CN1217300A - 用于灯泡的含碱土金属的硼铝硅酸盐玻璃及其应用 - Google Patents
用于灯泡的含碱土金属的硼铝硅酸盐玻璃及其应用 Download PDFInfo
- Publication number
- CN1217300A CN1217300A CN98124554A CN98124554A CN1217300A CN 1217300 A CN1217300 A CN 1217300A CN 98124554 A CN98124554 A CN 98124554A CN 98124554 A CN98124554 A CN 98124554A CN 1217300 A CN1217300 A CN 1217300A
- Authority
- CN
- China
- Prior art keywords
- glass
- bulb
- weight
- content
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000011521 glass Substances 0.000 title claims abstract description 92
- 150000001342 alkaline earth metals Chemical class 0.000 title abstract description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 title abstract description 5
- 239000005995 Aluminium silicate Substances 0.000 title description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 title description 2
- FGUJWQZQKHUJMW-UHFFFAOYSA-N [AlH3].[B] Chemical compound [AlH3].[B] FGUJWQZQKHUJMW-UHFFFAOYSA-N 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001868 water Inorganic materials 0.000 claims abstract description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 238000009835 boiling Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 239000005368 silicate glass Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 239000011733 molybdenum Substances 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000005407 aluminoborosilicate glass Substances 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000007772 electrode material Substances 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- 230000014509 gene expression Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 206010027146 Melanoderma Diseases 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000007507 annealing of glass Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- 239000005341 toughened glass Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000003258 bubble free glass Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 210000002189 macula lutea Anatomy 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RECVMTHOQWMYFX-UHFFFAOYSA-N oxygen(1+) dihydride Chemical compound [OH2+] RECVMTHOQWMYFX-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
Classifications
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/21—Silica-free oxide glass compositions containing phosphorus containing titanium, zirconium, vanadium, tungsten or molybdenum
