For large-scale, clean industrial production.
  • Fig. 1 is a schematic flow diagram of a manufacturing method of low dielectric glass fiber according to the present invention.
  • the present invention provides a low-dielectric glass fiber component, in terms of mass fraction, including the following components:
  • the bond energy of this bond is greater than the Si-O bond energy, which can stabilize the glass network structure and limit the polarization of oxygen ions in the glass; therefore Appropriate addition of B 2 O 3 can optimize the dielectric properties of the glass; at the same time, because B 3+ has a smaller electronic polarizability than Si 4+ and Al 3+ , increasing its content will help reduce the dielectric constant; Al 2 O 3 is also the oxide that forms the framework of the glass structure network.
  • Al 2 O 3 can reduce the phase separation and crystallization tendency of the glass, improve the chemical stability, and improve the thermal stability; but its content will increase the high temperature viscosity of the glass , Leading to difficulties in melting and clarification, so the present invention limits the content of Al 2 O 3 to 12-15%; and the addition of a small amount of ZrO 2 and TiO 2 can improve the water resistance, acid and alkali resistance of the glass.
  • the main technical innovation of the present invention is to ensure the amount of SiO 2 , B 2 O 3 , and Al 2 O 3 , and at the same time, by optimizing the design of the content and combination of alkaline earth metal RO, accurately regulating the ratio of CaO ⁇ MgO ⁇ ZnO and strengthening the ternary mixing Alkaline earth metal effect, and introduce a certain amount of B 2 O 3 into the composition, without introducing Li, Na, K and other alkaline earth metals and F into the composition.
  • These measures are conducive to improving the melting effect of the glass, reducing the phase separation and crystallization tendency of the glass, lowering the drawing operation temperature, and obtaining a relatively low glass dielectric constant and dielectric loss, while ensuring good water resistance and acid resistance And other performance.
  • the glass composition provided by the present invention includes the following main components in mass%: SiO 2 : 54.0-57.0%, Al 2 O 3 : 12.0-15.0%, B 2 O 3 : 16.0-25.0%, CaO: 1.0- 2.5%, MgO: 2.0-5.0%, ZnO: 2.0-4.0%, TiO 2 : 0.4-2.0%, ZrO 2 : 0-0.5%, Bi 2 O 3 : 0.1-1.5%.
  • the total amount of RO does not exceed 10%.
  • This application introduces Bi 2 O 3 in the composition for the first time.
  • Bi exists in two forms in glass, [BiO 6 ] and [BiO 3 ].
  • the structure system uses [BiO 6 ] as a network outer body
  • the form of the product exists in the glass structure, and the degree of network connection of the structure is appropriately reduced to reduce the high-temperature viscosity of the glass melt, so as to achieve the efficiency of lowering the melting temperature and energy saving and emission reduction in glass production, while not damaging the dielectric properties of the glass.
  • it if it is introduced too much, it will be easily polarized due to its large ion radius, which will damage the network structure of the glass and cause the dielectric constant to increase.
  • Alkaline earth metal oxides form the outer body of glass and are the main provider of free oxygen. They play the role of bond breaking and have a great influence on the coordination number of boron and aluminum in the alkali-free boroaluminosilicate system. At the same time, alkaline earth metal cations are the accumulation of broken bonds. Therefore, the influence of alkaline earth metals on the physical and chemical properties of alkali-free boroaluminosilicate glass is multifaceted.
  • the main influencing factors of the glass dielectric constant are the ion polarizability and mobility of the elements in the glass composition.
  • Si 4+ , Al 3+ , and B 3+ plasma are all high-field-strength ions with very low mobility, so
  • the dielectric properties mainly depend on the polarizability of ions.
  • the polarizabilities of Mg 2+ , Ca 2+ , and Zn 2+ are all greater than that of Si 4+ . Therefore, when the content of RO oxide introduced increases, the ion polarizability can be increased, thereby increasing the dielectric constant.
  • the main factors affecting polarization are the radius and mass of ions.
  • SiO 2 is a glass structure network forming body, and it is also the main component for obtaining low dielectric glass.
  • the SiO 2 content is less than 55%, the dielectric constant of the glass is relatively large, but too high SiO 2 content will cause the glass melting temperature to rise, the viscosity of the glass liquid increases, and defects such as wire breakage are likely to occur during wire drawing.
