CN101633560B - Lead-free low-melting-point glass and preparation method thereof - Google Patents

Lead-free low-melting-point glass and preparation method thereof Download PDF

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CN101633560B
CN101633560B CN 200810117033 CN200810117033A CN101633560B CN 101633560 B CN101633560 B CN 101633560B CN 200810117033 CN200810117033 CN 200810117033 CN 200810117033 A CN200810117033 A CN 200810117033A CN 101633560 B CN101633560 B CN 101633560B
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glass
percent
low
melting
lead
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朱庆山
李洪钟
谢朝晖
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中国科学院过程工程研究所
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Abstract

The invention relates to a lead-free low-melting-point glass and a preparation method thereof, which belongs to the technical field of glass production. The low-melting-point glass takes V2O5, B2O3, ZnO, P2O5, Bi2O3 and Fe2O3 as essential components, and comprises the following components in percentage by weight: 5 to 29.9 percent of the V2O5, 2 to 17.9 percent of the B2O3, 5 to 30 percent of the ZnO, 5 to 29.9 percent of the P2O5, 1 to 15 percent of the Bi2O3, 1 to 15 percent of the Fe2O3, 0 to 29.9 percent of BaO, 0 to 20 percent of Sb2O3, 0 to 25 percent of SnO, 0 to 5 percent of Al2O3, and 0 to 5 percent of SiO2. The low-melting-point glass can be mixed together with a filler to prepare sealing glass powder, wherein the filler adopts one of aluminum titanate, beta-eucryptite, aluminum oxide, zircon and quartz sand, and the weight ratio of the filler to the low-melting-point glass is 0-40:100. The invention aims to obtain a piece of glass, which has the advantages of low sealing temperature, appropriate thermal expansion coefficient, good chemical stability and small amount of raw material components and is applied to sealing electronic display glasses.

Description

一种无铅低熔玻璃及其制备方法 A lead-free low-melting glass and preparation method

技术领域 FIELD

[0001] 本发明涉及一种应用于电子显示器封接的无铅低熔玻璃材料,属于玻璃生产技术领域。 [0001] The present invention relates to lead-free low-melting glass material which is applied to the sealing of an electronic display, belonging to the field of glass production.

背景技术 Background technique

[0002] 等离子显示器、液晶显示屏、和真空荧光显示屏等电子显示器的制作过程中,都需用封接玻璃进行封接。 Production process of an electronic display [0002] plasma display, LCD, vacuum fluorescent display and the like, are required for sealing glass sealing. 由于这种封接作业是在400°C〜500°C左右的较低温度下进行的,所以要求封接玻璃的软化温度较低。 Due to this sealing operation is carried out at a relatively low temperature of about 400 ° C~500 ° C, it requires the softening temperature of the sealing glass is low. 传统上都是采用含氧化铅比例较高的玻璃作为封接材料。 Traditionally use lead oxide containing a higher proportion of glass as the sealing material. 但是随着这类电子产品的大规模应用,废弃物中的含铅材料不能有效回收,给环境造成很大污染,威胁到人类健康。 But with such large-scale application of electronic products, lead-containing waste material can not be effectively recycled, cause great pollution to the environment, threaten human health. 近年来人们一直在努力寻找不含铅的低温封接玻璃。 In recent years, people have been trying to find lead-free low-temperature sealing glasses.