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
- C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
-
- 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
-
- 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
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J61/00—Gas-discharge or vapour-discharge lamps
- H01J61/02—Details
- H01J61/30—Vessels; Containers
- H01J61/302—Vessels; Containers characterised by the material of the vessel
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01K—ELECTRIC INCANDESCENT LAMPS
- H01K1/00—Details
- H01K1/28—Envelopes; Vessels
Landscapes
- 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
本发明涉及一种用于含钼元件和灯泡温度最大为650℃灯泡的含碱土金属的硼铝硅酸盐玻璃,该玻璃具有以下组成(重量%、以氧化物为基准):SiO259-61;Al2O313.5-15.5;B2O33-5;MgO2.3-5;CaO8.2-10.5;BaO8.5-9.5;CeO20.03-0.3;其中,(MgO+CaO)/BaO< 1.60;CaO/MgO< 4.2,并且碱金属氧化物的含量< 0.08重量%,而水的含量≤0.02重量%。
Description
本发明涉及一种用于含钼元件和灯泡温度大约为550-650℃的灯泡的含碱土金属的硼铝硅酸盐玻璃及其应用。
已知上述用途的玻璃不得含有碱金属氧化物,因为碱金属离子干扰灯泡的蓄热卤循环。这是因为灯泡在使用期间,来自灯丝的钨蒸气和卤/惰性气体混合物达成卤化钨形成和分解之间的平衡。分解反应在比形成反应高的温度下进行,以便钨重新沉积在灯丝上。如果这一循环被污染成分例如碱金属离子干扰,钨就不会沉沉积在灯丝上而是沉积在玻璃泡的内壁上,形成不希望有的磨光黑色涂层。出于这个原因,对这类玻璃在无碱金属氧化物方面有较高的要求。
对可蓄热卤循环具有坏作用的污染物不仅可通过玻璃引入,而且可通过灯泡生产的实际过程引入。因此所用的电极材料的纯度也是至关重要的。纯化过程例如通过退火对电极进行预处理特别复杂和昂贵。对碱金属含量较高的玻璃泡进行回火同样也是非常复杂和昂贵的。
为了将灯泡玻璃用于含有钼元件作为电极源的灯泡,玻璃的热膨胀在灯泡的整个温度范围内要与钼的热膨胀相适应,以确保在玻璃和电极源之间的不透气密封。与钼相比,玻璃在其凝固温度(凝固点)处具有较高的膨胀,即钼和玻璃之间的膨胀差必须是正的,以便在玻璃中获得有利于密封Mo电极源的径向压应力。因此玻璃应该具有4.4×10-6/K-4.7×10-6/K的膨胀系数α20/300。
对于在灯泡使用期间不会导致使玻璃变形的灯泡温度而言,玻璃必须具有足够的热稳定性。
对适合于在灯泡中作灯泡玻璃的玻璃的另一个要求是它应适合于管拉制。可能是出于这个原因,玻璃的晶化必须足够稳定。
专利文献已经描述了众多涉及白炽灯玻璃的公开文件。
与碱金属离子一样,水和氢离子也影响卤循环。出于这个原因,US4163171也描述了一种其中玻璃不仅仅“必须没有碱金属”,而且也可能又含有少于0.03重量%水的白炽灯。
DE3305587A1描述了一种由BaO含量(11-16重量%)较高的玻璃泡制得的白炽灯。DE2930249C2涉及BaO含量(10-23重量%)也较高的玻璃组合物作为灯泡材料的应用,而且,在组合物中,BaO∶CaO的重量比为2.3-3.5(CaO∶BaO为0.28-0.43)。据说后一文献描述的玻璃改进了对称之为重沸的现象的抵抗力。重沸是指玻璃用火焰进行进一步处理或再次加热时形成大量包含有气体的微小气泡的趋势。它有损于光的传播并使再次加热的区域变得脆弱。
BaO含量很高的玻璃的缺点是与其他碱土金属氧化物含量较高的玻璃相比,它们具有较高的熔融温度和工作温度。较高的熔融点要负担较高的电力消耗、较高的熔融成本、并对池窑材料产生较大的腐蚀。
US 3496401描述了一种由铝硅酸盐玻璃制得的白炽灯,它含有碱土金属和碱金属氧化物的最大含量为0.1重量%的,特别是所述白炽灯由包括SiO2,Al2O3,10-25重量%碱土金属氧化物的玻璃制得,没有进一步地详细给出其特定的含量,B2O3仅是一种任选成分。
US3310413描述了一种含有碱土金属并用于密封钼的硼铝硅酸盐玻璃,该玻璃在各碱土金属氧化物之间具有确定的比例。因此,MgO作为任选的成分时,MgO与BaO之比被限制为小于0.75,而CaO与MgO和CaO的总量之比被限制为0.6-2.0。
在US4394453中描述的用于钨/卤灯的玻璃密封件含有大量的Al2O3(至少16重量%),这就致使SiO2/Al2O3之比较低。
US4409337也描述了用于钨/卤灯玻璃密封件的玻璃,相对于Ai2O3含量,它的SiO2含量较低,其用SiO2/Ai2O3重量比(在该文献中为3.1-3.7)来表示。
