WO2014005406A1 - 一种无铅易熔绿色环保玻璃及其制备方法 - Google Patents

一种无铅易熔绿色环保玻璃及其制备方法 Download PDF

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Publication number
WO2014005406A1
WO2014005406A1 PCT/CN2012/086896 CN2012086896W WO2014005406A1 WO 2014005406 A1 WO2014005406 A1 WO 2014005406A1 CN 2012086896 W CN2012086896 W CN 2012086896W WO 2014005406 A1 WO2014005406 A1 WO 2014005406A1
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glass
lead
low
melting
free
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PCT/CN2012/086896
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English (en)
French (fr)
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郑锦清
余其俊
郑铁励
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华南理工大学
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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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • 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
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C03C3/112—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine
    • C03C3/115—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron
    • C03C3/118—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen containing fluorine containing boron containing aluminium
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc

Definitions

  • the invention relates to the technical field of glass materials, in particular to a green glass material with low melting point and no lead and a preparation method thereof.
  • Low temperature glass is an important material widely used in the sealing and protection of electrical products, the surface protection of metal parts and products, and the decoration of low temperature glazes. At present, low temperature glass solder, low temperature glass coating and its manufacturing and application technology are very mature.
  • the lead-free fusible glass material of the present invention and its method of preparation can overcome many of the shortcomings of the prior art. It is an inexpensive, lead-free, fusible, high-tech green glass material.
  • the object of the present invention is to overcome the shortcomings of the prior art, and to provide a lead-free fusible green glass and a preparation method thereof.
  • the prepared glass has high chemical stability, low coefficient of linear expansion, low suitable softening temperature, and is free of lead and a class of low melting point precious metals and non-metal compounds.
  • the glass composition of the present invention not only uses a small number of low-cost raw materials, but also has a very simple preparation process: simple mixing of raw materials, low melting temperature, and short holding time.
  • the prepared glass is transparent and does not recrystallize. Due to its high chemical stability, low coefficient of linear expansion, and low suitable softening temperature, it is used alone or in combination with other compounds as a main component of solder and glaze. It has a linear expansion coefficient and a high softening temperature. Mobility is a high-performance, low-cost, environmentally-friendly green material.
  • the present invention is achieved by the following technical solutions.
  • the lead-free fusible green glass does not contain lead and the commonly used low-melting precious metals and non-metals.
  • the typically used low-melting metal having a relatively high price is one or more of ruthenium, osmium, vanadium, niobium and tantalum.
  • the typical low-melting non-metal which is commonly used at a relatively high price is one or more of arsenic and antimony.
  • the preparation method of the above lead-free low-melting green glass includes the following steps:
  • the raw materials are placed in a mixer and stirred for 10-20 seconds according to claim 1, and poured into the furnace at one time. Or pour into a molten glass furnace at one time;
  • the temperature of the melting furnace is raised to a set temperature between 1000-1100 ° C and held for 15-30 minutes.
  • the glass is in a state of low viscosity and fully melted, and after being taken out, it is cooled or poured into water to be quenched into glass particles.
  • the glass particles are also pulverized by a crusher to form a glass frit.
  • step 2) is heated to 1000-1100 ° C at 400 ° C / hour.
  • step 2 continuous production is carried out by batch feeding and discharging through a melting furnace.
  • the preparation method of the above lead-free low-melting green glass includes the following steps:
  • the raw materials are placed in a mixer and stirred for 10-20 seconds according to claim 1, and poured into the furnace at one time. Or pour into a molten glass furnace at one time;
  • the temperature of the melting furnace is raised to a set temperature between 1000-1100 ° C and held for 15-30 minutes.
  • the glass is in a state of low viscosity and fully melted, and after being taken out, it is cooled or poured into water to be quenched into glass particles.
  • the glass particles are also pulverized by a crusher to form a glass frit.
  • the step 2) is heated to 1000-1100 ° C at 400 ° C / hour.
  • the lead-free low-melting green glass prepared by the invention is widely used for thick film circuit components such as conduction band, resistance, capacitance and sensation of glass sealing thick film integrated circuit printing of electronic components or related equipment parts which are required to be subjected to low-temperature sealing welding.