[0003] 较早提出的无铅低温封接玻璃产品主要是磷酸盐系玻璃,如美国专利US 5246890、日本专利JP2003146691、及中国专利CN 93109196. 9、和CN95103974. 1 等,都是含有Sn0、ai0、Ba0的二元或三元磷酸盐系玻璃。 [0003] An earlier unleaded low-temperature sealing glass products mainly phosphate-based glass, such as the US patent US 5246890, Japanese Patent JP2003146691, and Chinese patent CN 93109196. 9, and CN95103974. 1, are contained Sn0, ai0, di- or tri-phosphate glass of Ba0. 由于磷酸盐系封接玻璃的膨胀系数较高,化学稳定性较差,即使添加多种填料组分也不能达到使用要求,所以难以推向应用。 Since the phosphate-based glass sealing high coefficient of expansion, poor chemical stability, even if adding more filler components can not meet the requirements, it is difficult to push the application. 另有钒酸盐系玻璃和铋酸盐系玻璃的软化温度也较低,化学稳定性优于磷酸盐系玻璃,但是这两个体系玻璃存在着原料成本高、线胀系数大的缺点,单独的钒酸盐系玻璃或铋酸盐系玻璃也难以作为电子显示器封接材料。 Another softening temperature vanadate and bismuth-based glass-based glass is low, the chemical stability is better than phosphate-based glass, but the two systems there are high raw material cost of the glass, a large linear expansion coefficient disadvantages alone vanadate glass-based or bismuth-based glass is also difficult to use as an electronic display sealing material. 近年来低温封接玻璃有向混合体系玻璃发展的趋势。 In recent years, the development of low-temperature sealing glass has a tendency to mix glass system.

[0004] 美国专利US6809049采用SiO-B2O3-P2O5玻璃体系,重量百分比组成为:ZnO 45〜 80%,B2O3 5〜45%、P205 1〜35%。 [0004] U.S. Patent No. US6809049 using SiO-B2O3-P2O5 glass system, in weight%: ZnO 45~ 80%, B2O3 5~45%, P205 1~35%. 由于采用的SiO和化03的比例较高,玻璃软化温度高达500〜580°C,所以封接温度偏高。 Due to the high proportion of SiO and 03 employed, the glass transition temperature up to 500~580 ° C, so that the sealing temperature is high.

[0005] 美国专利US6309989公开的玻璃组分的摩尔百分数为:SnO 30〜70%、B2O3 5〜 30%,P20524. 1〜45%,并且Β203/Ρ205 > 0. 2。 [0005] The mole percent of the glass composition is disclosed in U.S. Patent No. US6309989: SnO 30~70%, B2O3 5~ 30%, P20524 1~45%, and Β203 / Ρ205> 0. 2.. 其封接温度约500°C,热膨胀系数在10. 5〜 15X10—6范围,这两个参数都偏高。 Its sealing temperature of about 500 ° C, a thermal expansion coefficient in the range of 10. 5~ 15X10-6, both parameters are high.

[0006] 中国专利CN 200310103589. X,提出一种V2O5-P2O5-Sb2O3体系封接玻璃,采用重量百分比组成为:V205 30〜70%,P205 10〜30% JPSb2O3 0.5〜25%。 [0006] Chinese Patent CN 200310103589. X, proposes a V2O5-P2O5-Sb2O3 system sealing glass, use of percent by weight: V205 30~70%, P205 10~30% JPSb2O3 0.5~25%. 其中V2O5比例较高, 一般在50%以上。 Wherein the ratio of V2O5 higher, generally above 50%. 因而仍然具有钒酸盐系玻璃的缺点,如原料昂贵、熔制过程易起泡、不耐酸洗。 Therefore still has the drawback of vanadate-based glass, such as an expensive raw material, foaming the melting process, pickling intolerance.

[0007] 中国专利200310103592. 1在V2O5-P2O5-Sb2O3体系玻璃基础上,加入重量百分比分别不超过ιο%的sio2、aiO、Ai2o3、&o、&o3、Tio2、wo2、或碱金属氧化物,作为玻璃稳定组分。 [0007] Chinese Patent No. 200310103592.1 in the V2O5-P2O5-Sb2O3 glass system based on the addition of the weight percentage does not exceed ιο% of sio2, aiO, Ai2o3, & o, & o3, Tio2, wo2, or an alkali metal oxide, a glass stabilizing components. 另外还包括分别不超过5%的Sn、Zn、或Ca的卤化物。 Also included halide does not exceed 5% of Sn, Zn, or Ca. 但是采用的V2O5比例仍然较高。 But a higher proportion of V2O5 is still used.

