CN100515971C - Leadless phosphate seal glass and its preparation method - Google Patents

Leadless phosphate seal glass and its preparation method Download PDF

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Publication number
CN100515971C
CN100515971C CN 200610024793 CN200610024793A CN100515971C CN 100515971 C CN100515971 C CN 100515971C CN 200610024793 CN200610024793 CN 200610024793 CN 200610024793 A CN200610024793 A CN 200610024793A CN 100515971 C CN100515971 C CN 100515971C
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glass
annealing
sealing
temperature
oxide
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CN 200610024793
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CN1830856A (en )
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夏秀峰
贺雅飞
培 陈
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东华大学
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    • CCHEMISTRY; METALLURGY
    • 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • CCHEMISTRY; METALLURGY
    • 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
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • C03C3/19Silica-free oxide glass compositions containing phosphorus containing boron

Abstract

本发明公开了一种无铅磷酸盐封接玻璃,不含有氧化铅,其制备方法包括如下步骤:a、引入氧化物的原料称量混合均匀;b、在硅碳棒电炉中,温度在1000~1200℃进行熔制,保温0.5~1.5小时,其中在200~500℃内,采用的升温速度为2~3℃/min;c、对熔制好的玻璃液,进行浇铸,并及时将玻璃样品放入退火炉中进行退火,退火温度为350~400℃,保温1小时后随炉冷却;d、退火后的玻璃按测试要求加工成型。 The present invention discloses a lead-free sealing glass phosphate, containing no lead oxide, the preparation method comprising the steps: a, the introduction of the weighed raw materials mixed oxide; B, the silicon carbide electric furnace at a temperature 1000 ~ 1200 ℃ for melting, for 0.5 to 1.5 hours, wherein in the 200 ~ 500 ℃, temperature rise rate used is 2 ~ 3 ℃ / min; c, a good melting of the molten glass, cast, glass and promptly sample is placed in an annealing furnace for annealing an annealing temperature of 350 ~ 400 ℃, for 1 hour after cooling with the furnace; D, after annealing the glass molding process according to test requirements. 有益效果是:不含有氧化铅;熔点低;化学稳定性良好,可广泛用于各种玻璃、陶瓷与金属零部件之间的连接、封接、密封等。 Beneficial effects: that does not contain lead oxide; low melting point; chemical stability, is widely used to connect various glass, ceramic and metal parts, sealing and sealing.

Description

一种无铅磷酸盐封接玻璃及其制备方法 A lead-free sealing glass phosphate and preparation method

技术领域 FIELD

本发明涉及一种无铅磷酸盐封接玻璃及其制备方法,特别是涉及一种广泛应用于通讯、测量、传输、显示等仪器仪表或电子元器件的无铅磷酸盐封接玻璃及其制备方法。 The present invention relates to a lead-free sealing glass phosphate and its preparation method, particularly to a widely used in communications, measurements, transmission, or display instrument electronic components and lead-free sealing glass preparation phosphate method. 背景技术 Background technique

因仪器仪表或电子元器件的制造和使用对温度有严格的要求,所以大多要求封接玻璃的使用温度尽量低。 Due to manufacturing and use of instrumentation or electronic components have strict requirements on temperature, so that the sealing glass is often required to use temperatures as low as possible. 通常用在仪器仪表或电子元器件起连接、封接、 Since instrument commonly used in electronic components or connections, sealing,

涂层、密封等作用的封接玻璃,要求其使用温度在400〜60(TC之间,最高不超过700°C,目前,能满足这一要求的封接玻璃大多数以含氧化铅的封接玻璃为主。 Effect sealing glass coating, sealing, requires the use of temperature between 400~60 (TC, not exceeding 700 ° C, at present, to meet this requirement sealing glass containing most of the lead oxide capped ground glass-based.

研究表明,铅被人体吸收后将抑制人体内的蛋白质的正常合成功能,侵害人体中枢神经,引起贫血和高血压等疾病,尤其是对儿童的侵害更甚。 Studies have shown that lead is absorbed by the body will inhibit the normal function of the protein synthesis of the human body, against the human central nervous system, causing anemia and high blood pressure and other diseases, especially against children is even worse. 因此, 使用无铅封接玻璃代替含铅封接玻璃,是势在必行、大势所趋。 Thus, instead of using lead-free sealing glass containing lead sealing glass it is imperative, the general trend.

