CN1241855C - Glass for sealing with metal or alloy - Google Patents

Glass for sealing with metal or alloy Download PDF

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Publication number
CN1241855C
CN1241855C CN 03156720 CN03156720A CN1241855C CN 1241855 C CN1241855 C CN 1241855C CN 03156720 CN03156720 CN 03156720 CN 03156720 A CN03156720 A CN 03156720A CN 1241855 C CN1241855 C CN 1241855C
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oxide
glass
sealing
alloy
metal
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CN1594166A (en
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郭柏驿
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Platinum Beijing Au Optronics Co
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郭柏驿
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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
    • 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
    • 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
    • C03C3/089—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
    • 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
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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

Abstract

The present invention relates to glass for sealing metal or alloy. The glass is composed of compositions by molar ratio: 70.0% to 80.0% of silicon oxide, 0.0% to 4.0% of alumina, 12.0% to 19.0% of boron oxide, 0.0% to 4.0% of lithium oxide, 0.0% to 6.0% of sodium oxide, 0.0% to 8.0% of potassium oxide, 0.0% to 2.0% of magnesium oxide, 0.0% to 2.0% of calcium oxide, 0.0% to 2.0% of strontium oxide, 0.0% to 2.0% of barium oxide, 0.0% to 2.0% of zinc oxide, 0.0% to 1.0% of arsenic oxide and 0.0% to 1.0% of cerium dioxide, wherein the total sum of the lithium oxide, the sodium oxide and the potassium oxide is between 3.0% and 11.0%; the total sum of the magnesium oxide, the calcium oxide, the strontium oxide and the barium oxide is between 0.0% and 4.0%; the total sum of the arsenic oxide and the cerium dioxide is between 0.05% and 1.0%. The glass has the characteristics of similar expansion coefficients of sealing metal, low air bubble generation quantity, low glass liquid phase temperature, etc.

Description

A kind of and metal or alloy glass for sealing
Technical field
The invention relates to a kind of and the metal or alloy glass for sealing, be meant especially and tungsten (W), molybdenum metal and the close alloy sealing glass of character thereof such as (Mo), and can be applicable to fluorescent tube.
Background technology
Generally speaking, utilize glass-sealed material a lot, include various metals, alloy, pottery and sintered glass ceramics, wherein using maximum is the sealing-in of glass and metal.The history of glass-to-metal seal is of long duration, and as far back as 1820s, just the someone carries out the sealing-in experiment of platinum and soft glass.Even to this day, the sealing-in of glass has become various high-quality electric light sources such as luminescent lamp, electron tube and the requisite technology of other electron tube made, particularly as the fluorescent tube bulb of liquid-crystal display (LCD) back light.In addition, along with the trend of compactization of electronic product, the resistance to air loss of fluorescent tube bulb and the requirement of reliability are improved constantly.Glass-to-metal seal is defined as: heating glass makes itself and preoxidized metal or alloy surface reach good infiltration and closely combines, subsequently with glass and metal cools to room temperature, glass and metal still can be sealed securely, become as a whole.Glass and metallic substance have very many kinds, if they closely will be combined, must consider its fundamental characteristics earlier.Basically, both coefficients of expansion (Coefficient of thermal expansion, CTE) very approaching, if both rate of expansion are different with contraction rate, when temperature variation, glass and metal all can produce stress, when in case stress value surpasses the ultimate strength of glass, sealing-in place promptly can be split, and causes assembly gas leakage, causes briliancy (Luminance) reduction of luminescent lamp even not light a lamp.