  • the glass binder of the slurry, the conduction band of the thick film integrated circuit and the surface of the thick film element cover the protective glass glaze, the metal surface protection and the decorative surface glaze.
  • the present invention has the following advantages:
  • the material prepared by the invention is a fusible glass which is lead-free and does not contain a combination of a conventional lead metal and some noble metal or non-metal compound having a low melting point, and is an environmentally friendly green material.
  • the material prepared by the invention has the advantages of high chemical stability, low linear expansion coefficient, good glass transmittance, no crystallization, and high scratch resistance mechanical strength.
  • the glass itself is introduced into other applications as a main component of the glaze, its properties are more adapted to the wide range of composition adjustments.
  • the material preparation process of the invention is simple, the melting temperature is low, the heat preservation time is short, the corrosion of the crucible and the furnace body is small, and the low-cost industrial pure grade raw materials can be used for rapid production.
  • the material of the present invention is a low cost, high performance product.
  • composition is shown in Table 1 below.
  • the raw materials were weighed according to the above ratio, and stirred and mixed for 10 seconds in a blender. After being taken out, the high-aluminum crucible was placed in a melting furnace at a time. According to the heating system of 400 °C / hour, the furnace temperature reached 800 °C, after 10 minutes of heat preservation, the furnace temperature was raised to 1100 °C and kept for 15 minutes according to the heating system of 600 °C / hour. The furnace was quickly taken out and the molten glass was poured. The glass is pulverized in water, filtered, and dried in an oven. After cooling, it is placed in a crusher and a ball mill and pulverized and passed through a 400 mesh sieve to prepare a glass frit of the present invention.
  • composition is shown in Table 2.
  • the raw materials were weighed according to the above ratio, and stirred and mixed for 10 seconds in a blender. After being taken out, the high-aluminum crucible was placed in a melting furnace at a time.
  • 400 °C / hour heating system to achieve a furnace temperature of 800 ° C, after 10 minutes of insulation, according to the 600 ° C / hour heating system to raise the furnace temperature to 1080 °C and keep warm for 15 minutes, quickly remove the crucible after stopping the furnace, and pour the molten glass into water to quench the glass to produce the glass crumb. After filtering off the water, it is dried in the oven, cooled and placed in the crusher and ball mill to be crushed and passed.
  • a 400 mesh sieve that is, a glass frit of the present invention.
  • composition is shown in Table 3.
  • the raw materials were weighed according to the above ratio, and stirred and mixed for 10 seconds in a blender. After being taken out, the high-aluminum crucible was placed in a melting furnace at a time.
  • the furnace temperature is up to 800 ° C according to the heating system of 400 ° C / hour, and the temperature is kept for 10 minutes and then 600 ° C / hour.
  • the furnace temperature is raised to 1050 ° C and kept for 15 minutes, the furnace is quickly taken out, and the molten glass liquid is poured into water to quench the glass to produce the glass crumb, the water is filtered off, dried in an oven, cooled and placed in a crusher and a ball mill.
  • the glass powder of the present invention is prepared by pulverizing and passing through a 400 mesh sieve.
  • the fusible glass obtained can achieve the following technical and economic indicators:
  • Linear expansion coefficient 5 ⁇ 8 ⁇ 10-6/°C (-5 ⁇ 300°C interval);
  • the material cost of the formulation provided by the present invention is 5,000-6,000 yuan/ton.
  • the lead-free fusible glass of the present invention can be put into the following application examples:
  • glass frit is prepared according to the examples, and the solder powder is processed by using the glass frit alone or by adding a tint as required.
  • Glass frits were prepared as in the examples within the defined compositional composition. Glass powder is used as the main component of the glaze or coating, and then an appropriate amount of colored oxide, BaO, ZnO, B2O3 is added as required to prepare a glaze coating powder. Finally, according to the requirements of the viscosity of a certain application of glaze, coating powder requirements water and adhesive, fully stirred to make glaze slurry, water-based paint or printing paste.
  • the surface of the workpiece can be coated by spraying, dip coating, printing, etc., and can be quickly fired at a low temperature after being dried.
  • the application method is suitable for surface coating, surface covering protection, surface decoration, etc. of metal and ceramics, and is also suitable for printing tapes on the surface of thick film circuits and printing pastes for surface protection of several types of surface printing elements.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