无铅低熔点封接玻璃不仅仅要无铅,而且必须具有含铅封接玻璃使用温度低的特性,还同时必须满足仪器仪表或电子元器件的一些特定性能要求,如绝缘性、气密性、耐压性、化学稳定性等。 Lead-free low-melting lead-free sealing glass is not only to be, and must lead sealing glass having a low temperature properties, and must also meet certain performance requirements instruments or electronic components, such as insulation, air tightness , pressure resistance, chemical stability.

美国专利第6306783号公开的玻璃组成的摩尔百分数为:SnO 30〜80%, B203 5〜60%, P205 5〜24%, ZnO 0〜25%, W03 3〜20%, Mo03 3〜5%, Ti02 0〜15%,Zr02 0〜15%, CuO0〜10%, R20 2〜35%。 Mole percent U.S. Patent No. 6,306,783 discloses glass composition is: SnO 30~80%, B203 5~60%, P205 5~24%, ZnO 0~25%, W03 3~20%, Mo03 3~5%, Ti02 0~15%, Zr02 0~15%, CuO0~10%, R20 2~35%. 该系统的玻璃的转变温度为280〜380。 The glass transition temperature of the system is 280~380. C , 热膨胀系数为90〜110X1(T7。C,玻璃的熔融温度为450〜500。C,流动半径为22〜26mm。该专利没有提到玻璃的化学稳定性。 C, the thermal expansion coefficient of 90~110X1 (T7.C, melting temperature of glass is 450~500.C, flow radius 22~26mm. This patent does not mention the chemical stability of the glass.

美国专利第5021366号公幵的是无氟磷酸盐玻璃的组成,摩尔百分数为:P205 30〜36%, Zr02 10〜33%,碱金属氧化物15〜25%,碱土金属氧化物15〜25%, 以及氧化铝、氧化锡、氧化铅等组分。 U.S. Patent No. 5,021,366 is well-Jian fluorine-free phosphate glass composition, the molar percentage: P205 30~36%, Zr02 10~33%, 15~25% alkali metal oxides, alkaline earth metal oxide 15~25% , and aluminum oxide, tin oxide, lead oxide component. 玻璃的软化温度为400〜430'C ,热膨胀系数为145〜170X10—7'C,该组分的玻璃的热膨胀系数比较大,可用于一些高膨胀系数的金属材料的封接,不能用于中、低膨胀系数的金属材料的封接,也不能用于金属与玻璃、陶瓷等材料之间的封接。 The softening temperature of the glass is 400~430'C, coefficient of thermal expansion 145~170X10-7'C, the thermal expansion coefficient of the glass component is relatively large, the metallic material can be used for sealing some high expansion coefficient, it can not be used in , low expansion coefficient of the metallic material of the sealing, sealing can not be used between the metal and glass, ceramics and other materials.

日本专利第H7-69672号公开的玻璃组成的摩尔百分数为:P205 25〜50%, SnO 30〜70%, ZnO 0〜25%,在此基础上添加适量的8203, W03, Li20等。 The mole percent of the glass composition disclosed in Japanese Patent No. H7-69672 is: P205 25~50%, SnO 30~70%, ZnO 0~25%, an appropriate amount of 8203, W03, Li20 or the like based on this. 该系统的玻璃组成中的SnO/ZnO大于5: 1,玻璃的使用温度为350〜450。 The glass composition of the system of SnO / ZnO is greater than 5: 1, temperature of 350~450 glass. C ,热膨胀系数大于120X10—7°C,专利中采用填充剂的方法来降低玻璃的膨胀系数,填充剂的加入影响到玻璃封接时的流动性和封接器件的气密性。 C, a thermal expansion coefficient greater than 120X10-7 ° C, using the method of Patent filler to lower the expansion coefficient of the glass filler is added to affect the flowability of the glass sealing hermetically sealed and connected devices. 发明内容 SUMMARY

本发明所要解决的技术问题是提供一种无铅磷酸盐封接玻璃及其制备方法,以弥补现有技术的不足或缺陷,满足生产和生活的需要。 The present invention solves the technical problem is to provide a lead-free sealing glass needs phosphate and its preparation method, to fill gaps or defects in the prior art, to meet production and life.