  • the content of SiO 2 is limited to 54 to 57%.
  • B 2 O 3 Adding B 2 O 3 to the glass to introduce B 3+ to form BO, the bond energy of this bond is larger than the Si-O bond energy, which can stabilize the glass network structure and limit the polarization of oxygen ions in the glass. Therefore, proper addition of B 2 O 3 can optimize the dielectric properties of the glass.
  • B 3+ since B 3+ has a smaller electronic polarizability than Si 4+ and Al 3+ , the increase in its content will help reduce the dielectric constant.
  • B 2 O 3 is volatile at high temperature and will pollute the environment. At the same time, too high content reduces the chemical stability of the glass, so the dosage should be strictly controlled during the production process. In the present invention, the content of B 2 O 3 is limited to 16% to 25%.
  • Al 2 O 3 is also an oxide that forms the network framework of the glass structure.
  • the appropriate addition of Al 2 O 3 can reduce the phase separation and crystallization tendency of the glass, improve chemical stability, and improve thermal stability. However, if its content is too high, it will increase the high-temperature viscosity of the glass and cause difficulties in melting and clarification. Therefore, the present invention limits the content of Al 2 O 3 to 12-15%.
  • the addition of a small amount of ZrO 2 and TiO 2 can improve the water resistance, acid and alkali resistance of the glass.
  • a low-dielectric glass fiber component in terms of mass fraction, includes the following components:
  • the dielectric constant is 4.9
  • the fiber forming temperature is 1320°C
  • the liquidus temperature is 1050°C
  • the ⁇ T is 270°C
  • the water-soluble amount is 0.8%
  • the acid-soluble amount is 32.9%
  • the alkali-soluble amount is 9.8%.
  • a low-dielectric glass fiber component in terms of mass fraction, includes the following components:
  • the dielectric constant is 4.8
  • the fiber forming temperature is 1310°C
  • the liquidus temperature is 1050°C
  • the ⁇ T is 260°C
  • the water-soluble amount is 0.8%
  • the acid-soluble amount is 30.8%
  • the alkali-soluble amount is 10.2%.
  • a low-dielectric glass fiber component in terms of mass fraction, includes the following components:
  • the dielectric constant is 4.7
  • the fiber forming temperature is 1310°C
  • the liquidus temperature is 1050°C
  • the ⁇ T is 260°C
  • the water-soluble amount is 0.8%
  • the acid-soluble amount is 30.4%
  • the alkali-soluble amount is 9.9%.
  • a low-dielectric glass fiber component in terms of mass fraction, includes the following components:
  • the dielectric constant is 4.8
  • the fiber forming temperature is 1320°C
  • the liquidus temperature is 1020°C
  • the ⁇ T is 300°C
  • the water-soluble amount is 0.9%
  • the acid-soluble amount is 32.5%
  • the alkali-soluble amount is 10.7%.
  • a low-dielectric glass fiber component in terms of mass fraction, includes the following components:
  • the dielectric constant is 4.9
  • the fiber forming temperature is 1310°C
  • the liquidus temperature is 1030°C
  • the ⁇ T is 280°C
  • the water-soluble amount is 0.8%
  • the acid-soluble amount is 30.7%
  • the alkali-soluble amount is 10.8%.
  • the dielectric constant is 4.6
  • the fiber forming temperature is 1325°C
  • the liquidus temperature is 1070°C
  • the ⁇ T is 255°C
  • the water-soluble content is 0.9%
  • the acid-soluble content is 40%.
  • the dielectric constant is 6.6
  • the fiber forming temperature is 1200°C
  • the liquidus temperature is 1065°C
  • the ⁇ T is 135°C
  • the water-soluble amount is 0.5%
  • the acid-soluble amount is 20%
  • the alkali-soluble amount is 6.1%.
  • the present invention provides a method for manufacturing low-dielectric glass fiber, as shown in Figure 1: It includes the following steps: weighing the raw materials according to the composition of the formula, and then mixing them for use; melting, homogenizing and clarifying the mixture obtained in step S1 ; Pour the molten glass in step S2 into a preheated mold, anneal at 600°C for 3 hours and then cool to room temperature in the furnace, and perform performance testing after processing. In this way, by optimizing the composition of the ternary mixed alkaline earth oxide and introducing a small amount of bismuth oxide, a glass with higher melting quality is obtained.
