CN1012731B - 高压放电灯的复合坯体 - Google Patents

高压放电灯的复合坯体

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CN1012731B
CN1012731B CN87101811A CN87101811A CN1012731B CN 1012731 B CN1012731 B CN 1012731B CN 87101811 A CN87101811 A CN 87101811A CN 87101811 A CN87101811 A CN 87101811A CN 1012731 B CN1012731 B CN 1012731B
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fused ceramic
packing material
composite body
ceramic
oxide
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CN87101811A (zh
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乔里斯·简·乌门
简·威廉·鲁文达尔
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Koninklijke Philips NV
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Philips Gloeilampenfabrieken NV
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Abstract

本发明涉及一种高压放电灯的复合坯体,它包括:第一部分陶瓷材料借助于熔融陶瓷和第二部分金属材料、陶瓷材料或金属和陶瓷的混合材料相接合。所述的熔融陶瓷除了含A12O3外,或者还包含一种或多种碱土金属氧化物,或者还包含一种或多种稀土金属氧化物,或者还包含上述两种氧化物的混合物。
按本发明,该熔融陶瓷含有填充材料,该材料遍布于熔融陶瓷体积中,占熔融陶瓷的体积至少为20%,至多50%。

Description

本发明涉及一种用于高压放电灯的陶瓷复合坯体。这种复合坯体包括:将第一部分陶瓷材料利用陶瓷而和第二部分金属材料、陶瓷材料或金属和陶瓷的混合材料相接合。该熔融陶瓷除了含氧化铝外,或者还包含一种或多种碱土金属氧化物,或者还包含一种或多种稀土金属氧化物,或者还包含上述两种氧化物的组合物。
本说明书和权利要求书中所用的术语“陶瓷材料”可理解为一种至少含氧化铝的结晶的氧化物材料。例如,这种材料可能是单晶蓝宝石。另一种可能性是致密烧结的多晶氧化铝或铝酸钇石榴石。
这些适于作高压放电灯放电容器壁材的材料,可在温度约1300℃长时间地受热,且在此温度具有很高的抗碱土金属和卤化物侵蚀的性能。在1300℃以上长时间地受热,一般会引起有关材料的大量蒸发。而在1750℃至1800℃短时间地受热不产生不利的后果。然而,当加热超过1750℃至1800℃,即使时间很短,会产生显著的上述蒸发现象,甚至于造成自发的破裂。
这里所指的“稀土金属氧化物”包括下列氧化物:
Sc2O3、Y2O3、La2O3、Ce2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3
本说明书和权利要求书中所说的熔融陶瓷是指一种接合材料。它比复合坯体的各部分具有更低软化温度,它可以玻璃相、结晶相以及该两相组合的形式存在。
从欧洲专利申请0060582A1(PHN9968EU)可以了解本说明书第一段所 述类型的复合坯体。这种复合坯体可以是一种具有放电容器的高压放电灯,其放电容器的壁材为陶瓷材料,电流引入线元件通过该放电容器壁,借助于熔融陶瓷以气密方式与壁连接。常用的高压放电灯为高压钠灯和高压金属卤化物灯。就这两种类型的灯而言,在工作状态下,放电容器要经受高温,并且放电容器的填入物质有部分发生电离。因此,用于这类放电灯的熔融陶瓷,在高温应能抵抗钠和金属卤化物的侵蚀。
通过采用已知的熔融陶瓷得到的气密接合提供很高的抗钠和抗卤化物侵蚀的性能。一般来说,通过熔融陶瓷的细晶化作用,就可达到气密的接合。应该注意到,互接合部件的热膨胀系数一般是各不相同的,因此在熔融陶瓷中会产生应力。在细晶化的场合,其产生破裂的可能性小于粗结晶熔融陶瓷。这里所用的术语“粗结晶”可理解为80%的晶粒尺寸为10微米或10微米以上。当熔融陶瓷的80%的晶粒尺寸在1至5微米之间时,可认为这种熔融陶瓷是细结晶的。