The coefficient of expansion according to different metal changes, and corresponding glass for sealing is formed also different.Roughly can be divided into two classes: during the high soft glass sealing-in of () and the coefficient of expansion, can use platinum (Pt), iron-nickel (Fe-Ni) alloy or contain chromium (Cr) alloy.Platinum and iron nickel alloy have that Qu Fudian (Yield point) is low, the high characteristic of electroconductibility (Conductivity), but because the cost height of platinum, generally are rich in the iron nickel wire of copper with use, and promptly Dumet wire replaces; During (two) with the low hard glass sealing-in of the coefficient of expansion, can use tungsten, molybdenum and alloy thereof or iron-cobalt-nickel (Fe-Co-Ni) alloy.Tungsten and molybdenum are a kind of hard, crisp and metallic substance that purity is high, also be unique energy directly and the hard glass metal that carries out sealing-in.Therefore the ductility of molybdenum is better than tungsten, but all oxidations at low temperatures easily of tungsten and molybdenum the iron-cobalt-nickel alloy of molybdenum occurred replacing, as Femico alloy or Kovar alloy.The expansion curve of this class alloy is bent upwards in 400-450 ℃ of scope gradually, and is quite approaching with the expansion curve of hard glass, and sealing-in therefore can match each other.
On the other hand, if in the sealing-in process, sealing-in place has the generation of a large amount of bubbles can reduce physical strength and causes chronic leakage, also can cause the briliancy of luminescent lamp to reduce even the generation of lamplerss situation.In addition, the Glass tubing that the is used in luminescent lamp consideration transparence of still needing, the too many or too high devitrification that causes of liquidus temperature as the bubble of glass itself, promptly crystallization increases, and all can influence the transparence of glass.In addition, in the characteristic of selecting not only will to consider on the seal, sealing materials metal and seal glass, the composition that also must consider Glass tubing why.If contain plumbous oxide (PbO) in the composition of Glass tubing,, the Lead contamination of unsettled phenomenon and environment in the production process will be caused because plumbous oxide volatilizees easily.And if for example Glass tubing contains weisspiessglanz (Sb in forming 2O 3), will cause glass blackout in the sealing-in process, influence the transparence of fluorescent tube.
In recent years, because the increase of LCD application is also studied widely as the fluorescent tube bulb of its backlight assembly light source.Although have many documents to inquire into the research glass for sealing, wherein still have many problems to overcome.The Japanese Patent spy opens the disclosed packaged glass of 2002-187734, and it has the too much puzzlement of bubble when sealing-in, can influence the resistance to air loss of sealing-in.The Japanese Patent spy opens 2001-220175 and Chinese patent bulletin CN1339016A, when carrying out sealing-in according to the disclosed glass composition of this patent, then because of containing plumbous oxide and weisspiessglanz, can cause the Lead contamination of unsettled phenomenon and environment in the production process, cause the situation of glass blackout in the sealing-in process.United States Patent (USP) 5,747,399 disclosed glass are formed, and its liquidus temperature is too high, and crystallization increases, and causes devitrification, and because of containing plumbous oxide, causes the Lead contamination of unsettled phenomenon and environment in the production process.The disclosed glass of Chinese patent bulletin CN1350989A is formed when being used for sealing-in, and then too high because of its coefficient of expansion, and the inapplicable alloy close with tungsten, molybdenum and character thereof done sealing-in.
Summary of the invention
The invention provides a kind of glass for sealing that is applicable to metal and the close alloy of character thereof, it consists of molar percentage and is respectively: 70.0% to 80.0% silicon oxide sio 2, 0.0% to 4.0% aluminium oxide Al 2O 3, 12.0% to 19.0% boron oxide B 2O 3, 0.0% to 4.0% Lithium Oxide 98min Li 2O, 0.0% to 6.0% sodium oxide Na 2O, 0.0% to 8.0% potassium oxide K 2O, wherein Lithium Oxide 98min Li 2O, sodium oxide Na 2O and potassium oxide K 2The summation of O between 3.0% to 11.0%, 0.0% to 2.0% magnesium oxide MgO, 0.0% to 2.0% calcium oxide CaO, 0.0% to 2.0% strontium oxide SrO, 0.0% to 2.0% barium oxide BaO, wherein the summation of magnesium oxide MgO, calcium oxide CaO, strontium oxide SrO and barium oxide BaO between 0.0% to 4.0%, 0.0% to 2.0% zinc oxide ZnO, 0.0% to 1.0% arsenic oxide arsenoxide As 2O 3, 0.0% to 1.0% cerium oxide CeO 2, arsenic oxide arsenoxide As wherein 2O 3With cerium oxide CeO 2Summation between 0.05% to 1.0%.