  • the glass of the present invention has a relatively low The dielectric constant of the glass, while ensuring a good balance of water resistance, acid resistance, alkali resistance, etc., and taking into account the realization of the key goal to be solved; the composition does not contain F, which is beneficial to environmental protection, and is suitable for large-scale, clean Industrial production.
  • the low dielectric glass is manufactured and tested according to the following steps
  • the ingredients are prepared according to the composition in Table 1 above, and the raw materials used are quartz, boric acid, alumina, calcium carbonate, magnesium oxide, zinc oxide, titanium dioxide, and bismuth oxide.
  • the weighed raw materials are mixed in a dry powder mixer and homogenized.
  • step S1 pour the uniformly mixed batch material in step S1 into a platinum crucible, and melt it in a high-temperature electric furnace.
  • the melting temperature is controlled at 1600° C., and the temperature is kept at the highest temperature for 3 hours to obtain a uniform molten glass.
  • step S2 Pour the molten glass that has been clarified in step S2 into a preheated mold, and after annealing at 600°C for 3 hours, it is cooled to room temperature in the furnace.
  • the glass is processed into a glass block of a certain size, and the two sides are rough ground, fine ground, and polished.
  • the surface is ultrasonically cleaned, and then placed in an oven to dry.
  • the dielectric constant and dielectric loss performance are tested at 1MHz using a precision impedance meter.
  • Use a high temperature viscometer to test the high temperature viscosity, and take the temperature corresponding to 1000 poise as the drawing temperature.
  • the chemical stability of glass was determined by powder weight loss method.
  • the glass particle size used is 0.3-0.5mm.
  • the water resistance, acid resistance, and alkali resistance experiments were carried out at 98°C, and the immersion time was 24 hours.