为了解决上述技术问题,本发明所采用的技术方案之一是: 一种无 In order to solve the above problems, one aspect of the present invention is used: a non-

铅磷酸盐封接玻璃,其组分及含量按摩尔百分比计算如下: Phosphate lead sealing glass, the components and content in mole percent is calculated as follows:

P205 20〜50% ZnO 10〜26%Si02 0〜15% P205 20~50% ZnO 10~26% Si02 0~15%

A1203 0〜10% A1203 0~10%

Na20+Li20 大于0且小于10% Na20 + Li20 greater than 0 and less than 10%

Sb203 0〜5% Sb203 0~5%

FeA 0〜2% FeA 0~2%

Mn02 0〜5% Mn02 0~5%

Cr203 0〜2% Cr203 0~2%

其中,Si02与A1203的含量之和为3. 9〜15%。 Wherein the total content of Si02 and A1203 3. 9~15%.

本发明所采用的技术方案之二是: 一种无铅磷酸盐封接玻璃的制备方法,包括如下步骤: Used in the present invention, the technical solutions of the two is: A process for preparing lead-free sealing glass is a phosphate, comprising the steps of:

a、 引入氧化物的原料:氧化磷由磷酸铵引入,氧化硼由硼酸引入,氧化钠, 氧化锂分别由各自的碳酸盐引入,氧化铝由氢氧化铝引入,其余组分由各自的氧化物引入,根据封接玻璃的摩尔百分比的组成范围,确定玻璃配方,计算出玻璃的重量百分比,然后称量混合均匀; a, an oxide material is introduced: ammonium introduced by phosphorus oxide, boron oxide introduced by boric acid, sodium oxide, lithium oxide, respectively, introduced by the respective aluminum carbonate aluminum hydroxide is introduced, the remaining components of the respective oxide was introduced, the molar percentage depending on the composition of the sealing glass, glass formulation is determined, the calculated weight percent of the glass, were weighed and then mixed;

b、 选用石英坩埚,在硅碳棒电炉中,温度在1000〜1200'C进行熔制,保温0. 5〜1. 5小时,其中在200〜500'C内,采用的升温速度为2〜3TVmin, 以便化合物的分解和结晶水的排除; B, the choice of the quartz crucible, the silicon carbide electric furnace in the melting temperature 1000~1200'C, incubated 0.5 5~1. 5 hours, wherein the rate of temperature rise in the 200~500'C, used was 2 ~ 3TVmin, in order to exclude water of crystallization and decomposition of the compound;

c、 对熔制好的玻璃液,进行浇铸,并及时将玻璃样品放入退火炉中进行退火,退火温度为350〜40CTC,保温l小时后随炉冷却; C, good melting of the molten glass, cast, and promptly placed in the glass sample was annealed in an annealing furnace, annealing temperature 350~40CTC, l h after incubation cooling with the furnace;

d、 退火后的玻璃按测试要求加工成型。 d, after annealing the glass molding process according to test requirements.

步骤b中在200〜50(TC内,升温时间控制在1〜2小时。本发明的原理是这样的:为了调节封接玻璃的膨胀系数,改善玻璃的化学 In step b 200~50 (TC, ~ 2 hours in heating time control principle of the invention is as follows: For adjusting the expansion coefficient of the glass seal, glass improved chemical

稳定性,在玻璃中加入氧化硅和氧化铝,但是,大量的实验表明,Si02与AlA的含量之和不宜超过15%,否则,玻璃的转变温度和熔封温度都会明显提高。 Stability, addition of silica and alumina in the glass, however, a large number of experiments indicated that the content of Si02 and AlA not more than 15% and, otherwise, the glass transition temperature and melting temperature are significantly improved sealing.