细结晶熔融陶瓷的另一优点在于:在结晶过程中,出现夹杂物及微细裂缝的可能性大大地小于粗结晶熔融陶瓷的情形。
已发现,尽管已知的熔融陶瓷大部分是细结晶的,然而,在给定的情况下,它仍然会形成大的晶粒(>20微米),而且还会包含气泡形的空穴。这种气泡形的空穴是由于熔融陶瓷加工过程中的气体脱附作用所致。在实践中,大晶粒总是伴随微空穴而存在的。微空穴和气泡对熔融陶瓷的强度和抗侵蚀能力是不利的。
在实践中出现的另一个问题是,在熔封过程中会形成β铝酸盐晶体结构。已发现,在熔封过程中,当温度在最高范围内的较高值时,形成β铝酸盐晶体结构的可能性就大大增加。
β铝酸盐晶体结构非常容易受到侵蚀,尤其是受钠的侵蚀。因此,如果将熔融陶瓷用于钠或卤化钠填充成分的放电灯,是很不理想的。
本发明的目的在于提供一种方法,通过这种方法,可使复合坯体各 部分之间的接合基本上既不含大的晶粒、也不含β铝酸盐晶体结构,同时保留熔融陶瓷的有利性质。
为此,根据本发明开头第一段中所述的那种复合坯体即供此目的之用,其特征在于所述熔融陶瓷含有填充材料,这种填充材料遍布于熔融陶瓷的体积中,占熔融陶瓷的体积至少为20%,至多为50%。
本说明书和权利要求书中所用的术语“填充材料”可理解为熔融陶瓷的一种成分,它作为隔离相而存在于熔融陶瓷的其余各相之间。填充材料最好能充分均匀地遍布于熔融陶瓷体积中。填充材料的平均粒径,可根据熔融陶瓷所存在间隙的大小在一个稍为宽的范围内来选择。所选择的填充材料的粒径最好能保证在间隙尺寸为10至100微米之间时,至少有80%的粒径小于10微米。另外,所选择的粒径的分布应能保证填充材料的比表面积小于60m2/cm3(按理论密度为基准)。
已发现,具有填充材料的陶瓷材料完全可以避免大晶粒的出现。令人惊奇的是同时也避免了气泡形的空穴产生。另一优点是可使软化温度保持在1750℃以下。此外还显示出,产生β铝酸盐晶体结构的可能性也大大降低。
已发现,填充材料含量小于20%(体积)时,不能令人满意地抵制因气体脱附作用而导致的气泡和微空穴的形成。在这些条件下,产生β铝酸盐晶体结构的可能性基本上保持不变。
填充材料还会影响熔融陶瓷的粘度,并因此影响熔融陶瓷在复合坯体两部分之间所要填充的间隙中的迁移。如果填充材料所占的百分比不多于50%(体积),那么就显示能在广泛的各种不同的情况下保证含填充材料的熔融陶瓷的良好迁移。如果填充比例较高,则导致阻碍熔融陶瓷的迁移,这样会引致触变性效应,尤其是与填充材料的离析。
从德国专利公开说明书2,032,277号了解到,可以用某些材料作为熔融陶瓷的添加物。在此文献中,涉及使用添加物时是将之溶解于熔融 陶瓷中。一方面,从所述的专利公开说明书中得不到确定所需添加物用量的规则或说明。另一方面,事实上,使用了这些添加物,得到一种新的熔融陶瓷,它具有独特的结晶、抗金属蒸汽和粘附性能。
按本发明,最理想的是复合坯体中的填充材料由下列一种或多种金属氧化物组成:
氧化铝、
氧化锆、
氧化铪、
氧化钍、
氧化铀。
这些金属氧化物具有较宽范围的填充百分比,而不致有或基本上没有被溶解于熔融陶瓷的倾向。此外,加入这些材料作为填充材料仅仅引起熔融陶瓷软化温度稍微上升。
更具体地说,最佳的复合坯体,其中的填充材料是由HfO2组成,其用量占所述熔融陶瓷的20-40%(体积)。已发现,含20%到40%(体积)HfO2作为填充材料的熔融陶瓷通常会在复合坯体各部分之间产生最佳的接合。
参考附图更详细地介绍本发明复合坯体的实施方案。
附图显示一种高压钠灯的一个端部。这种灯本身是已知的,例如可参阅美国专利说明书3,716,743号,所以这里不作进一步的说明。所显示的钠灯的端部是一个复合坯体,包括由致密烧结的氧化铝(PCA)制成的灯管1和圆盘2组成的第一部分。由空心铌质套管3组成的第二部分气密地熔接入圆盘2。由带有钨螺旋线的钨销钉组成的电极4借助于钛钎焊料固定于套管3。按本发明,套管3借助于熔融陶瓷5气密地连接到圆盘2和灯管1。
实施例
大量的属于附图所示类型的高压钠灯放电容器中,其铌质套管与PCA圆盘之间的气密接合是借助于采用一种具有填充材料的熔融陶瓷而实现的。为了作出令人满意的比较,采用了相同尺寸的放电容器。最重要的尺寸为:
灯管1内径    5.1毫米
圆盘2内径    2.08毫米
套管3外径    2毫米
圆盘2高度    3毫米
采用熔融陶瓷而得到第一组的接合。该熔融陶瓷除了具有填充材料外,还包含Al2O3以及碱土金属氧化物为主,即按组成以摩尔%表示如下:
Al2O332.9