一种无铅易熔绿色环保玻璃及其制备方法，该制备方法包括：按配比把称取的原材料混合，然后置于熔制坩埚或熔制玻璃熔体的炉膛中升温至设定温度并保温一定时间，得到组成均匀的无铅玻璃熔体，最后经冷却及粉碎。该方法避免了常规低软化点玻璃组分中大量铅及低熔点贵金属化合物的引入，得到的玻璃的软化温度为480°C-600°C，物理化学性能稳定、不析晶，具有低线性膨胀系数、高抗刮蹭机械强度等特点。所述的玻璃可广泛应用于低温密封焊接焊料，也可作为厚膜电路导带及元件浆料的玻璃粘结剂及厚膜电路覆盖保护釉料，还可作为金属及一些材料部件的低温表面处理、涂覆、装饰、保护作用的粉体涂料釉料组分。

Description

一种无铅易熔绿色环保玻璃及其制备方法
技术领域
本发明涉及玻璃材料技术领域，具体涉及一种低熔点不含铅的绿色环保玻璃材料及其制备方法。
背景技术
低温玻璃是一类广泛用于电气产品封接及保护、金属部件及制品表面保护及装饰低温釉料的重要材料。目前，低温玻璃焊料，低温玻璃涂料及其制造、应用技术已十分成熟。
从配方类看，无论是有氧的、无氧的或两者的混合型玻璃，其组分除了许多必加的共有化合物（如SiO2、B2O3及硼酸等）外，大都含有较大组分比的铅及一些低熔点贵金属及非金属（如铋、铊、钒、碲、锗、锑、砷等）化合物。尽管大组分的铅的引入及其它贵金属及非金属化合物的搭配制备了各种各样的具有合适软化温度，线性膨胀系数及一定的化学稳定性的易熔玻璃，但在玻璃熔制的过程，作为玻璃形成体的Pb-Si-O网络仍然会使大量的铅形成PbO气氛挥发，造成严重的环境污染。重金属铅对人体实际上是一种超毒物质。2003年1月27日欧洲议会及参议会指令2002/95/EC《限制在电气及电子设备中使用某种有害物质》（RoHS），要求确保2006年7月1日起投入市场的产品不含有某种有害物质。铅为RoHS指定归属重毒金属，是一种损害人体大脑、神经系统、记忆、注意力及听力的致癌物质，其在物质的相关制品中的限量仅为1000 ppm。自此，产品的无铅化已成为多年来新材料及相关制备工艺研究的一大热门课题。另外，铅的严重腐蚀性对玻璃熔制设备（如炉膛、炉体、刚玉和高铝坩埚甚至白金坩埚）也有极高的腐蚀破坏性。这从另一角度大大地增加了产品的成本。
本发明的无铅易熔玻璃材料及其制备方法，可以克服现有技术的许多缺点。是一种廉价的无铅易熔高技术性能的环保绿色玻璃材料。
发明内容
本发明的目的在于克服目前已有技术的缺点，提供一种无铅易熔绿色环保玻璃及其制备方法。所制备的玻璃具有高化学稳定性、低线膨胀系数、低的合适的软化温度，不含铅及一类低熔点贵金属及非金属化合物。本发明的玻璃组成不仅采用低成本的少数种类的原材料，制备工艺也极其简单：原材料简单混合、熔制温度低、保温时间短。制备的玻璃通透不重结晶。由于其高的化学稳定性、低线膨胀系数、低的合适的软化温度，使其单独或与其它化合物结合作为焊料、釉料的主要组分，具有对线膨胀系数，软化温度可调的高能动性，是一种高性能廉价的环保绿色材料。本发明通过如下技术方案实现。
一种无铅易熔绿色环保玻璃，其特征在于以重量份数计，由以下的成分组成：
SiO2 50-70
Al2O3 0-12
TiO2 0-8
ZnO 4-7
K2SiF6 4-10
B2O3 10-15 。
上述的无铅易熔绿色环保玻璃中，无铅易熔绿色环保玻璃不含铅及典型常用的低熔点贵金属及非金属。所述典型常用的价格较为昂贵的低熔点金属为铋、铊、钒、锗、锑中一种以上，所述典型常用的价格较为昂贵的低熔点非金属为砷和碲中一种以上。
上述无铅低熔点绿色环保玻璃的制备方法，包括下述步骤：
1） 依据熔具坩埚或玻璃熔制炉炉膛生料化合物的合适承装或装填量，按权利要求1将各原料置于搅拌机内搅拌混合10-20秒钟，并一次性倒入坩埚放入炉中或一次性倒入装盛熔制玻璃炉膛；
2） 使熔制炉炉温升至1000-1100℃间的设定温度点并保温15-30分钟，玻璃处于低粘度充分熔融的状态，取出后经冷却或倒入水中淬火成玻璃颗粒。
进一步优化的，所述玻璃颗粒还经破碎机粉碎制成玻璃粉。
进一步优化的，步骤2）以400℃/小时升温至1000-1100℃。
进一步优化的，结合步骤2）中通过熔制炉分批进料及出料实行连续性生产。
上述的无铅低熔点绿色环保玻璃的制备方法，包括下述步骤：
1） 依据熔具坩埚或玻璃熔制炉炉膛生料化合物的合适承装或装填量，按权利要求1将各原料置于搅拌机内搅拌混合10-20秒钟，并一次性倒入坩埚放入炉中或一次性倒入装盛熔制玻璃炉膛；