碱金属氧化物的加入可改善封接玻璃熔封时的流动性,使封接玻璃与被封接材料(金属、玻璃、陶瓷)之间的密着更好。 Alkali metal oxides may improve the sealing contact when the flowability glassivation the sealing glass with the better adhesion between the sealing material (metal, glass, ceramic). 但碱金属氧化物的加入,会使 However, addition of alkali metal oxide, will

封接玻璃的膨胀系数上升,因此Na20+Li20的含量应控制在0〜10%的范围内。 Expansion coefficient of the sealing glass is increased, and therefore the content of Na20 + Li20 should be controlled within a range of 0 ~ 10%.

Sb203、 Fe203、 Mn02、 0203的引入,是为了提高玻璃的耐水性。 Sb203, Fe203, Mn02, 0203 introduced, in order to improve the water resistance of the glass. 这些过渡金属氧化物填充在玻璃网络空隙中,堵塞了水分子进一步进入网络中与水解金属氧化物进行反应。 The transition metal oxide is filled in the gap in the glass network, the blocked further into the network of water molecules react with the metal oxide hydrolysis. 一般来说,随着金属离子的化合价的提高,玻璃的水解越困难, 玻璃的化学稳定性越好。 In general, with the increase of the valence of the metal ion, the more difficult hydrolysis of the glass, the better the chemical stability of the glass.

本发明的有益效果是:本发明的封接玻璃中不含有氧化铅,消除了含铅封接玻璃生产或使用过程中对人体和环境的污染和破坏,能代替含铅封接玻璃用于各种电子元器件的封接中;熔点低,玻璃的软化温度440〜500°C ,熔封温度低于70(TC,能满足电子元器件的低温封接要求;热膨胀系数在65〜 100X1(T/。C范围内,化学稳定性良好,可广泛用于各种玻璃、陶瓷与金属零部件之间的连接、封接、密封等。 具体实施方式 Advantageous effects of the present invention is that: the sealing glass of the present invention does not contain lead oxide, lead eliminates the sealing glass during the production or use of the pollution and damage to human body and the environment, can replace lead-containing sealing glass used for each sealing electronic components; and a low melting point, the softening temperature of the glass 440~500 ° C, a temperature below the fusion seal 70 (TC, to meet the low temperature requirements of the electronic component sealing; thermal expansion coefficient 65~ 100X1 (T /.C within the range, good chemical stability, is widely used to connect various glass, ceramic and metal parts, seals, seal, etc. DETAILED DESCRIPTION

下面结合具体实施例对本发明作进一步详细阐述。 In conjunction with the specific embodiments of the present invention will be below explained in further detail. 根据上述的无铅低熔点封接玻璃的摩尔百分比的组成范围,确定玻璃配方,计算出玻璃的重量百分比进行配料,按照上述的玻璃的加工制备方法进行玻璃的熔制、成型和研磨,对加工后的样品进行测试,测试方法为:玻璃的热膨胀系数a (X 10—7°C)、玻璃的转变温度TgCC)和软化温度Tf CC)的测量使用常规的膨胀系数测量仪测量。 The mole percent of the above composition range of the low melting point lead-free sealing glass, glass formulation is determined, calculate the weight percentage of glass compounded, for glass melting, shaping and milling processing according to the production method of the above-mentioned glass, for processing after the samples were tested, test method: the thermal expansion coefficient of the glass of a (X 10-7 ° C), glass transition temperature TGCC) and the softening temperature Tf CC) is measured using a conventional measuring instrument measuring expansion coefficient. 玻璃的耐水性测量是在7(TC蒸溜水中进行,时间24小时,样品尺寸为20X20X2mm,考虑到玻璃的化学稳定性与玻璃的表面积有关,所以根据侵蚀量计算单位面积的失重(g/cm2)。实施例的玻璃组成(重量百分比)见下表l: Water resistance measurement of the glass is in the 7 (TC distilled water for, 24 hours, sample size was 20X20X2mm, taking into account the surface area of ​​the chemical stability of the glass of the glass concerned, the computing unit area weight loss (g / cm2 The erosion) the glass composition of Example (wt%) in the table below l:

表1 Table 1

<table>table see original document page 8</column></row> <table>实施例1:按表1中的组成进行配料,Na20+Li20的加入起调节玻璃的膨胀系数、改善玻璃封接时的流动性的作用。 When Table 1 composition of ingredients, from the addition of Na20 + Li20 adjustment coefficient of the glass expansion, improved glass sealing: <table> table see original document page 8 </ column> </ row> <table> Example 1 flowability effect.