[0008] 中国专利2006101U901. 5提出在V2O5-P2O5Ib2O3系统中加稀土氧化物。 [0008] Chinese Patent 2006101U901. 5 made of rare earth oxide added to the V2O5-P2O5Ib2O3 system. 玻璃基本组分中含有氧化物的重量百分比为=V2O5 30 -80%,P2O5 10〜60%、SId203 2〜40%,可以加入化030 〜25%、Al2O3 0 〜5%、Bi2O3 0 〜10%、Fii2O3 0 〜8%、SiO2 0 〜8%,以及少量碱金属氧化物、碱土金属氧化物、卤化物和一定的稀土氧化物。 Basic glass component contained in the weight percent oxide = V2O5 30 -80%, P2O5 10~60%, SId203 2~40%, may be added of 030 ~25%, Al2O3 0 ~5%, Bi2O3 0 ~10% , Fii2O3 0 ~8%, SiO2 0 ~8%, and small amounts of alkali metal oxides, alkaline earth metal oxides, halides and certain rare earth oxides. 加入多组分的目的在于降低玻璃熔融温度,降低热膨胀系数,提高化学稳定性。 Object is to reduce the addition of the multicomponent glass melting temperature, lowering the thermal expansion coefficient and improve chemical stability. 由于这个玻璃是在V2O5-P2O5-Sb2O3 体系玻璃基础上发展而来的,仍含有较高的V2O5,同样较大程度上保留了钒酸盐系玻璃的缺点。 Since this glass is a glass base V2O5-P2O5-Sb2O3 system developed on, still contains a high V2O5, retained the shortcomings of the Department of vanadate glass is also to a large extent. 而且卤化物在真空条件下会有一定挥发,对电极有腐蚀作用。 And there will be some volatile halide under vacuum conditions have a corrosive effect on the electrode. 另外,原料组分过多,给玻璃生产带来不便。 Further, excessive feed components, inconvenience for glass production.

[0009] 中国专利公开2006100416¾. 2提出一种用于金属氧化物避雷器的密封玻璃,属于V2O5-B2O3-ZnO体系。 [0009] Chinese Patent Publication 2006100416¾. 2 proposes a sealing glass for metal oxide surge arresters, belonging V2O5-B2O3-ZnO system. 它含有氧化物组分重量百分比为=V2O5 20〜30%、B203 18〜对%、 Zn045 〜55%,以及P2O5 0 〜3%、Bi2O3 0 〜10%、MO3 0 ~ 5%, BaO 0 〜5%等。 Containing oxide component weight percent = V2O5 20~30%, B203 18~ to%, Zn045 ~55%, and P2O5 0 ~3%, Bi2O3 0 ~10%, MO3 0 ~ 5%, BaO 0 ~5 %Wait. 这个玻璃的缺点是软化温度偏高,封接温度高达530°C,不适用于显示器玻璃的封接。 The disadvantage is that the glass softening temperature is high, the sealing temperature up to 530 ° C, does not apply to the display glass sealing.

发明内容 SUMMARY

[0010] 针对原有无铅封接玻璃的不足,本发明提出一种不含铅的低熔玻璃,目的在于使这种材料满足封接温度低、热膨胀系数适当、化学稳定性好、原料组分数量较少的要求。 [0010] For the existing lead-free sealing glass is insufficient, the present invention provides a lead-free low-melting glass material satisfying this purpose is to make a low sealing temperature, an appropriate coefficient of thermal expansion, chemical stability, material groups It requires a smaller number of points. 本发明的另一目的在于提供一种制造上述低熔玻璃的方法,以便使玻璃的制备易于进行。 Another object of the present invention is to provide a process for producing the low-melting glass, so as to be readily prepared glass.