US5489568描述了一种特别适合于用作平板显示器的玻璃。这些玻璃含有大量的Al2O3(≥18重量%)而具有较低的SiO2含量(≤55重量%)或具有较低的Al2O3含量(≤13重量%)而具有较高的SiO2含量(≥55重量%)。结果它们所具有的粘度特性,特别适合平板玻璃拉制工艺,而较少适用于生产灯泡的拉管工艺。这些玻璃特别适应于a-硅和聚硅而很少适应于Mo。同样可应用在EP0672629A2和US5508237中公开的玻璃。
上述用途的商购玻璃是由本申请人生产并具有以下组成(重量%)的玻璃8252:60SiO2,4.5B2O3,14.5Al2O3,2MgO,10CaO,9BaO。由于其整体性能(如α20/300为4.6×10-6/K、Tg为720℃)好,它非常适合作温度大约为550-650℃的灯泡玻璃。
然而,对于由该玻璃生产的灯泡和由前述玻璃生产的灯泡而言,污染物很容易损害灯泡的功能是确确实实的,不管它们是由玻璃产生的还是由安装在灯泡上的电极材料产生的,就像上述由于卤循环受到干扰而导致的在玻璃泡内壁上的黑斑所证明的那样。因此,对纯度,特别是无碱金属的要求很高是必然的。
因此,本发明的目的是发现一种玻璃,当其用作灯泡玻璃时,能以较低的成本防止所说的黑斑。
通过使用本发明的含氧化铈和碱土金属的硼铝硅盐酸玻璃就达到了本目的。
玻璃含有59-61%重量的SiO2。较高的SiO2含量使得热膨胀特别低,而较低的SiO2含量导致热膨胀系数非常高,并将减少转变温度。
玻璃含有13.5-15.5重量%的Al2O3。偏离这一范围将导致偏离所希望的热膨胀值,并因此导致不能良好的膨胀。另外,对粘度参数也有不良影响。甚至最小的SiO2含量和最大的Al2O3含量也要确保SiO2/Al2O3重量比较高,这对玻璃形成性能和玻璃的粘接强度有益。较高的SiO2含量(特别是相对于Al2O3含量)能减少玻璃的重沸并对密封有益。在本发明优选的技术方案中,这一比例至少为4.00。
SiO2和Al2O3具有提高转变温度Tg和工作温度VA的作用,而B2O3和碱土金属氧化物能减少粘度。
玻璃具有3-5.5重量%的B2O3含量。3.1-5重量%是优选的。氧化硼能有利地便于熔融。含量较高将过分地减少玻璃的转变温度Tg并因此提高在热载条件下灯泡的稳定性。
各碱土金属氧化物对减少粘度和增加热膨胀的贡献是不同的:BaO比MgO更能提高粘度,CaO的效果介于二者之间。相反,CaO增加热膨胀的程度比MgO和BaO大。因此玻璃含有特定数量的碱土金属氧化物,并且在各成分之间具有特定的比例:
玻璃中BaO的含量是8.5-9.5重量%,玻璃中CaO的含量是8.2-10.5重量%。而且,玻璃含有2.3-5重量%的MgO。
另一方面,CaO和MgO的总量与BaO的重量比((CaO+MgO)/BaO)应小于1.60。CaO与MgO的重量比也是重要的并应小于4.20。
令人吃惊地是,现已发现向组成在上述范围的玻璃中加入氧化铈能减少由这些玻璃生产的灯泡产生的黑斑。因此,本发明玻璃含有0.03-0.3重量%的CeO2。在该浓度范围内,氧化铈对灯泡玻璃所要求的物理性能没有任何不良影响。较高的含量将导致对玻璃干扰而出现黄斑,这是由于CeO2将玻璃的UV边缘移向长波处的缘故。还有,CeO2也是一种良好的澄清剂,其原因是它不需要另外的澄清剂就能达到满意的无气泡的玻璃质量。由于氧化铈良好的澄清作用,玻璃的重沸温度也增加了。重沸温度是指在该处室温下肉眼看不见气泡的玻璃试样当温度升高时在与金属(试样夹持物,Mo)的界面处突然形成气泡的温度。因此,当熔合Mo时,本发明玻璃比澄清较差的玻璃具有更小的重沸趋势。
通常玻璃的使用温度越高,对碱金属氧化物和其他杂质的含量(极低)就要求越严,在玻璃和电极材料中,现已令人吃惊地发现:本发明玻璃由于其热载的稳定性良好,适合于用作灯泡温度最大为650℃灯泡的灯泡材料,<0.08重量%的碱金属氧化物含量是允许的。为了说明在不干涉敏感***和不致导玻璃黑斑的条件下可允许较大数量的杂质的事实,给出以下实施例作为参考。
在本发明玻璃中,0.03重量%,即≤0.08重量%的碱金属氧化物含量是允许的,这一事实意味着简化了玻璃和灯泡的生产,并且使得费用降低。因为这一上限值并不要求所有的氧化物原料都具有极低的碱金属含量。
如上所述,玻璃中水的含量也是重要的。其应该保持最大为0.02重量%的限值。通过适当地选择原料和熔融条件,将水的含量保持在合适的较低水平上也是可能的。例如通过使用氧化铝取代氢氧化铝可减少水的含量。
本发明玻璃具有4.4×10-6/K-4.7×10-6/K的热膨胀系数α200/300和大于710℃的转变温度Tg,这也说明本发明玻璃在灯泡试验(如下)中在热载条件下具有足够的稳定性,并且表明它们自身适合用作灯泡温度最大为650℃灯泡的灯泡材料。至少为1430℃的重沸温度表明其耐重沸性良好。
实施例
为了生产本实施例的玻璃,用作特定氧化物成分的原料是硅砂、硼酸、氧化铝、白云石、碳酸钙/碳酸钡、和氧化铈,碳酸钡具有较低的碱金属含量,而其他原料具有工业玻璃的标准纯度。例如V2(参见表1),所用的所有原料都具有较低的碱土金属含量。在1550-1600℃下熔融均化良好的批料,并澄清和均化。然后拉管。该管表明玻璃质量很好并且尺寸精度较高,但没有干扰晶体。
表1表示本发明玻璃的两个实例(A)和三个比较例(V),还有其组成(重量%、以氧化物为基准)和不可缺少的性能:
除了热膨胀系数α200/300,转变温度(Tg),粘度为1013dPas时的温度(AP)、粘度为107.6dPas时的温度(Ew)和粘度为104dPas时的温度(VA)外,也给出了重沸温度,该重沸温度越高,当密封Mo时玻璃形成气泡的趋势就越小。