2） 使熔制炉炉温升至1000-1100℃间的设定温度点并保温15-30分钟，玻璃处于低粘度充分熔融的状态，取出后经冷却或倒入水中淬火成玻璃颗粒。
上述的无铅低熔点绿色环保玻璃的制备方法中，所述玻璃颗粒还经破碎机粉碎制成玻璃粉。
上述的无铅低熔点绿色环保玻璃的制备方法中，步骤2）以400℃/小时升温至1000-1100℃。
本发明制得的无铅低熔点绿色环保玻璃广泛用于必须进行低温密封焊接的电子器件或相关设备部件的玻璃封焊厚膜集成电路印刷的导带、阻、容、感等厚膜电路元件的浆料的玻璃粘结剂、厚膜集成电路的导带及厚膜元件表面覆盖保护玻璃釉、金属表面保护和装饰的表面漆釉等。
与现有技术相比，本发明具有下述优点：
1、 本发明制备的材料是一种无铅及不含有传统采用铅及一些具有低熔点的贵金属或非金属的化合物结合制备的易熔玻璃，是一种环保的绿色材料。
2、 本发明制备的材料具有高的化学稳定性、低线膨胀系数、玻璃透光性好、不析晶、抗刮蹭机械强度高等综合优点。当玻璃自身作为釉料的主成分引入其他应用时，其性能更适应组分的广泛范围调整。
3、 本发明的材料制备工艺简单，其熔制温度低、保温时间短、对坩埚及炉体腐蚀少，可采用廉价工业纯级的原材料进行速续生产等。本发明的材料是一种低成本高性能的产品。
具体实施方式
下述结合具体实施例对本发明的实施作进一步说明，但本发明的实施和保护不限于此。
实施例 1
组成如下表 1 所示。
表 1
原材料 配比（重量份）
SiO2 56
Al2O3 12
TiO2 8
ZnO 4
K2SiF6 8
B2O3 12
按上述配比称好原材料，并置于搅拌机内搅拌混合10秒钟，取出后一次性装入高铝坩埚置于熔制炉中。按400℃/小时升温制度使炉温达到800℃，保温10分钟后按600℃/小时升温制度使炉温升至1100℃并保温15分钟，停炉快速取出坩埚，并把熔融玻璃液倒入水中淬火产生玻璃碎粒，滤去水份后于烘箱烘干，冷却后置于破碎机及球磨机中再行粉碎并过400目筛，即制成本发明的一种玻璃粉。
实施例 2
组成如表 2 所示。
表 2
原材料 配比（重量份）
SiO2 60
Al2O3 8
TiO2 0
ZnO 7
K2SiF6 10
B2O3 15
按上述配比称好原材料，并置于搅拌机内搅拌混合10秒钟，取出后一次性装入高铝坩埚置于熔制炉中。按400 ℃/小时升温制度使炉温达到800℃，保温10分钟后按600℃/小时升温制度使炉温升至1080 ℃并保温15分钟，停炉快速取出坩埚，并把熔融玻璃液倒入水中淬火产生玻璃碎粒，滤去水份后于烘箱烘干，冷却后置于破碎机及球磨机中再行粉碎并过400目筛，即制成本发明的一种玻璃粉。
实施例 3
组成如表3所示。
表 3
原材料 配比（重量份）
SiO2 68
Al2O3 0
TiO2 1
ZnO 6
K2SiF6 10
B2O3 15
按上述配比称好原材料，并置于搅拌机内搅拌混合10秒钟，取出后一次性装入高铝坩埚置于熔制炉中。按400℃/小时升温制度使炉温达到800℃，保温10分钟后按600℃/小时 使炉温升温至1050℃并保持15分钟，停炉快速取出坩埚，并把熔融玻璃液倒入水中淬火产生玻璃碎粒，滤去水份后于烘箱烘干，冷却后置于破碎机及球磨机中再行粉碎并过400目筛，即制成本发明的一种玻璃粉。
本发明的实施可依上述实施例在玻璃熔制炉中连续性生产进行。
采用本发明所提供的玻璃配方及制备方法，制得的易熔玻璃可达到下述的技术经济指标：
1、 软化温度：480~600℃；
2、 线膨胀系数：5~8×10-6/℃（-5~300℃区间）；
3、 化学稳定性：100℃沸水中10h，重量损失≤0.1%；
4、 本发明提供的配方的材料成本为5，000-6，000元/吨。
本发明的无铅易熔玻璃可以投入如下的应用例：
1、 在所限定的成分组成范围内，按实施例制备玻璃粉，单独用这种玻璃粉或按要求加入调色料加工制成封焊焊料粉体。
2、 在所限定的成分组成范围内，按实施例制备玻璃粉。以玻璃粉作为釉料或涂料的主成分，再按要求加入适量的着色氧化物、BaO、ZnO、B2O3制成釉料涂料粉体。最后，再根据要求在某应用专项的釉料、涂料粉体中对粘度的要求称取水及粘合剂，充分搅拌后制成釉浆料、水性漆涂料或印刷浆料。可以采取喷涂、浸涂、印刷等工艺对工件实施表面生料涂覆，待料干后可即进行低温快速烧成。该应用法适用于金属、陶瓷的表面涂覆、表面覆盖保护、表面装饰等，同时也适用于厚膜电路表面印刷导带和若干种类的表面印刷元件表面覆盖保护用的印刷浆料。