[0011] 为实现上述目的,本发明所采用的技术方案之一是: [0011] To achieve the above object, one aspect of the present invention is employed:

[0012] 一种无铅低熔玻璃,其特征在于,该低熔玻璃以V205、B203、Zn0、P205、Bi203、和Fe2O3 为必备成分,重量百分数组成范围为:V2O5 5〜29.9%、化03 2〜17.9%、SiO 5〜30%、 P2055 〜29. 9%, Bi2O3 1 〜15%、Fe2O3 1 〜15%,BaO 0 〜29. 9%, Sb2O3 0 〜20%、SnO 0 〜25%、A1203 0 〜5%、Si& 0 〜5%。 [0012] A lead-free low-melting glass, characterized in that the low-melting glass to V205, B203, Zn0, P205, Bi203, and Fe2O3 as an essential component, the weight percent composition ranges: V2O5 5~29.9%, of 03 2~17.9%, SiO 5~30%, P2055 ~29. 9%, Bi2O3 1 ~15%, Fe2O3 1 ~15%, BaO 0 ~29. 9%, Sb2O3 0 ~20%, SnO 0 ~25% , A1203 0 ~5%, Si & 0 ~5%.

[0013] 该低熔玻璃可以与填料混合制备成封接玻璃粉,用于玻璃与玻璃、或玻璃与陶瓷之间的封接,所采用的填料是钛酸铝、锂霞石、三氧化二铝、锆英石、和石英砂中的一种, 并且填料与低熔玻璃的重量比为0〜40 : 100。 [0013] The low-melting glass with the filler may be mixed to prepare a sealing glass frit, the glass and the glass, or sealing between the glass and the ceramic filler used is aluminum titanate, eucryptite trioxide aluminum, zircon, quartz sand, and in one, the filler and the weight ratio of the low melting glass is 0 to 40: 100.

[0014] 本发明所采用的技术方案之二是:一种无铅低熔玻璃的制备方法,至少包括以下步骤: [0014] used in the present invention, the technical solutions of the two is: A method for preparing lead-free low-melting glass, comprising at least the steps of:

[0015] 步骤1 :按所确定的玻璃成分配比称取原料,其中化03由硼酸引入、P2O5由磷酸二氢铵引入,BaO由碳酸钡引入,其余成分直接由其氧化物形式引入,将原料混勻制成配合料; [0015] Step 1: glass component according to the determined ratio of weighed material, wherein the introduction of the boric acid 03, P2O5 introduced by ammonium dihydrogen phosphate, BaO introduced by barium, the remaining components form oxides by the direct introduction of the made from raw batch mix;

[0016] 步骤2 :将配合料在200〜300°C下预烧2_3小时,然后研磨成分散的粉末; [0016] Step 2: The batch calcined 2_3 hours at 200~300 ° C, and then ground into a powder dispersion;

[0017] 步骤3 :将粉末放入氧化铝或石英坩埚,放入电炉升温,在1000〜1200°C下保温0. 5〜1. 5小时; [0017] Step 3: The powder was placed in an alumina or quartz crucible, heated in an electric furnace, and kept at 1000~1200 ° C 0. 5~1 5 hours;.

[0018] 步骤4 :将玻璃熔体迅速倒入水中进行水淬得到玻璃颗粒,或将玻璃熔体倒在金属板上得到玻璃块体。 [0018] Step 4: The glass melt was rapidly quenched by water was poured into water to obtain glass particles, or glass melt poured onto a metal plate to obtain a glass block.