  • the acid resistance experiment used 10% H 2 SO 4
  • the alkali resistance experiment used 10% NaOH.
  • the liquidus temperature refers to the temperature at which crystal nuclei begin to form when the glass melt is cooled, that is, the upper limit temperature of glass crystallization, which is measured by the gradient furnace method.
  • the ⁇ T value that is, the difference between the wire drawing temperature and the liquidus temperature, represents the temperature range of wire drawing.

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Abstract

一种低介电玻璃纤维组分，按质量分数计，包括如下组分：SiO 2:54.0-57.0％，Al 2O 3：12.0-15.0％，B 2O 3：16.0-25.0％，CaO：1.0-2.5％，MgO：2.0-5.0％，ZnO：2.0-4.0％，TiO 2：0.4-2.0％,ZrO 2：0-0.5％,Bi 2O 3：0.1-1.5％；除了控制SiO 2、Al 2O 3、B 2O 3氧化物组成在一定范围内，还利用混合碱土效应，控制RO总量小于10％，特别是MgO/RO＝0.3～0.5，ZnO/RO＝0.2～0.5，以控制玻璃的分相、析晶范围，并且通过复合添加少量ZrO 2和TiO 2，改善玻璃的耐水、耐酸碱性。在组成中引入少量Bi 2O 3，使玻璃熔体高温粘度降低，从而实现玻璃生产中降低熔制温度和节能减排的效能，同时不损害玻璃的介电性能。

Description

一种低介电玻璃纤维组分及其制造方法 技术领域
本发明涉及电子信息基板材料领域，尤其涉及一种低介电玻璃纤维组分及其制造方法。
背景技术
目前，在电子信息工业中，玻璃纤维广泛应用于增强覆铜板(CCL)、印刷电路板(PCB)等基板材料。随着产品功能的迭代，除了要求电子玻璃纤维具有抗拉强度高、电绝缘性能好、耐热性和抗腐蚀性能好等基本条件外，其介电性能指标也日趋重要。介电常数越低，电路板中信号的传输速度就越快，传输过程中的能量损失就越低。因此需要构成基板复合材料的玻璃纤维也具有低的介电常数和低的正切损耗。在无机非金属材料中，SiO 2和B 2O 3具有较低的介电常数，因此高二氧化硅、高氧化硼含量的玻璃具有较小的介电常数。如D玻璃纤维具有非常优异的介电性能，其组成以质量百分比计为：72％～76％的SiO 2，0％～5％的Al 2O 3，20％～25％的B 2O 3，3％～5％的Na 2O+K 2O。其介电常数为3.8-4.2，介电损耗约为8×10 -4，但由于该组成中含有较多的SiO 2(70％wt以上),导致其熔融温度较高，拉丝作业温度较高，在拉丝过程中易产生气泡或条纹造成断丝。同时，D玻璃耐水性差，与树脂的粘合性不佳；而常见的E玻璃纤维具有较好的各项性能指标，在市场上得以广泛应用，但其在1MHz时的相对介电常数为6.8，不符合现代电子信息工业对基板复合材料介电常数的要求。
针对D玻璃和E玻璃的以上不足，国内外研究者在组成上进行了一些改 进。
日本专利JP2009286686提出的改进组成为质量分数为45-65％SiO 2，10-20％Al 2O 3,13-25％B 2O 3,5.5-9％MgO,0-10％CaO，0-1％Li 2O+Na 2O+K 2O。
日本纺织(株)特开平10-120437提出的改进组成以质量百分比计为：50-56％SiO 2，10-18％Al 2O 3,18-25％B 2O 3,0-4％MgO,10-17％CaO，0-1％Li 2O+Na 2O+K 2O,0-2％F。
AGY专利CN101594987B以质量百分比计实质上包含52-60％SiO 2、11-16％Al 2O 3、20-30％B 2O 3和4-8％CaO，并且基本不含MgO、基本不含Li 2O、基本不含Na 2O、基本不含K 2O以及基本不含TiO 2。
中国专利CN107298531(A)提出的改进组成为：质量分数62-65％SiO 2,11-13％Al 2O 3,13-15％B 2O 3,5-8％CaO,0.5-2％TiO 2,0.5-2％Li 2O及0.5-2％La 2O 3。