The composition of preferred embodiment of the present invention is that close with tungsten, molybdenum and character thereof respectively alloy is done sealing-in.Glass among the embodiment is formed part and is had the coefficient of expansion close with tungsten, molybdenum and alloy thereof respectively, low bubble produces property and lower liquidus temperature, and characteristics such as oxious component such as oxygen-free lead, weisspiessglanz.
Embodiment
The present invention is described in detail now to cooperate the following example.
Each composition of the molar percentage of glass for sealing is according to the present invention:
(1) 70.0%-80.0% silicon oxide sio 2
(2) 0.0%-4.0% aluminium oxide Al 2O 3
(3) 12.0%-19.0% boron oxide B 2O 3
(4) 0.0%-4.0% Lithium Oxide 98min Li 2O;
(5) 0.0%-6.0% sodium oxide Na 2O;
(6) 0.0%-8.0% potassium oxide K 2O;
Lithium Oxide 98min Li wherein 2O, sodium oxide Na 2O and potassium oxide K 2The summation of O is between 3.0%-11.0%;
(7) 0.0%-2.0% magnesium oxide MgO;
(8) 0.0%-2.0% calcium oxide CaO;
(9) 0.0%-2.0% strontium oxide SrO;
(10) 0.0%-2.0% barium oxide BaO;
Wherein the summation of magnesium oxide MgO, calcium oxide CaO, strontium oxide SrO and barium oxide BaO is between 0.0%-4.0%;
(11) 0.0%-2.0% zinc oxide ZnO;
(12) 0.0%-1.0% arsenic oxide arsenoxide As 2O 3
(13) 0.0%-1.0% cerium oxide CeO 2
Arsenic oxide arsenoxide As wherein 2O 3With cerium oxide CeO 2Summation between 0.05%-1.0%.
Its preferable proportion of composing and function when below each composition material of this glass for sealing of explanation is used for tungsten group metal or alloy.
Silicon oxide sio 2Be the main body that glass is formed, preferable content is 72.0% to 80.0%.If silica content is less than 72.0%, produced glass swelling coefficient is too high, is not suitable for and the sealing-in of tungsten group metal or alloy.If silica content more than 80.0%, will cause the too high processing difficulties of melting temperature (Tm) of glass, and the easy devitrification of made glass.
Aluminium oxide Al 2O 3For being used for improving the intensity of glass structure, preferable content is between 0.0% to 4.0%.If alumina content is more than 4.0%, viscosity is too high in the time of will causing glass sealing, and operational difficulty can't fully soak into the metallic surface to form tight sealing-in.
Boron oxide B 2O 3Act as fusing assistant, the main viscosity of glass cream when reducing fusion cast glass, its preferable content is 12.0% to 19.0%.If boron oxide content is less than 12.0%, its effect of fluxing promptly can't be given full play to.If boron oxide content more than 19.0%, owing to the volatilization of boron oxide, is difficult for making the glass of homogeneous.
Lithium Oxide 98min Li 2O, sodium oxide Na 2O and potassium oxide K 2O act as fusing assistant, the main viscosity of glass cream when reducing fusion cast glass, and adjust the coefficient of expansion of glass.Preferable content is respectively Lithium Oxide 98min Li 2O 0.0% to 3.0%, sodium oxide Na 2O 0.0% to 6.0% and potassium oxide K 2O0.0% to 4.0%, and total content is between 3.0% to 8.0%.If total content is less than 3.0%, will cause the glass swelling coefficient too low.If total content more than 8.0%, will cause the glass swelling coefficient too high.