对于灯泡试验来说,以常规方法用管来生产卤灯(每个实施例不大于45个灯泡)。使用纯度不同的电极材料(在表1中表示为“纯”、或“不纯”)。在大约为640℃的灯泡温度下使用灯泡。一方面,在实施例V2和V3(cf表1)情况下,对不纯的电极材料(1)进行退火(参见2a),而另一方面,对玻璃泡进行回火(参见2b)。这两个复杂的处理步骤不适合于经济化生产。例如在灯泡试验中,玻璃泡内壁变黑,在表1中指出了变黑的灯泡的质量(实际由“变黑的程度”决定)和数量(%)。在这方面,0表示没有变黑,1表示轻微变黑,2表示中度变黑,3表示变得非常黑。
对于实施例A1,确定最大的晶体生长率CG最大和最大的反玻化温度UDT(液体温度)。CG最大=0.11微米/分钟和UDT=1180℃(在Va下为58K)的结果证明本发明玻璃对晶化具有足够的稳定性。
该实施例说明向玻璃中加入铈使得灯泡可允许有较大数量的玻璃杂质(碱金属氧化物)和电极材料杂质,尽管如此,比起用不含氧化铈的玻璃生产的灯泡,该灯泡在灯泡试验中还继续表现出满意的结果。
作为对玻璃原料和电极材料及生产条件的要求放松的结果,使用本发明玻璃生产灯泡将更加简化和经济。表1
典型的技术方案(A)和对比例(V):
玻璃的组成(重量%)及其重要性能
n.d=未测试
V1 | V2 | A1 | A2 | V3 | |
SiO2 | 59.1 | 59.1 | 59.1 | 59.8 | 56.3 |
Al2O3 | 14.5 | 14.5 | 14.5 | 14.5 | 15.7 |
B2O3 | 4.85 | 4.85 | 4.85 | 3.5 | 4.65 |
MgO | 2.5 | 2.5 | 2.5 | 5.0 | 5.6 |
CaO | 10.3 | 10.3 | 10.3 | 8.4 | 8.3 |
BaO | 8.85 | 8.75 | 8.75 | 8.8 | 8.1 |
CeO2 | - | - | 0.3 | 0.03 | - |
Sb2O3 | 0.17 | 0.1 | - | - | - |
Na2O | 0.11 | 0.02 | 0.06 | 0.065 | 0.03 |
K2O- | 0.02 | 0.01 | 0.01 | 0.006 | 0.02 |
水(重量%) | 0.016 | 0.020 | 0.019 | 0.011 | 0.017 |
α20/300(10-6/K) | 4.58 | 4.55 | 4.54 | 4.59 | 4.45 |
Tg(℃) | 719 | 715 | 714 | 725 | 714 |
AP(℃) | 725 | 725 | 725 | n.d | 726 |
Ew(℃) | 940 | 940 | 940 | n.d | n.d |
VA(℃) | 1237 | 1236 | 1238 | 1244 | 1180 |
重沸温度(℃) | n.d | 1465 | 1482 | 1470 | 1430 |
电极材料 | 纯 | 1)不纯2a)退火2b)回火玻璃 | 不纯 | 1)不纯2a)退火2b)回火玻璃 | |
“灯泡试验” | 变黑 | 1)变黑2a)变黑2b)不变黑 | 不变黑 | 不变黑 | 1)变黑2a)不变黑2b)不变黑 |
变黑程度:‰ | n.d | 1)0∶7;1∶8;2∶18;3∶66 | - | 1)0∶37;1∶23;2∶17;3∶23 |
Claims (5)
1.用于含有钼元件和灯泡温度最大为650℃灯泡的含碱土金属的硼铝硅酸盐玻璃,其特征在于:它具有以下组成(重量%、以氧化物为基准):
SiO2 59 -61
Al2O3 13.5 -15.5
B2O3 3 -5.5
MgO 2.3 -5
CaO 8.2 -10.5
BaO 8.5 -9.5
CeO2 0.03 -0.3
其中
MgO+CaO <1.60
BaO
CaO/MgO <4.2
并且碱金属氧化物的含量<0.08重量%,而水的含量≤0.02重量%。
2.根据权利要求1的玻璃,其特征在于:它含有3.1-5重量%的B2O3。
3.根据权利要求1或2的玻璃,其特征在于:SiO2/Al2O3的重量比≥4.00。
4.根据权利要求1-3至少之一的玻璃,其具有4.4×10-6/K-4.7×10-6/K的热膨胀系数α20/300、大于710℃的转变温度Tg和至少1430℃的重沸温度。
5.根据权利要求1-4至少之一的玻璃的应用,其用作灯泡温度大约为550-650℃灯泡的灯泡材料。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19747354A DE19747354C1 (de) | 1997-10-27 | 1997-10-27 | Erdalkalialuminoborosilicatglas für Lampenkolben und dessen Verwendung |
DE19747354.7 | 1997-10-27 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1217300A true CN1217300A (zh) | 1999-05-26 |
CN1102915C CN1102915C (zh) | 2003-03-12 |
Family
ID=7846720
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN98124554A Expired - Fee Related CN1102915C (zh) | 1997-10-27 | 1998-10-27 | 用于灯泡的含碱土金属的硼铝硅酸盐玻璃及其应用 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6074969A (zh) |