上述专利组成的玻璃介电常数约为4.5～5.5，组成中F元素的引入虽然可以降低玻璃高温粘度，有利于作业成型，但会在生产中对环境造成污染。
发明内容
本发明所要解决的技术问题是提供一种低介电玻璃纤维组分，同时保证该玻璃具有较好的耐水、耐酸、耐碱等性能的均衡，并控制玻璃的分相、析晶范围，避免生产中F挥发造成的污染环境问题。
本发明解决上述技术问题的技术方案如下：一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:54.0-57.0％，Al 2O 3：12.0-15.0％，B 2O 3：16.0-25.0％，CaO：1.0-2.5％，MgO：2.0-5.0％，ZnO：2.0-4.0％，TiO 2：0.4-2.0％,ZrO 2：0-0.5％,Bi 2O 3：0.1-1.5％，所述MgO、CaO和ZnO的质量和小于总质量的10％，MgO /RO＝0.3-0.5,ZnO/RO＝0.2-0.5。
进一步，按质量分数计，包括如下组分：
SiO 2:55.5-56.0％，Al 2O 3：12.5-13.0％，B 2O 3：20.0-22.5％，CaO：1.5-2.0％，MgO：3.5-4.0％，ZnO：2.5-3.0％，TiO 2：0.5-1.2％,ZrO 2：0.3-0.5％,Bi 2O 3：0.5-1.0％。
进一步，按质量分数计，包括如下组分：
SiO 2:55.8％，Al 2O 3：12.5％，B 2O 3：21.5％，CaO：1.7％，MgO：3.8％，ZnO：2.6％，TiO 2：1.0％,ZrO 2：0.5％,Bi 2O 3：0.6％。
一种低介电玻璃纤维的制造方法，包括如下步骤：
S1：按照配方组成进行原料称量，然后混合备用；
S2：将步骤S1所得的混合料进行熔融、均化和澄清；
S3：将步骤S2熔融澄清好的玻璃液倒在预热的模具里，600℃退火3小时后随炉冷却至室温，加工后进行性能测试。
进一步，所述步骤S1中的原料为石英、硼酸、氧化铝、碳酸钙、氧化镁、氧化锌，二氧化钛和氧化铋。
进一步，所述步骤S2中，熔融、均化是将步骤S1混合均匀的配合料倒入铂金坩埚中，在高温电炉中进行熔化，熔化温度控制在1600℃，并在最高温度保温3小时，得到均匀的玻璃液。
进一步，所述步骤S3中，模具在玻璃液倒入前经预热处理。
进一步，所述步骤S3前进行拉丝实验。
进一步，所述拉丝实验将步骤2熔融澄清好的玻璃液流入铂金漏板，进行拉丝，通过冷却气体以及冷却水进行冷却得到玻璃纤维，并通过控制拉丝机转速调整玻璃纤维的直径参数。
本发明提供一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:54.0-57.0％，Al 2O 3：12.0-15.0％，B 2O 3：16.0-25.0％，CaO： 1.0-2.5％，MgO：2.0-5.0％，ZnO：2.0-4.0％，TiO 2：0.4-2.0％,ZrO 2：0-0.5％,Bi 2O 3：0.1-1.5％，所述MgO、CaO和ZnO的质量和小于总质量的10％，MgO/RO＝0.3-0.5,ZnO/RO＝0.2-0.5。这样，在玻璃中添加B 2O 3引入B 3+形成B-O，该键的键能较Si-O键能大，在玻璃中可以起到稳定玻璃网络结构并且限制氧离子极化的作用；因此适量添加B 2O 3可以优化玻璃的介电性能；同时由于B 3+有比Si 4+和Al 3+更小的电子极化率，它的含量增加有利于降低介电常数；Al 2O 3也是形成玻璃结构网络骨架的氧化物，Al 2O 3适量的添加可以降低玻璃的分相、析晶倾向、提高化学稳定性、改善热稳定性；但其含量太高会使增加玻璃高温粘度，导致熔化、澄清困难，故本发明限定Al 2O 3含量范围为12～15％；并且少量ZrO 2和TiO 2的添加，可以改善玻璃的耐水、耐酸碱性。同时，通过优化的三元混合碱土氧化物组成，并引入少量氧化铋，得到了熔融质量较高的玻璃。本发明提供一种低介电玻璃纤维的制造方法，包括如下步骤：按照配方组成进行原料称量，然后混合备用；将步骤S1所得的混合料进行熔融、均化和澄清；将步骤S2熔融澄清好的玻璃液倒在预热的模具里，600℃退火3小时后随炉冷却至室温，加工后进行性能测试。本发明所获得的玻璃具有较低的介电常数，拉丝温度较低，拉丝成型温度与玻璃液相线温度之差都远大于200℃，便于生产控制；与现有技术相比，本发明的玻璃具有相对较低的玻璃介电常数，同时保证了具有较好的耐水、耐酸、耐碱等性能的均衡，兼顾实现了所要解决的关键目标；成分中不含F,有利于环境保护，适用于大规模、清洁化的工业生产。
附图说明