[0019] 在上述封接玻璃的基础玻璃中,V2O5, P205、Bi2O3三组分在一定范围内配合可以使玻璃软化温度降低;但是过多使用这三种组分任一种都会导致膨胀系数过大和玻璃化学稳定性降低、过少则不能形成玻璃,因此将它们分别控制在V2O5 5〜四.9%、P2O5 5〜四.9、 Bi2O3 1〜15% ;适量的化03和ZnO可以提高玻璃稳定性,但是过多的化03或ZnO会导致软化点升高、过少则不起提高玻璃稳定性作用,因此将化03控制在2〜17. 9%, ZnO控制在5〜30% ;Fe2O3可以改善含磷玻璃的抗水性能,但是过多的F^O3会使玻璃膨胀系数加大、 过少则对玻璃抗水性能影响不显著,因此将I^e2O3控制在1〜15% ;引入少量的Ba0、Sb203、 A1203、SiO2可以进一步改善玻璃稳定性,但是这些组分过高会使玻璃软化温度升高,因此将它们分别控制在BaOO〜四.9%、Sb2O3 0〜20%、Al2O3 0〜5%、禾口SiO2 0〜5% ;引入少量SnO有助 [0019] On the basis of the above-described glass in the sealing glass, V2O5, P205, Bi2O3 three-component complex may be within a certain range of the glass softening temperature decrease; however, excessive use of any of these three components will cause one kind of over-expansion coefficient Japanese reduced chemical stability of glass, the glass is not formed is too small, so they are controlled V2O5 5~ four .9%, P2O5 5~ four .9, Bi2O3 1~15%; amount of ZnO and 03 of the glass can be improved stability, but too much of the 03 lead to the softening point or ZnO increased, too little effect to improve the glass stability can not afford, and therefore the control 03 of 2~17 9%, ZnO 5~30% control.; Fe2O3 phosphorus-containing glass can be improved water resistance, but too much F ^ O3 would increase the expansion coefficient of glass, the water is too small, the anti-impact properties of glass is not significant, thus controlling the I ^ e2O3 1~15%; introducing a small amount of Ba0, Sb203, A1203, SiO2 can be further improved stability of the glass, but these components are excessively high glass transition temperature will increase, and therefore they were controlled BaOO~ four .9%, Sb2O3 0~20%, Al2O3 0~5%, Hekou SiO2 0~5%; introducing a small amount SnO help 于进一步降低玻璃软化温度,但是过量的SnO会使玻璃熔化时气氛控制变得困难,因此将SnO控制在0〜25%。 To further reduce the glass transition temperature, but an excess of SnO melting glass will be difficult to control the atmosphere, thus the control 0~25% SnO. 加入上述填料的目的是为了调节封接玻璃的热膨胀系数。 The purpose of adding the filler is to adjust the thermal expansion coefficient of the sealing glass. [0020] 本发明的有益效果是:所提供的低熔玻璃不含铅,可以替代含铅封接玻璃,消除铅玻璃对环境的污染;玻璃中v205、P2O5, Bi2O3含量适中,既保证玻璃软化点较低,又克服了它们在高含量时各自所具有的缺点;所采用的多种网络形成剂同时存在,可以使玻璃软化点进一步降低;所采用的原料种类较少,便于玻璃制备。 [0020] Advantageous effects of the present invention are: to provide the lead-free low-melting glass, may be substituted for lead sealing glass, lead glass eliminate pollution of the environment; glass v205, P2O5, Bi2O3 content is moderate, both to ensure the glass softening lower point and overcomes each of them at high levels has the drawback; more network formers employed exist, can further reduce the softening point of the glass; less types of raw materials used, to facilitate the preparation of the glass. 这种无铅低熔玻璃的软化点在280〜 360°C,热膨胀系数在80〜110X10_7°C范围,可以广泛用于各种玻璃与玻璃、或玻璃与陶瓷之间的密封封接。 Such a softening point of lead-free low-melting glass at 280~ 360 ° C, a thermal expansion coefficient in the range 80~110X10_7 ° C, can be used in a wide variety of glass and glass, or sealing between the sealing glass and ceramics.

具体实施方式 detailed description

[0021] 表1.实施例玻璃的重量百分比组成 [0021] Table 1. Embodiment weight percentage of the glass composition

[0022] [0022]

Figure CN101633560BD00051

[0023]实施例 1 :按表1 所列1# 样品的配比称取V205、H3B03、ai0、NH4H2P04、Bi203、和F%03、 Sb203> SnO混勻制成的配合料。 [0023] Example 1: According to the components listed in Table 1. Sample 1 weighed V205, H3B03, ai0, NH4H2P04, Bi203, and F% 03, Sb203> batch mixing SnO made. 将配合料在200°C下预烧2小时,然后研磨成分散的粉末。 The batch at 200 ° C for calcined for 2 hours and then ground to a powder dispersion. 将粉末放入氧化铝坩埚,在1100°C下熔化1小时,然后将玻璃熔体迅速倒在钢板上冷却,得到无铅低熔玻璃。 The powder was placed in an alumina crucible, melted at 1100 ° C 1 hour and then the glass melt was poured onto the steel sheet was cooled rapidly to give a low-melting lead-free glass.