EP (1) | EP0913366B1 (zh) |
JP (1) | JPH11217236A (zh) |
KR (1) | KR100518357B1 (zh) |
CN (1) | CN1102915C (zh) |
AR (1) | AR017521A1 (zh) |
BR (1) | BR9804064A (zh) |
DE (2) | DE19747354C1 (zh) |
ES (1) | ES2190028T3 (zh) |
HU (1) | HUP9802469A3 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101279815B (zh) * | 2002-02-01 | 2011-05-11 | 肖特股份有限公司 | 碱土铝硅酸盐玻璃及其应用 |
CN101585659B (zh) * | 2003-08-08 | 2011-10-19 | 日本电气硝子株式会社 | 外套容器用玻璃 |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6323585B1 (en) * | 1998-11-02 | 2001-11-27 | Corning Incorporated | Ultraviolet absorbing and yellow light filtering glasses for lamp envelopes |
DE19903788B4 (de) * | 1999-02-01 | 2005-04-28 | Schott Ag | Verfahren zur Läuterung von Glasschmelzen |
DE19939771B4 (de) * | 1999-08-21 | 2004-04-15 | Schott Glas | Verfahren zur Läuterung von Glasschmelzen |
US7211957B2 (en) * | 2000-05-05 | 2007-05-01 | Telux-Spezialglas Gmbh | Alumino earth-alkali silicate glasses with high thermal capacity for light bulbs and use thereof |
DE10022769A1 (de) * | 2000-05-05 | 2001-11-08 | Telux Lampenrohr Gmbh | Thermisch hoch belastbare Alumoerdalkalisilikatgläser für Lampenkolben und Verwendung |
DE10034985C1 (de) † | 2000-07-19 | 2001-09-06 | Schott Glas | Verfahren zur Herstellung von Aluminosilicatgläsern, Aluminosilicatgläser sowie deren Verwendungen |
DE10204149C1 (de) | 2002-02-01 | 2003-07-10 | Schott Glas | Erdalkalialuminosilicatglas für Lampenkolben sowie Verwendung |
DE10306427B4 (de) | 2002-03-26 | 2016-07-07 | Schott Ag | Verwendung eines Glases zur Herstellung von Lampenkolben von Fluoreszenzlampen und Lampenkolben von Fluoreszenzlampen |
AT6924U1 (de) | 2003-05-27 | 2004-05-25 | Plansee Ag | Kaltkathoden-fluoreszenzlampe mit molybdän-stromdurchführungen |
US9000667B2 (en) * | 2009-08-26 | 2015-04-07 | Ocean's King Lighting Science & Technology Co., Ltd. | Luminescent element, preparation method thereof and luminescence method |
DE102009039071B3 (de) | 2009-08-27 | 2011-02-24 | Schott Ag | Thermisch hochbelastbares Glas für Lampenkolben und dessen Verwendung |
US10035727B2 (en) | 2013-07-15 | 2018-07-31 | Ppg Industries Ohio, Inc. | Glass compositions, fiberizable glass compositions, and glass fibers made therefrom |
US9278883B2 (en) * | 2013-07-15 | 2016-03-08 | Ppg Industries Ohio, Inc. | Glass compositions, fiberizable glass compositions, and glass fibers made therefrom |