图1为本发明一种低介电玻璃纤维的制造方法的流程示意图。
具体实施方式
以下结合附图对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
如图1所示，本发明提供一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:54.0-57.0％，Al 2O 3：12.0-15.0％，B 2O 3：16.0-25.0％，CaO：1.0-2.5％，MgO：2.0-5.0％，ZnO：2.0-4.0％，TiO 2：0.4-2.0％,ZrO 2：0-0.5％,Bi 2O 3：0.1-1.5％，所述MgO、CaO和ZnO的质量和小于总质量的10％，MgO/RO＝0.3-0.5,ZnO/RO＝0.2-0.5。这样，在玻璃中添加B 2O 3引入B 3+形成B-O，该键的键能较Si-O键能大，在玻璃中可以起到稳定玻璃网络结构并且限制氧离子极化的作用；因此适量添加B 2O 3可以优化玻璃的介电性能；同时由于B 3+有比Si 4+和Al 3+更小的电子极化率，它的含量增加有利于降低介电常数；Al 2O 3也是形成玻璃结构网络骨架的氧化物，Al 2O 3适量的添加可以降低玻璃的分相、析晶倾向、提高化学稳定性、改善热稳定性；但其含量太高会使增加玻璃高温粘度，导致熔化、澄清困难，故本发明限定Al 2O 3含量范围为12～15％；并且少量ZrO 2和TiO 2的添加，可以改善玻璃的耐水、耐酸碱性。
本发明主要技术创新是在保证SiO 2、B 2O 3、Al 2O 3用量的同时，通过优化设计碱土金属RO的含量及组合方式，精确调控CaO\MgO\ZnO的比例，强化三元混合碱土金属效应，并在组成中引入一定量B 2O 3，组成中不引入Li、Na、K等碱土金属和F。这些措施有利于改善玻璃的熔制效果，降低玻璃的分相、析晶倾向，降低拉丝作业温度，并获得相对较低的玻璃介电常数和介电损耗，同时保证具有较好的耐水、耐酸等性能。由于组成中不含F，可以避免生产过程中F挥发对环境造成污染。本发明提供的玻璃组成，以质量％计，包括以下主要组分：SiO 2:54.0-57.0％，Al 2O 3：12.0-15.0％，B 2O 3：16.0-25.0％，CaO：1.0-2.5％，MgO：2.0-5.0％，ZnO：2.0-4.0％，TiO 2：0.4-2.0％,ZrO 2：0-0.5％,Bi 2O 3：0.1-1.5％。RO总量不超过10％。
在低介电玻璃的熔化过程中，由于组成中玻璃网络形成体氧化物含量高，使其熔化温度相对过高，高温粘度较大，澄清困难，作业时易发生分相。在低介电玻璃大规模工业化过程中，如何在保持玻璃性能不发生较大改变的情况下，降低其熔化温度，提高其玻璃的熔制质量一直是长期存在的关键问题。
本申请在组成中首次引入Bi 2O 3，Bi在玻璃中有两种存在形式，[BiO 6]及[BiO 3]，在其含量较少时在结构体系中以[BiO 6]网络外体的形式体存在于玻璃结构中，适当降低结构的网络连接程度，使玻璃熔体高温粘度降低、从而实现玻璃生产中降低熔制温度和节能减排的效能，同时不损害玻璃的介电性能。但若引入过多，会由于其离子半径大，易于极化，破坏玻璃的网络结构，导致介电常数增大。
碱土金属氧化物是玻璃形成外体，是游离氧的主要提供者，起断键的作用，对无碱硼铝硅酸盐体系中的硼和铝的配位数有很大的影响。同时碱土金属阳离子又是断键的聚积者，因此碱土金属对无碱硼铝硅酸盐玻璃的理化性能的影响具有多面性。玻璃介电常数的主要影响因素是玻璃组成中元素的离子极化率和迁移率的大小，Si 4+、Al 3+、B 3+等离子均为高场强离子，可迁移性非常低，所以介电性能主要取决于离子的极化率。Mg 2+、Ca 2+、Zn 2+的极化率均大于Si 4+的极化率，因此引入的RO氧化物含量升高时，能增加离子极化率，从而使介电常数提高。影响极化(电子位移极化和离子位移极化)的主要因素是离子的半径和质量。在单独引入一种碱土金属离子时，Ca 2+的质量大于Mg 2+，所以Ca 2+的离子位移极化小于Mg 2+，所以引入Ca 2+的玻璃介电常数较小。但是对于Zn 2+，一方面其质量大于Mg 2+、Ca 2+，离子位移极化较大，另一方面，其具有18个电子的外层结构，电子位移极化会小于Mg 2+、Ca 2+。因此，通过复合引入Mg 2+、Ca 2+，Zn 2+时，它们协同作用的结果会与引入单个离子时的情况大不相同。由于混合碱土金属效应，本发明中精确改变其比 例时会出现介电常数和介电损耗数据的拐点。在该发明中，控制RO总量小于10％，特别是MgO/RO＝0.3-0.5,ZnO/RO＝0.2-0.5。