Claims (7)

  1. 一种无铅易熔绿色环保玻璃，其特征在于以重量份数计，由以下的成分组成：
    SiO2 50-70
    Al2O3 0-12
    TiO2 0-8
    ZnO 4-7
    K2SiF6 4-10
    B2O3 10-15 。
  2. 根据权利要求1 所述的 无铅易熔绿色 环保玻璃，其特征在于不含铅及典型常用的昂贵低熔点金属、非金属材料及其化合物。
  3. 根据权利要求2所述的无铅易熔绿色环保玻璃，其特征在于所述典型常用的昂贵低熔点金属为铋、铊、钒、锗、锑中一种以上，所述典型常用的昂贵低熔点非金属为砷和碲中一种以上。
  4. 权利要求1所述的无铅低熔点绿色环保玻璃的制备方法，其特征在于包括下述步骤：
    1） 依据熔具坩埚或玻璃熔制炉炉膛生料化合物的合适承装或装填量，按权利要求1将各原料置于搅拌机内搅拌混合10-20秒钟，并一次性倒入坩埚放入炉中或一次性倒入装盛熔制玻璃炉膛；
    2） 使熔制炉炉温升至1000-1100℃间的设定温度点并保温15-30分钟，玻璃处于低粘度充分熔融的状态，取出后经冷却或倒入水中淬火成玻璃颗粒。
  5. 根据权利要求4所述的无铅低熔点绿色环保玻璃的制备方法，其特征在于所述玻璃颗粒还经破碎机粉碎制成玻璃粉。
  6. 根据权利要求4所述的无铅低熔点绿色环保玻璃的制备方法，其特征在于步骤2）以400℃/小时升温至1000-1100℃。
  7. 根据权利要求4所述的无铅低熔点绿色玻璃的制备方法，其特征在于结合步骤2）中通过熔制炉分批进料及出料实行连续性生产。
PCT/CN2012/086896 2012-07-03 2012-12-19 一种无铅易熔绿色环保玻璃及其制备方法 WO2014005406A1 (zh)

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