PT3887329T (pt) | 2018-11-26 | 2024-05-27 | Owens Corning Intellectual Capital Llc | Composição de fibra de vidro de alto desempenho com módulo de elástico melhorado |
MX2021005663A (es) | 2018-11-26 | 2021-07-07 | Owens Corning Intellectual Capital Llc | Composicion de fibra de vidrio de alto rendimiento con modulo especifico mejorado. |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE259099C (zh) * | ||||
NL125167C (zh) * | 1963-01-17 | |||
US3496401A (en) * | 1965-12-30 | 1970-02-17 | Corning Glass Works | Glass envelopes for iodine cycle incandescent lamps |
JPS5186515A (ja) * | 1975-01-28 | 1976-07-29 | Tokyo Shibaura Electric Co | Kankyuyogarasu |
US4060423A (en) * | 1976-07-27 | 1977-11-29 | General Electric Company | High-temperature glass composition |
SU642265A1 (ru) * | 1976-09-15 | 1979-01-15 | Предприятие П/Я Х-5382 | Стекло |
DE2650298A1 (de) * | 1976-11-02 | 1978-05-03 | Patra Patent Treuhand | Halogengluehlampe |
GB2032909B (en) * | 1978-08-09 | 1982-12-22 | Gen Electric | Sealing glass compositions |
DE2941215C2 (de) * | 1979-10-11 | 1988-05-26 | Schott Glaswerke, 6500 Mainz | Gelbe alkalifreie thermisch hoch belastbare Einschmelzgläser im System SiO↓2↓-Al↓2↓O↓3↓-Erdalkalioxide für Molybdän |
US4394453A (en) * | 1981-09-08 | 1983-07-19 | Corning Glass Works | Envelopes for tungsten-halogen lamps |
US4441051A (en) * | 1982-02-22 | 1984-04-03 | General Electric Company | Lamp seal glass |
US4409337A (en) * | 1982-11-12 | 1983-10-11 | Corning Glass Works | Glass envelopes for tungsten-halogen lamps |
US4677081A (en) * | 1985-10-07 | 1987-06-30 | General Electric Company | Arsenic-free lead silicate vacuum tube glass |
DD259099A3 (de) * | 1986-04-23 | 1988-08-17 | Molybdäneinschmelzglas für die Herstellung von Halogenkreislauflampen | |
ES2148139T3 (es) * | 1989-11-16 | 2000-10-16 | Libbey Owens Ford Co | Composicion de vidrio verde absorbente de la radiacion infrarroja y ultravioleta. |
JP2966161B2 (ja) * | 1991-09-06 | 1999-10-25 | 旭テクノグラス株式会社 | Hidランプ用前面ガラス |
JP2532045B2 (ja) * | 1992-02-05 | 1996-09-11 | 東芝硝子株式会社 | 照明用ガラス組成物 |
TW226472B (zh) * | 1992-06-01 | 1994-07-11 | Gen Electric | |
US5350972A (en) * | 1993-05-25 | 1994-09-27 | General Electric Company | UV absorbing lamp glass |