SiO 2是玻璃结构网络形成体，同时也是获得低介电玻璃的主成分。当SiO 2含量低于55％时，玻璃的介电常数较大，但SiO 2含量太高，会导致玻璃熔化温度的升高，玻璃液粘度增大，拉丝时易出现断丝等缺陷。本申请中限定SiO 2含量54～57％。
在玻璃中添加B 2O 3引入B 3+形成B-O，该键的键能较Si-O键能大，在玻璃中可以起到稳定玻璃网络结构并且限制氧离子极化的作用。因此适量添加B 2O 3可以优化玻璃的介电性能。同时由于B 3+有比Si 4+和Al 3+更小的电子极化率，它的含量增加有利于降低介电常数。但B 2O 3高温易挥发，会对环境造成污染，同时含量过高降低玻璃化学稳定性，在生产过程中应严格控制用量。在本发明中限定B 2O 3含量16％～25％。
Al 2O 3也是形成玻璃结构网络骨架的氧化物，Al 2O 3适量的添加可以降低玻璃的分相、析晶倾向、提高化学稳定性、改善热稳定性。但其含量太高会使增加玻璃高温粘度，导致熔化、澄清困难，故本发明限定Al 2O 3含量范围为12～15％
少量ZrO 2和TiO 2的添加，可以改善玻璃的耐水、耐酸碱性。
实施例1
一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:54.0％，Al 2O 3：12.0％，B 2O 3：25.0％，CaO：1.0％，MgO：5.0％，ZnO：2.0％，TiO 2：0.4％，ZrO 2：0.5％,Bi 2O 3：0.1％。
介电常数为4.9，纤维成型温度为1320℃，液相线温度1050℃，△T为270℃，水溶量为0.8％，酸溶量为32.9％，碱溶量为9.8％。
实施例2
一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:55.5％，Al 2O 3：12.5％，B 2O 3：22.5％，CaO：1.5％，MgO：4.0％，ZnO：2.5％，TiO 2：0.5％，ZrO 2：0.5％,Bi 2O 3：0.5％。
介电常数为4.8，纤维成型温度为1310℃，液相线温度1050℃，△T为260℃，水溶量为0.8％，酸溶量为30.8％，碱溶量为10.2％。
实施例3
一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:55.8％，Al 2O 3：12.5％，B 2O 3：21.5％，CaO：1.7％，MgO：3.8％，ZnO：2.6％，TiO 2：1.0％，ZrO 2：0.5％，Bi 2O 3：0.6％。
介电常数为4.7，纤维成型温度为1310℃，液相线温度1050℃，△T为260℃，水溶量为0.8％，酸溶量为30.4％，碱溶量为9.9％。
实施例4
一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:56.0％，Al 2O 3：13.0％，B 2O 3：20.0％，CaO：2.0％，MgO：3.5％，ZnO：3.0％，TiO 2：1.2％，ZrO 2：0.3％，Bi 2O 3：1.0％。
介电常数为4.8，纤维成型温度为1320℃，液相线温度1020℃，△T为300℃，水溶量为0.9％，酸溶量为32.5％，碱溶量为10.7％。
实施例5
一种低介电玻璃纤维组分，按质量分数计，包括如下组分：
SiO 2:57.0％，Al 2O 3：15.0％，B 2O 3：16.0％，CaO：2.5％，MgO：2.0％，ZnO：4.0％，TiO 2：2.0％，Bi 2O 3：1.5％。
介电常数为4.9，纤维成型温度为1310℃，液相线温度1030℃，△T为280℃，水溶量为0.8％，酸溶量为30.7％，碱溶量为10.8％。
对比例1
SiO 2:54.48％，Al 2O 3：14.92％，B 2O 3：19.89％，CaO：3.98％，MgO：3.98％，TiO 2：1.99％，F:0.50％,Li 2O:0.15％,R 2O：0.09％。
介电常数为4.6，纤维成型温度为1325℃，液相线温度1070℃，△T为255℃，水溶量为0.9％，酸溶量为40％。
对比例2
SiO 2:54.61％，Al 2O 3：14.11％，B 2O 3：6.08％，CaO：22.39％，MgO：1.17％，TiO 2：0.27％，F:0.60％,R 2O：0.58％。
介电常数为6.6，纤维成型温度为1200℃，液相线温度1065℃，△T为135℃，水溶量为0.5％，酸溶量为20％，碱溶量为6.1％。
表1：实施例对照表
Figure PCTCN2020073474-appb-000001
