CN1657460B - 适配于玻璃-金属复合物的玻璃的应用 - Google Patents

适配于玻璃-金属复合物的玻璃的应用 Download PDF

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CN1657460B
CN1657460B CN2005100093331A CN200510009333A CN1657460B CN 1657460 B CN1657460 B CN 1657460B CN 2005100093331 A CN2005100093331 A CN 2005100093331A CN 200510009333 A CN200510009333 A CN 200510009333A CN 1657460 B CN1657460 B CN 1657460B
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T·库克尔科恩
G·鲍尔
N·本茨
F·-D·德尼茨
R·曼尔
M·米勒
M·西勒
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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
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/02—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing by fusing glass directly to metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S10/00—Solar heat collectors using working fluids
    • F24S10/40—Solar heat collectors using working fluids in absorbing elements surrounded by transparent enclosures, e.g. evacuated solar collectors
    • F24S10/45—Solar heat collectors using working fluids in absorbing elements surrounded by transparent enclosures, e.g. evacuated solar collectors the enclosure being cylindrical
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S25/00—Arrangement of stationary mountings or supports for solar heat collector modules
    • F24S25/60—Fixation means, e.g. fasteners, specially adapted for supporting solar heat collector modules
    • F24S2025/6012—Joining different materials
    • F24S2025/6013—Joining glass with non-glass elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2235/00—X-ray tubes
    • H01J2235/16—Vessels
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y02E10/44—Heat exchange systems

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Abstract

适配于玻璃-金属复合物的玻璃的应用本发明涉及用具有下列组成的玻璃作含玻璃-金属复合物的真空管集电极中的玻璃管或含玻璃-金属复合物的X-射线管的应用：B2O3 8-11.5重量％Al2O3 5-9重量％Na2O 5-9重量％K2O 0-5重量％CaO 0.4-1.5重量％SiO2 余量。