DE4325656C2 (de) * | 1993-07-30 | 1996-08-29 | Schott Glaswerke | Verwendung eines Glaskörpers zur Erzeugung eines als Brandschutzsicherheitsglas geeigneten vorgespannten Glaskörpers auf einer herkömmlichen Luftvorspannanlage |
KR950007895A (ko) * | 1993-09-24 | 1995-04-15 | 박경팔 | 메탈 할라이드 램프 |
JPH07206466A (ja) * | 1994-01-10 | 1995-08-08 | Asahi Glass Co Ltd | 陰極線管のフェイス用ガラス組成物 |
US5508237A (en) * | 1994-03-14 | 1996-04-16 | Corning Incorporated | Flat panel display |
US5489558A (en) * | 1994-03-14 | 1996-02-06 | Corning Incorporated | Glasses for flat panel display |
DE4428839C2 (de) * | 1994-08-01 | 1997-01-23 | Ivoclar Ag | Alkali-Zink-Silicat-Glaskeramiken und -Gläser und Verfahren zur Herstellung der Glaskeramiken |
FR2727399B1 (fr) * | 1994-10-13 | 1997-01-31 | Saint Gobain Vitrage | Compositions de verre silico-sodo-calciques et leurs applications |
HUP9602086A2 (hu) * | 1996-07-30 | 1999-06-28 | General Electric Company | Üvegkompozíció |
US5843855A (en) * | 1997-01-15 | 1998-12-01 | General Electric Company | Glass |
US6118216A (en) * | 1997-06-02 | 2000-09-12 | Osram Sylvania Inc. | Lead and arsenic free borosilicate glass and lamp containing same |
-
1997
- 1997-10-27 DE DE19747354A patent/DE19747354C1/de not_active Expired - Fee Related
-
1998
- 1998-10-05 DE DE59806857T patent/DE59806857D1/de not_active Expired - Lifetime
- 1998-10-05 ES ES98118761T patent/ES2190028T3/es not_active Expired - Lifetime
- 1998-10-05 EP EP98118761A patent/EP0913366B1/de not_active Expired - Lifetime
- 1998-10-23 BR BR9804064-2A patent/BR9804064A/pt not_active Application Discontinuation
- 1998-10-26 US US09/178,670 patent/US6074969A/en not_active Expired - Lifetime
- 1998-10-26 AR ARP980105343A patent/AR017521A1/es unknown
- 1998-10-26 HU HU9802469A patent/HUP9802469A3/hu unknown
- 1998-10-26 JP JP10304497A patent/JPH11217236A/ja active Pending
- 1998-10-27 CN CN98124554A patent/CN1102915C/zh not_active Expired - Fee Related
- 1998-10-27 KR KR10-1998-0044980A patent/KR100518357B1/ko not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101279815B (zh) * | 2002-02-01 | 2011-05-11 | 肖特股份有限公司 | 碱土铝硅酸盐玻璃及其应用 |
CN101585659B (zh) * | 2003-08-08 | 2011-10-19 | 日本电气硝子株式会社 | 外套容器用玻璃 |
Also Published As
Publication number | Publication date |
---|---|
EP0913366A1 (de) | 1999-05-06 |
HUP9802469A2 (hu) | 1999-07-28 |
US6074969A (en) | 2000-06-13 |
JPH11217236A (ja) | 1999-08-10 |
AR017521A1 (es) | 2001-09-12 |
KR19990037407A (ko) | 1999-05-25 |