本发明提供一种低介电玻璃纤维的制造方法，如图1所示：包括如下步骤：按照配方组成进行原料称量，然后混合备用；将步骤S1所得的混合料进行熔融、均化和澄清；将步骤S2熔融澄清好的玻璃液倒在预热的模具里，600℃退火3小时后随炉冷却至室温，加工后进行性能测试。这样，通过优 化的三元混合碱土氧化物组成，并引入少量氧化铋，得到了熔融质量较高的玻璃。它具有较低的介电常数，拉丝温度较低，拉丝成型温度与玻璃液相线温度之差都远大于200℃，便于生产控制；与现有技术相比，本发明的玻璃具有相对较低的玻璃介电常数，同时保证了具有较好的耐水、耐酸、耐碱等性能的均衡，兼顾实现了所要解决的关键目标；成分中不含F,有利于环境保护，适用于大规模、清洁化的工业生产。
实施例
所述的低介电玻璃按照以下步骤进行制造和性能测试
(1)配料：
按照上述表1的组成进行配料，采用的原料为石英、硼酸、氧化铝、碳酸钙、氧化镁、氧化锌，二氧化钛、氧化铋。将所称取的原料在干粉混合机中进行混合，均化。
(2)玻璃熔制
将步骤S1混合均匀的配合料倒入铂金坩埚中，在高温电炉中进行熔化，熔化温度控制在1600℃，并在最高温度保温3小时，得到均匀的玻璃液。
(3)玻璃退火
将步骤S2熔融澄清好的玻璃液倒在预热的模具里，600℃的退火3小时后随炉冷却至室温。
(4)性能测试
将玻璃加工成一定尺寸的玻璃块，然后将两面粗磨、细磨、抛光后，超声清理表面，然后放入烘箱干燥，利用精密阻抗仪在1MHz进行介电常数和介电损耗性能测试。利用高温粘度仪测试高温粘度，并取1000泊对应的温度为拉丝温度。利用粉末失重法测定玻璃化学稳定性。采用的玻璃粒度为0.3～0.5mm。耐水和耐酸、耐碱实验均在98℃进行，浸泡时间为24小时，耐酸实验采用10％H 2SO 4，耐碱实验采用10％NaOH。液相线温度是指对应 于玻璃熔体冷却时晶核开始形成的温度，即玻璃析晶的上限温度，通过梯度炉法测定。△T值，即拉丝成型温度与液相线温度之差，表示拉丝成型的温度范围。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (9)

  1. 一种低介电玻璃纤维组分，其特征在于，按质量分数计，包括如下组分：
    SiO 2:54.0-57.0％，Al 2O 3：12.0-15.0％，B 2O 3：16.0-25.0％，CaO：1.0-2.5％，MgO：2.0-5.0％，ZnO：2.0-4.0％，TiO 2：0.4-2.0％,ZrO 2：0-0.5％,Bi 2O 3：0.1-1.5％，所述MgO、CaO和ZnO的质量和小于总质量的10％，MgO/RO＝0.3-0.5,ZnO/RO＝0.2-0.5。
  2. 根据权利要求1所述的低介电玻璃纤维组分，其特征在于，按质量分数计，包括如下组分：
    SiO 2:55.5-56.0％，Al 2O 3：12.5-13.0％，B 2O 3：20.0-22.5％，CaO：1.5-2.0％，MgO：3.5-4.0％，ZnO：2.5-3.0％，TiO 2：0.5-1.2％,ZrO 2：0.3-0.5％,Bi 2O 3：0.5-1.0％。
  3. 根据权利要求2所述的低介电玻璃纤维组分，其特征在于，按质量分数计，包括如下组分：
    SiO 2:55.8％，Al 2O 3：12.5％，B 2O 3：21.5％，CaO：1.7％，MgO：3.8％，ZnO：2.6％，TiO 2：1.0％,ZrO 2：0.5％,Bi 2O 3：0.6％。
  4. 一种低介电玻璃纤维的制造方法，其特征在于：包括如下步骤：
    S1：按照配方组成进行原料称量，然后混合备用；
    S2：将步骤S1所得的混合料进行熔融、均化和澄清；
    S3：将步骤S2熔融澄清好的玻璃液倒在预热的模具里，600℃退火3小时后随炉冷却至室温，加工后进行性能测试。
  5. 根据权利要求4所述的低介电玻璃纤维的制造方法，其特征在于：所述步骤S1中的原料为石英、硼酸、氧化铝、碳酸钙、氧化镁、氧化锌，二氧化钛和氧化铋。
  6. 根据权利要求4所述的低介电玻璃纤维的制造方法，其特征在于：所述步骤S2中，熔融、均化是指将步骤S1混合均匀的配合料倒入铂金坩埚中，在高温电炉中进行熔化，熔化温度控制在1600℃，并在最高温度保温3小时，得到均匀的玻璃液。
  7. 根据权利要求4所述的低介电玻璃纤维的制造方法，其特征在于：所述步骤S3中，模具在玻璃液倒入前经预热处理。
  8. 根据权利要求4所述的低介电玻璃纤维的制造方法，其特征在于：所述步骤S3前进行拉丝实验。
  9. 根据权利要求8所述的低介电玻璃纤维的制造方法，其特征在于：所述拉丝实验是将步骤2熔融澄清好的玻璃液流入铂金漏板，进行拉丝，通过冷却气体以及冷却水进行冷却得到玻璃纤维，并通过控制拉丝机转速调整玻璃纤维的直径参数。
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