[0024]实施例 2 :按表1 所列2# 样品的配比称取V205、H3B03、ai0、NH4H2P04、Bi203、和F%03、Sb203> SnO混勻制成的配合料。 [0024] Example 2: Sample No. 2 according to the ratio listed in Table 1 were weighed V205, H3B03, ai0, NH4H2P04, Bi203, and F% 03, Sb203> batch mixing SnO made. 将配合料在200°C下预烧2小时,然后研磨成分散的粉末。 The batch at 200 ° C for calcined for 2 hours and then ground to a powder dispersion. 将粉末放入氧化铝坩埚,在1100°C下熔化1小时,然后将玻璃熔体迅速倒在钢板上冷却,得到无铅低熔玻璃。 The powder was placed in an alumina crucible, melted at 1100 ° C 1 hour and then the glass melt was poured onto the steel sheet was cooled rapidly to give a low-melting lead-free glass. 将冷却后的玻璃砸碎,放入球磨罐进行球磨,将球磨后的玻璃粉过300目筛。 The cooled glass smashing, ball milling into a ball mill jar, after the glass frit is milled through 300 mesh sieve. 将石英砂粉磨后过300目筛,然后将石英砂细粉与玻璃粉按重量比30 : 100的比例混合均勻,得到封接玻璃粉。 After the quartz sand grinding through 300 mesh screen, and then the glass powder and quartz sand powder weight ratio of 30: 100 ratio uniformly mixed to obtain a glass frit seal.

[0025]实施例 3 :按表1 所列3# 样品的配比称取V205、H3BO3> ZnO, NH4H2PO4, Bi203、Fe203> BaC03>Sb2O3^Al (OH) 3、和活性SiO2,混勻制成的配合料。 [0025] Example 3: According to the components listed in Table 3 Sample 1 weighed V205, H3BO3> ZnO, NH4H2PO4, Bi203, Fe203> BaC03> Sb2O3 ^ Al (OH) 3, and the activity of SiO2, mix made the batch. 将配合料在200°C下预烧2小时,然后研磨成分散的粉末。 The batch at 200 ° C for calcined for 2 hours and then ground to a powder dispersion. 将粉末放入氧化铝坩埚,在1100°C下熔化1小时,然后将玻璃熔体迅速倒在钢板上冷却,得到无铅低熔玻璃。 The powder was placed in an alumina crucible, melted at 1100 ° C 1 hour and then the glass melt was poured onto the steel sheet was cooled rapidly to give a low-melting lead-free glass. 将冷却后的玻璃砸碎,放入球磨罐进行球磨,将球磨后的玻璃粉过300目筛。 The cooled glass smashing, ball milling into a ball mill jar, after the glass frit is milled through 300 mesh sieve. 将氧化铝粉磨后过300目筛,然后将氧化铝粉与玻璃粉按重量比30 : 100的比例混合均勻,得到封接玻璃粉。 After alumina grinding through 300 mesh screen, and then the glass powder and alumina powder by weight ratio of 30: uniformly mixing ratio of 100 to give the sealing glass frit.

[0026]实施例 4 :按表1 所列3# 样品的配比称取V205、H3BO3> ZnO, NH4H2PO4, Bi203、Fe203> BaC03、Sb2O3, SnO,混勻制成的配合料;将配合料在200°C下预烧2小时,然后研磨成分散的粉末。 [0026] Example 4: According to the components listed in Table 3 Sample 1 weighed V205, H3BO3> ZnO, NH4H2PO4, Bi203, Fe203> BaC03, Sb2O3, SnO, made of a batch mix; and in batch calcined for 2 hours at 200 ° C, and then ground into a powder dispersion. 将粉末放入氧化铝坩埚,在1100°C下熔化1小时;然后将玻璃熔体迅速倒在钢板上冷却,得到无铅低熔玻璃。 The powder was placed in an alumina crucible, melted at 1100 ° C 1 h; then the glass melt was poured onto the steel sheet was cooled rapidly to give a low-melting lead-free glass. 将冷却后的玻璃砸碎,放入球磨罐进行球磨,将球磨后的玻璃粉过300目筛。 The cooled glass smashing, ball milling into a ball mill jar, after the glass frit is milled through 300 mesh sieve. 将氧化铝粉磨后过300目筛,然后将氧化铝粉与玻璃粉按重量比30 : 100的比例混合均勻,得到封接玻璃粉。 After alumina grinding through 300 mesh screen, and then the glass powder and alumina powder by weight ratio of 30: uniformly mixing ratio of 100 to give the sealing glass frit.