MgO    10.3
CaO    50.8
BaO    4.2
B2O31.8
按以下所述,得到熔融陶瓷:将上述组成的氧化物(每种氧化物的纯度至少为99.9%)的混合物置于高频电炉中熔化成一种玻璃状的物料,或熔化成具有微小晶粒的玻璃状物料。冷却后,将这种物料粉碎,然后,将一种呈晶粒形式的填充材料加到由此得到的粉末中。小心混合后,通过压制形成熔融陶瓷环。由此形成的熔融陶瓷证实含少量的水分(0.04摩尔%至0.12摩尔%不等)。
表Ⅰ显示了若干实施例的编号及其所采用的填充材料的种类及用量。此外,还指出了熔接过程中的最高温度。所加入的填充材料颗粒中,约85%小于10微米,而Al2O3的比表面积为25m2/cm3,HfO2的比表面积为58m2/cm3,ZrO2的比表面积为39m2/cm3
表Ⅰ
编号    填充材料    填充材料用量%(体积)    最高温度(℃)
1 Al2O330 1500
2 Al2O340 1500
3 ZrO220 1450
4 ZrO230 1500
5 ZrO240 1500
6 HfO220 1400
7 HfO230 1450
8 HfO240 1550
由按下述方式进行的熔封过程中可获得接合物。首先,将所要互连的部分接到所要的位置,并在接合面配以经过选择的熔融陶瓷的环状物。将组合件置于炉中加热,温度由室温至最高温度Tmax(一般为1250℃至1550°),升温速率大约为10℃/秒,并在最高温度时保持不超过150秒。然后,以至少10℃/秒的速率,冷却至约1100℃。温度在1100℃时保持至少110秒钟,但不超过250秒钟。随后,以5℃/秒的速率冷却至室温。
第二组的实施例是借助于以Al2O3、碱土金属氧化物和稀土金属氧化物为主要成分的熔融陶瓷而获得。起始的陶瓷组成(摩尔%)为:
Al2O335.8
CaO    55.4
SrO    7.0
Y2O31.8
按第一组实施例所述的方法,可得到含填充材料的熔融陶瓷。表Ⅱ示出在第二组实施例的熔封过程中所用的填充材料、最高温度Tmax的有关数据。填充材料Al2O3、HfO2以及ZrO2与第一种组合实施例中所 使用的种类相同。此外,将ThO2用作填充材料,其中84%的晶粒小于5微米,比表面积为28m2/cm3
表Ⅱ
编号    填充材料    填充材料用量%(体积)    最高温度(℃)
9 Al2O320 1450
10 Al2O330 1500
11 ZrO230 1550
12 HfO220 1550
13 HfO230 1600
14 HfO240 1600
15 HfO250 1675
16 ThO220 1500
17 ThO230 1550
18 ThO240 1650
熔封过程与第一组实施例的熔封过程相似,但这次最高温度范围扩大到约1700℃。
作为第三组合实施例,借助于熔融陶瓷而形成放电容器,该熔融陶瓷除了含填充材料外,还包含Al2O3和稀土金属氧化物,其组成(摩尔%)如下:
Al2O365.0
Sc2O319.25
Y2O35.25
La2O310.5
制备这种含填充材料的熔融陶瓷,其方法与第一组合实施例中所采用的方法相似。第三组的实施例的熔封过程与第一组实施例的熔封过程也相似。最高温度Tmax范围为1650℃至1750℃。表Ⅲ示出第3组实施 例的填充材料和最高温度的有关数据。
填充材料Al2O3、HfO2和ZrO2与第一和第二种组合实施例中所使用的相同。此外采用了填充材料UO2,其中84%的晶粒小于4微米,比表面积为35m2/cm3
表Ⅲ
编号    填充材料    填充材料用量%(体积)    最高温度(℃)
19 Al2O330 1650
20 Al2O330 1675
21 Al2O340 1700
22 ZrO220 1650
23 ZrO230 1675
24 ZrO240 1700
25 HfO220 1650
26 HfO230 1675
27 HfO240 1725
28 UO220 1675
29 UO230 1700
30 UO240 1750
所制得的放电容器的铌质套管与圆盘之间达到良好的气密接合,而熔融陶瓷呈细结晶态,带有分得极细的填充材料晶粒。在大多数情况下,用熔融陶瓷完全填充PCA圆盘和铌质套管间的间隙形空隙,显示了该熔融陶瓷的良好迁移性质。
在各实施例中,均未发现β铝酸盐晶体结构。
在用熔融陶瓷对放电容器所作的熔封过程中,发现各表中使用编号为5、8、15、17和18的有关熔融陶瓷的粘度增加。在其中少数情况下,导致PCA圆盘和铌质套管间空隙只有部分的填充。然而,触变效应,例 如离析现象则未发现。