将玻璃浪合料置于石英坩埚内,在硅碳棒电炉内加热熔制,50(TC以下升温速度为3'C/min,然后快速升温到110(TC保温30 min。 The glass frit bonding waves placed in a quartz crucible, were heat produced in the silicon carbide furnace, 50 (TC the temperature rise rate of 3'C / min, and then quickly warmed to 110 (TC incubated 30 min.

熔制好的玻璃在经过预热的模具中成型,并快速放入马弗炉中退火,退火温度为35(TC,保温l小时后随炉冷却。 Good melting glass mold preheated molding, and quickly placed in a muffle furnace annealing, an annealing temperature of 35 (TC, l h after incubation cooling with the furnace.

退火后的样品经研磨加工后,进行性能分析,测试结果见表l。 The samples were milled after the annealing process, performance analysis, the test results in Table l. 实施例2: Example 2:

按表1中的组成进行配料,与实施例1比较,用氧化硅代替氧化铝,减少碱金属氧化物的用量,比较玻璃的热膨胀系数、软化温度的变化。 Compounding the composition in Table 1, Comparative Example 1, in place of silicon oxide, aluminum oxide, to reduce the amount of alkali metal oxide, the thermal expansion coefficient of the glass comparison, changes in softening temperature.

将玻璃混合料置于石英坩埚内,在硅碳棒电炉内加热熔制,50(TC以下升温速度为2XVmin,然后快速升温到100(TC保温40 min。 The mixture was placed in a quartz glass crucible, were heat produced in the silicon carbide furnace, 50 (TC the temperature rise rate is 2XVmin, then quickly warmed to 100 (TC incubated 40 min.

熔制好的玻璃在经过预热的模具中成型,并快速放入马弗炉中退火,退火温度为360°C,保温1小时后随炉冷却。 Good melting glass mold preheated molding, and quickly placed in a muffle furnace annealing, an annealing temperature of 360 ° C, for 1 hour after cooling with the furnace.

退火后的样品经研磨加工后,进行性能分析,测试结果见表l。 The samples were milled after the annealing process, performance analysis, the test results in Table l. 实施例3: Example 3:

按表1中的组成进行配料,与实施例1比较,减少碱金属氧化物的用量, 比较玻璃的热膨胀系数、软化温度的变化。 Compounding the composition in Table 1, Comparative Example 1 with variations embodiment, reduce the amount of alkali metal oxides, the glass thermal expansion coefficient comparison, softening temperature.

将玻璃混合料置于石英坩埚内,在硅碳棒电炉内加热熔制,50(TC以下升温速度为3°C/min,然后快速升温到1200'C保温1小时。 The mixture was placed in a quartz glass crucible, were heat produced in the silicon carbide furnace, 50 (TC the temperature rise rate of 3 ° C / min, then rapidly warmed to 1200'C for 1 hour.

熔制好的玻璃在经过预热的模具中成型,并快速放入马弗炉中退火,退火温度为40(TC,保温l小时后随炉冷却。退火后的样品经研磨加工后,进行性能分析,测试结果见表l。 实施例4: Good melting glass mold preheated molding, and quickly placed in a muffle furnace annealing, an annealing temperature of 40 (TC, l h after incubation and then cooled. After grinding the samples were annealed after performance analysis, the test results in Table l Example 4:

按表1中的组成进行配料,在组成中加入了氧化硅和氧化铝,以及1%的Sb203,目的是为了提高玻璃的化学稳定性。 Table 1 for ingredients in the composition, the added silica and alumina, and 1% of Sb203 in the composition, the purpose is to improve the chemical stability of the glass.