HU9802469D0 (en) | 1999-01-28 |
DE19747354C1 (de) | 1998-12-24 |
KR100518357B1 (ko) | 2005-12-09 |
DE59806857D1 (de) | 2003-02-13 |
ES2190028T3 (es) | 2003-07-16 |
BR9804064A (pt) | 1999-11-09 |
HUP9802469A3 (en) | 2000-04-28 |
EP0913366B1 (de) | 2003-01-08 |
CN1102915C (zh) | 2003-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1102915C (zh) | 用于灯泡的含碱土金属的硼铝硅酸盐玻璃及其应用 | |
CN1101347C (zh) | 耐高温灯泡玻璃及其应用 | |
TW527330B (en) | Process for producing aluminosilicate glasses | |
CN1113824C (zh) | 钠钙硅玻璃组合物及其用途 | |
US6069100A (en) | Glass for lamb bulbs capable of withstanding high temperatures | |
CA2239342C (en) | Lead and arsenic free borosilicate glass and lamp containing same | |
CA2023115C (en) | Flat glass composition with improved melting and tempering properties | |
CN1186280C (zh) | 荧光灯用钨密封玻璃 | |
CN1213957C (zh) | Li2O-Al2O3-SiO2结晶玻璃及其可结晶玻璃 | |
JPH07187707A (ja) | 紫外域での高透過率、低熱膨張及び高い化学的安定性を有するホウケイ酸ガラス、その製造方法及びその用途 | |
JP2011093792A (ja) | ホウ素フリーガラス | |
US7553786B2 (en) | Glass that withstands high-temperatures for lamp bulbs, and its use | |
JPH0867529A (ja) | ホウ酸低含有ホウケイ酸ガラス及びその応用 | |
JP2004026632A (ja) | 無アルカリアルミノ珪酸塩ガラスを製造するための方法 | |
CN1243682C (zh) | 防晒硼硅酸盐玻璃及其应用 | |
JP2002137935A (ja) | 蛍光ランプ用ガラス、蛍光ランプ用ガラス管及び蛍光ランプ | |
JPWO2010050591A1 (ja) | 太陽電池 | |
US4394453A (en) | Envelopes for tungsten-halogen lamps | |
JPWO2007086441A1 (ja) | ランプ用ガラス組成物の製造方法、ランプ用ガラス組成物およびランプ | |
CN1241855C (zh) | 一种与金属或合金封接用玻璃 | |
JP2000290038A (ja) | 蛍光ランプ用ガラス、蛍光ランプ用ガラス管、及び蛍光ランプ | |
JP2002187734A (ja) | 蛍光ランプ用コバールシールガラス | |
US7211957B2 (en) | Alumino earth-alkali silicate glasses with high thermal capacity for light bulbs and use thereof | |
KR100729419B1 (ko) | 전구용으로 사용되는 고열용량 알루미노 알칼리토실리케이트 유리 및 그 용도 | |
CN102515518A (zh) | 一种低钠无铅高透过率节能灯管玻璃及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
ASS | Succession or assignment of patent right |
Owner name: SCHOTT GLAS Free format text: FORMER OWNER: SCHOTT GLASS MFG. PLANT Effective date: 20050930 |
|
C41 | Transfer of patent application or patent right or utility model | ||
TR01 | Transfer of patent right |
Effective date of registration: 20050930 Address after: Germany Mainz Patentee after: Schott AG Address before: Germany Mainz Patentee before: Schott Glasswork |
|
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20030312 Termination date: 20171027 |
|
CF01 | Termination of patent right due to non-payment of annual fee |