Claims (6)

1、一种高压放电灯的复合坯体,该坯体包括由陶瓷材料制成的第一部分,通过一种熔融陶瓷和由金属材料、陶瓷材料或金属与陶瓷的混合材料所制成的第二部分相接合,所述的熔融陶瓷除了包含Al2O3外,或者还包含一种或多种碱土金属氧化物,或者还包含一种或多种稀土金属氧化物,或者是包含上述两类氧化物的组合物,其特征在于该熔融陶瓷含有填充材料,所述填充材料分布于熔融陶瓷整个体积中,并且占熔融陶瓷的体积为20%-50%。
2、按权利要求1的复合坯体,其特征在于该填充材料是由下列一种或多种金属氧化物所组成:
氧化铝、
氧化锆、
氧化铪、
氧化钍、
氧化铀。
3、按权利要求1或2的复合坯体,其特征在于该填充材料是由HfO2组成,HfO2的含量占所述熔融陶瓷的20-40%(体积)。
4、按权利要求1的复合坯体,其特征在于所述陶瓷材料是至少包含Al2O3的一种结晶的氧化物材料。
5、按权利要求1的复合坯体,其特征在于所述碱土金属氧化物是MgO、CaO、SrO或BaO。
6、按权利要求1的复合坯体,其特征在于所述稀土金属氧化物是Sc2O3、Y2O3、La2O3、Ce2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3或Lu2O3
CN87101811A 1986-03-11 1987-03-07 高压放电灯的复合坯体 Expired CN1012731B (zh)

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