将玻璃混合料置于石英坩埚内,在硅碳棒电炉内加热熔制,50(TC以下升温速度为3。C/min,然后快速升温到115(TC保温40 min。 The mixture was placed in a quartz glass crucible, were heat produced in the silicon carbide furnace, 50 (TC hereinafter heating rate 3.C / min, and then quickly warmed to 115 (TC incubated 40 min.

熔制好的玻璃在经过预热的模具中成型,并快速放入马弗炉中退火,退火温度为38(TC,保温l小时后随炉冷却。 Good melting glass mold preheated molding, and quickly placed in a muffle furnace annealing, an annealing temperature of 38 (TC, l h after incubation cooling with the furnace.

退火后的样品经研磨加工后,进行性能分析,测试结果见表l。 The samples were milled after the annealing process, performance analysis, the test results in Table l. 实施例5: Example 5:

按表1中的组成进行配料,与实施例4比较,用1%的Fe203代替1%的Sb203。 Compounding the composition in Table 1, Comparative Example 4, with 1% instead of 1% Fe203 Sb203.

将玻璃混合料置于石英坩埚内,在硅碳棒电炉内加热熔制,50(TC以下升温速度为2'C/min,然后快速升温到115(TC保温1. 5小时。 The mixture was placed in a quartz glass crucible, were heat produced in the silicon carbide furnace, 50 (TC hereinafter heating rate 2'C / min, and then quickly warmed to 115 (TC incubated 1.5 hours.

熔制好的玻璃在经过预热的模具中成型,并快速放入马弗炉中退火,退火温度为38(TC,保温l小时后随炉冷却。 Good melting glass mold preheated molding, and quickly placed in a muffle furnace annealing, an annealing temperature of 38 (TC, l h after incubation cooling with the furnace.

退火后的样品经研磨加工后,进行性能分析,测试结果见表l。 The samples were milled after the annealing process, performance analysis, the test results in Table l. 实施例6: Example 6:

按表1中的组成进行配料,与实施例4比较,用0. 3%的&203代替1%的Sb必,。 Compounding the composition in Table 1, Comparative Example 4, with 0.3% of & 1% Sb 203 will be replaced. 将玻璃混合料置于石英坩埚内,在硅碳棒电炉内加热熔制,50(TC以下升温 The mixture was placed in a quartz glass crucible, were heat produced in the silicon carbide furnace, 50 (TC hereinafter warmed

速度为3。 Rate of 3. C/min,然后快速升温到1100。 C / min, then rapidly heated to 1100. C保温40 min。 C incubated 40 min.

熔制好的玻璃在经过预热的模具中成型,并快速放入马弗炉中退火,退火 Good melting glass mold preheated molding, and quickly placed in a muffle furnace annealing, annealing

温度为40CTC,保温1小时后随炉冷却。 Temperature 40CTC, for 1 hour after cooling with the furnace. 退火后的样品经研磨加工后,进行性能分析,测试结果见表l。 The samples were milled after the annealing process, performance analysis, the test results in Table l.

Claims (3)