Description

适配于玻璃-金属复合物的玻璃的应用
技术领域
本发明涉及适于玻璃-金属复合物的玻璃的应用。
背景技术
玻璃-金属复合物例如用于真空管集电极和X-射线管。在真空管集电极中需要真空密封的玻璃金属复合件用于在由金属制成的吸收管和由玻璃制成的套管之间的绝热。
在抛物面槽型太阳能电站中，由在收集器中的聚焦辐照产生有强局部温差的达400℃的工作温度。此外，通过温度交变出现与白昼交替和暂时的云层相关的稳态负载。
在高温太阳能收集器情况下，至今是应用玻璃-金属复合物，如US1294466中所述。在这种所述的家用技术中，将具有约15×10-6K-1的高热膨胀系数的非常薄的金属簧片熔合进具有约3×10-6K-1的明显更低的热膨胀系数的耐温度交变的玻璃中。在温度负载中所预计的热应力由金属簧片的塑性变形吸收。但在太阳能收集器中不可避免的长期交变应力常导致在高负载区的机械失效和导致该玻璃-金属复合件出现大于每年4％的不可接受的高裂纹率。这对在电站领域广泛引入太阳能技术是一种严重的障碍。
这类玻璃-金属复合物被认为是不适配的复合物，因为玻璃和金属有不同的热膨胀系数。
这种技术也用于X-射线管中，如US 6324870 B1所述。
由X-射线管技术还已知应用所谓适配的玻璃-金属复合物。在此技术中将具有低膨胀系数的金属熔合到具有相同或相近膨胀系数的玻璃中。至今采用Schott 8250、Schott 8245
Figure 051093331_1
和8447作为熔合玻璃。该熔合玻璃的缺点是，与常用的硼硅酸盐玻璃(DURAN
Figure 051093331_3
、DIN ISO719、等级HGB1，S.1)相比其有明显较差的耐水性和耐酸性(DIN ISO719，等级HGB1，S.3-4)。
经由多种具有渐次变化的膨胀特性的所谓中间玻璃通过X-射线管技术中已知的熔合方法将热膨胀系数约为5×10-6K-1的金属与热膨胀系数约为3×10-6K-1的玻璃熔合可达较好的结果。此法非常可靠，但其缺点是，所用的中间玻璃是不耐腐蚀的，而这对太阳能收集器是绝对必要的前堤。为制备与稳定的硼硅酸盐玻璃3.3(Duran)的复合物，采用了其它的过渡玻璃。这类玻璃的已知复合物系列为：金属(如NiCo2918)-Schott 8448-Schott 8449
Figure 051093331_5
-Schott 8447
Figure 051093331_6
-Schott8330-Duran。
此外，这类中间玻璃由于玻璃工艺的原因不能制成外径大于100mm的管形。因此在X-射线管技术中实用的中间玻璃的手工多步熔合方法由于其成本原因就妨碍了太阳能收集器所需的自动化制备。由此总的来看，适于X-射线管的玻璃和金属的熔合法不可转用到高温太阳能收集器上。
此外，过渡玻璃的熔合在工艺上是昂贵的，并且增加了废品率和工艺成本。再则适于含多种过渡玻璃的玻璃-金属复合物的制备工艺在工业上不能自动化。
发明内客
本发明的目的在于提供一种用于适配的玻璃-金属复合物的玻璃，该玻璃同时满足耐温度交变性和耐气候性的要求。
本发明的目的是通过将有下列组成的玻璃用于具有含玻璃-金属复合物的真空管集电极的玻璃管达到的：
B2O3     8-11.5重量％
Al2O3    5-9重量％
Na2O     5-9重量％
K2O      0-5重量％
CaO      0.4-1.5重量％
SiO2     余量
另一应用是用于含玻璃-金属复合物的X-射线管。
这类无钡玻璃对于加工成吸饮安瓿、小瓶和其它的药物主包装介质是已知的，如适于喷射、Karpulen、笔头和试管。为制备这种药物主包装介质可采用最大外径为30mm的玻璃管。
至今还未曾考虑到用这类玻璃来制备适于太阳能的直径必须大于120mm的玻璃管和用于玻璃-金属复合物。其归因于至今还未认知这种玻璃兼有多种特性，使其适于在真空管集电极中应用。
该玻璃的热膨胀系数为5.5×10-6K-1，与常用的金属的热膨胀系数仅有约10％的偏差。此外，该玻璃耐酸和耐碱(按DIN 12116和DIN ISO 695为等级S1和A2)以及耐水(等级HGB1，DIN ISO 719)。再则该玻璃的铁含量少，这对真空管集电极的套管是特别重要的。此外还表明，它不仅可制备外径最大为30mm的管，而且这类玻璃还可顺利制成外径大于120mm的管。这种有利的特性使应用过渡玻璃成为不必要，使工业生产过程可实现自动化。
这种玻璃的优选组成为：
B2O3    9.5重量％
Al2O3   6.5重量％
Na2O    6.5重量％
K2O     2.5重量％
CaO     0.5重量％
SiO2   余量
该玻璃优选含铁小于400ppm，特别是含铁小于150ppm。所述金属含量来自组分、特别是SiO2组分的天然杂质。通过应用经特别挑选的原料可明显减少铁含量，以致可进一步提高适于真空管集电极的套管的适用性。
优选的应用是该玻璃-金属复合物的金属是DIN 17745的第1.3981组中的金属材料。这种材料具有下列组成(以％表示的重量含量)：
28-30Ni，达0.05C，16-18Co，余量为铁。
已表明该金属的膨胀系数为5×10-6K-1，并且与本发明种类的玻璃有特别持久的复合。
优选在熔合区的金属部件的厚度至少为0.5-1mm。这种措施也有利于稳定的玻璃-金属复合物，使得在高机械负载下也可保证具有长期的使用寿命。
附图简介
在附图中示例性给出由玻璃管1和金属管2构成的玻璃-金属复合物。金属管2的边缘无材料减少地以厚度D(如D＝1mm)直接(即无需中间玻璃)熔合进玻璃管1中。

Claims (8)

1.具有下列组成的玻璃用于含玻璃-金属复合物的真空管集电极中的玻璃管(1)的应用：
B2O3            8－11.5  重量%
Al2O3           5－9      重量%
Na2O            5－9     重量%
K2O              0－5     重量%
CaO             0.4－1.5重量%
SiO2             余量。
2.具有下列组成的玻璃用于含玻璃-金属复合物的X-射线管的应用：
B2O3            8－11.5  重量%
Al2O3           5－9       重量%
Na2O           5－9       重量%
K2O             0－5       重量%
CaO            0.4－1.5  重量%
SiO2            余量。
3.权利要求1或2的应用，其中所述玻璃具有下列组成：
B2O3            9.5  重量%
Al2O3           6.5  重量%
Na2O           6.5  重量%
K2O             2.5  重量%
CaO            0.5  重量%
SiO2            余量。
4.权利要求1或2的应用，其中所述玻璃的铁含量小于450 ppm。
5.权利要求4的应用，其中所述玻璃的铁含量小于150 ppm。
6.权利要求1或2的应用，其中所述玻璃-金属复合物的金属由DIN 17745的Nr.1.3981金属材料构成。
7.权利要求1或2的应用，其中所述金属部分在熔合区域的厚度为0.5－1 mm。
8.权利要求7的应用，其中所述金属部分在熔合区域的厚度至少为1 mm。
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US20050181925A1 (en) 2005-08-18
DE102004008559B9 (de) 2007-05-03
IL165922A0 (en) 2006-01-15

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