Claims (3)

  1. 1. 一种无铅低熔玻璃,其特征在于,所述低熔玻璃以V205、B203、Zn0、P205、Bi203、和Fii2O3 为必备成分,其质量百分数组成范围为=V2O5 5〜29. 9%,B2O3 2〜17. 9%,ZnO 5〜30%、 P2O5 5 〜29. 9%, Bi2O3 1 〜15%、Fii2O3 1 〜15%、BaO 0 〜29. 9%, Sb2O3 0 〜20%、SnO 0 〜25%、A1203 0 〜5%、Si& 0 〜5%。 1. A lead-free low-melting glass, characterized in that said low-melting glass to V205, B203, Zn0, P205, Bi203, and Fii2O3 essential component of which is the mass percentage composition range = V2O5 5~29. 9 %, B2O3 2~17. 9%, ZnO 5~30%, P2O5 5 ~29. 9%, Bi2O3 1 ~15%, Fii2O3 1 ~15%, BaO 0 ~29. 9%, Sb2O3 0 ~20%, SnO 0 ~25%, A1203 0 ~5%, Si & 0 ~5%.
  2. 2.根据权利要求1所述的无铅低熔玻璃,其特征在于,该低熔玻璃可以与填料混合制备成封接玻璃粉,用于玻璃与玻璃、或玻璃与陶瓷之间的封接,所采用的填料是钛酸铝、 β -锂霞石、三氧化二铝、锆英石、和石英砂中的一种,并且填料与低熔玻璃的重量比为0〜 40 : 100。 A lead-free low-melting glass according to claim 1, wherein the low-melting glass with the filler may be mixed to prepare a sealing glass frit, the glass and the glass, or sealing between the glass and ceramics, the filler used is aluminum titanate, β - eucryptite, alumina, zircon, and a silica sand, and the weight ratio of the filler with a low-melting glass is 0~ 40: 100.
  3. 3. 一种无铅低熔玻璃的制备方法,其特征在于,所述制备方法为用于制造权利要求1 所述低熔玻璃的方法,该制备方法至少包括以下步骤:步骤1 :按着所确定的玻璃成分配比称取原料,其中氏03由硼酸引入、P2O5由磷酸二氢铵引入、氧化钡由碳酸钡引入,其余成分直接由氧化物原料引入,将原料混勻制成配合料;步骤2 :将配合料在200〜300°C下预烧2〜3小时,然后研磨成分散的粉末;步骤3 :将粉末放入氧化铝或石英坩埚,放入电炉升温,在1000〜1200°C下保温0. 5〜 1. 5小时;步骤4 :将玻璃熔体迅速倒入水中进行水淬得到玻璃颗粒、或将玻璃熔体倒入金属板上得到玻璃块体。 3. A method for preparing lead-free low-melting glass, wherein said method is a method for producing a preparation as claimed in claim 1 said low melting glass, which method comprises preparing at least the following steps: Step 1: The pressing determining the ratio of the glass component weighed raw materials, boric acid is introduced 03 wherein s, P2O5 introduced by ammonium dihydrogen phosphate, barium carbonate, barium oxide introduced by the remaining oxide component is introduced directly from the raw materials, the raw mix is ​​made batch; step 2: the batch at 200~300 ° C calcined ~ 3 hours, then ground to a powder dispersion; step 3: the powder was placed in an alumina or quartz crucible, heated in an electric furnace at 1000~1200 ° incubated 1.5 hours at -5 to 0. C; step 4: the glass melt was rapidly quenched by water was poured into water to obtain glass particles, or glass melt is poured into a metal plate to obtain a glass block.
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