  1. 1、一种无铅磷酸盐封接玻璃,其特征在于:其组分及含量按摩尔百分比计算如下: P2O5 20~50% ZnO 10~26% SnO 20~40% B2O3 5~50% SiO2 0~15% Al2O3 0~10% Na2O+Li2O 大于0且小于10% Sb2O3 0~5% Fe2O3 0~2% MnO2 0~5% Cr2O3 0~2% 其中,SiO2与Al2O3的含量之和为3.9~15%。 A lead-free sealing glass phosphate, characterized in that: the components and content in mole percent is calculated as follows: P2O5 20 ~ 50% ZnO 10 ~ 26% SnO 20 ~ 40% B2O3 5 ~ 50% SiO2 0 ~ 15% Al2O3 0 ~ 10% Na2O + Li2O greater than 0 and less than 10% Sb2O3 0 ~ 5% Fe2O3 0 ~ 2% MnO2 0 ~ 5% Cr2O3 0 ~ 2% wherein the total content of SiO2 and Al2O3, and 3.9 to 15% .
  2. 2、 一种如权利要求l所述的封接玻璃的制备方法,其特征在于:包括如下步骤:a、 引入氧化物的原料:氧化磷由磷酸铵引入,氧化硼由硼酸引入,氧化钠,氧化锂分别由各自的碳酸盐引入,氧化铝由氢氧化铝引入,其余组分由各自的氧化物引入,根据封接玻璃的摩尔百分比的组成范围,确定玻璃配方,计算出玻璃的重量百分比,然后称量混合均匀;b、 选用石英坩埚,在硅碳棒电炉中,温度在1000〜120(TC进行熔制,保温0. 5〜1. 5小时,其中在200〜500°C内,采用的升温速度为2〜3°C/min;C、对熔制好的玻璃液,进行浇铸,并及时将玻璃样品放入退火炉中进行退火,退火温度为350〜400°C,保温l小时后随炉冷却;d、退火后的玻璃按测试要求加工成型。 2. A method as claimed in preparing a sealing glass according to claim l, characterized in that: comprising the steps of: a, an oxide feedstock is introduced: ammonium introduced by phosphorus oxide, boron oxide introduced by boric acid, sodium oxide, lithium oxide, respectively, introduced by the respective aluminum carbonate aluminum hydroxide is introduced, the remaining components introduced by the respective oxides, the molar percentage depending on the composition of the sealing glass, glass formulation is determined, calculate the weight percentage of glass , weighed and then mixed; B, with quartz crucible, the silicon carbide in an electric furnace, the temperature 1000~120 (TC for melting, holding 0.5 5~1 5 hours, wherein in 200~500 ° C,. temperature rise rate used is 2~3 ° C / min; C, good melting of the molten glass, cast, and promptly placed in the glass sample was annealed in an annealing furnace, an annealing temperature of 350~400 ° C, insulation l after furnace cooling h; d, after annealing the glass molding process according to test requirements.
  3. 3、根据权利要求2所述的制备方法,其特征在于:步骤b中在200〜500 'C内,升温时间控制在1〜2小时。 3, the production method according to claim 2, wherein: in step b 200~500 'C, the heating time control ~ 2 hours.
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CN101007706B (en) 2007-01-19 2010-06-30 东华大学 Lead-free phosphate sealed glass for electrothermal tube and its preparation method
CN100595171C (en) 2007-01-19 2010-03-24 东华大学 Large power tube lead-free sealed glass powder and its preparation method
CN101058477B (en) 2007-03-30 2011-02-09 东华大学 Electricity vacuum glass products lead-free seal glass and preparing method thereof
CN101113073B (en) 2007-06-29 2011-06-08 东华大学 Leadless low-melting glass powder for seal with metal or alloy and preparation method thereof
CN101298365B (en) 2008-04-17 2011-04-27 东华大学 Preparation and use of electronic device passivation encapsulation modified zinc-boron-silicon-lead glass powder
WO2012014619A1 (en) * 2010-07-28 2012-02-02 日本電気硝子株式会社 Sealing glass and sealing composite material
CN102173593B (en) * 2011-02-12 2013-03-27 刘国正 Lead-free glass powder, preparation method and application thereof
CN102173578B (en) * 2011-02-25 2013-04-03 东华大学 Alkali-free phosphate glass and preparation method thereof
CN102173582A (en) * 2011-02-25 2011-09-07 东华大学 Media glass used for infrared heating coating and preparation method thereof
CN103253866B (en) * 2013-05-24 2015-07-22 福州大学 SnO2-containing glass-sealing material preparation and application method
CN103332862B (en) * 2013-06-20 2015-06-17 齐鲁工业大学 Lead-free sealing glass with transitional expansion coefficient
CN103539356B (en) * 2013-10-25 2017-01-11 上海大学 Glass frit compositions and preparation method, the sealing glass frit based composition
CN103951189B (en) * 2014-04-09 2016-03-30 京东方科技集团股份有限公司 A lead-free sealing glass frit and preparation method
CN105522244B (en) * 2015-12-29 2018-01-30 哈尔滨工业大学 An auxiliary low-temperature glass ultrasonic soldering method
CN105499733B (en) * 2015-12-29 2018-03-16 哈尔滨工业大学 A micro-arc oxidation auxiliary brazing method of low-temperature glass

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