In addition, if Lithium Oxide 98min Li 2The content of O will cause glass swelling coefficient and liquidus temperature too high more than 3.0%.If sodium oxide Na 2The content of O will cause the glass swelling coefficient too high more than 6.0%, and in addition, the free sodium ion will pollute electronic package, make its electrical deterioration.If potassium oxide K 2O content also will cause the glass swelling coefficient too high more than 4.0%.
Magnesium oxide MgO, calcium oxide CaO, strontium oxide SrO and barium oxide BaO act as fusing assistant and reinforcing glass plasticity.Preferable content is respectively magnesium oxide MgO 0.0% to 2.0%, calcium oxide CaO 0.0% to 2.0%, strontium oxide SrO 0.0% to 2.0% and barium oxide BaO 0.0% to 2.0%, and its total content is between 0.0% to 4.0%.If total content more than 4.0%, will cause glass devitrification and plasticity bad.
In addition, if the content of magnesium oxide MgO more than 2.0%, will cause the glass chemical resistant properties to worsen.If calcium oxide CaO content more than 2.0%, will cause glass devitrification and plasticity bad.If strontium oxide SrO content more than 2.0%, will cause forming of glass bad.If barium oxide BaO content more than 2.0%, will cause forming of glass bad.
Zinc oxide ZnO is intensity and the chemical resistant properties that is used for improving glass structure, and preferable content is at 0.0% to 1.0%.If the zinc oxide ZnO content more than 1.0%, will cause the glass devitrification.
Arsenic oxide arsenoxide As 2O 3With cerium oxide CeO 2Effect be the glass finings and the defrother in when fusion.Preferable content is respectively arsenic oxide arsenoxide As 2O 30.0% to 1.0% with cerium oxide CeO 20.0% to 1.0%, its total content is 0.05% to 1.0%.If total content is less than 0.05%, its clarification and de-bubble effect promptly can't be given full play to.If total content, will cause glass blackout in the sealing-in process more than 1.0%, influence transparence.
In addition, if arsenic oxide arsenoxide As 2O 3Content will cause glass blackout in the sealing-in process more than 1.0%.If cerium oxide CeO 2Content will make the glass flavescence more than 1.0%, influence transparence.
Proportion of composing and characteristic when table one (example 1 is to example 5) is applied to tungsten group Metal and Alloy for the present invention.
The proportion of composing of table one glass for sealing and characteristic (when being applied to tungsten group Metal and Alloy).
Below consist of molar percentage (mol%) Embodiment
Example 1 Example 2 Example 3 Example 4 Example 5
Silicon oxide (SiO 2) 76.4 75.8 76.9 73.9 78.4
Aluminum oxide (Al 2O 3) 0.7 1.1 2.8 1.1 2.6
Boron oxide (B 2O 3) 16.3 15.9 13.4 14.5 13.6
Lithium Oxide 98min (Li 2O) 0.1 0 0.2 0.3 0.6
Sodium oxide (Na 2O) 4.2 3.8 2.2 5.1 2.4
Potassium oxide (K 2O) 0.6 2.1 1.4 1.9 0.7
Lithium Oxide 98min+sodium oxide+potassium oxide (Li 2O+Na 2O+K 2O) 4.9 5.9 3.8 7.3 3.7
Magnesium oxide (MgO) 0.6 0.1 0.9 1.1 0.3
Calcium oxide (CaO) 0.8 0.6 1.2 1.3 0.6
Strontium oxide (SrO) 0 0.1 0 0.1 0
Barium oxide (BaO) 0 0.1 0.4 0.2 0.3
Magnesium oxide+calcium oxide+strontium oxide+barium oxide (MgO+CaO+SrO+ BaO) 1.4 0.9 2.5 2.7 1.2
Zinc oxide (ZnO) 0 0 0.2 0.1 0.2
Arsenic oxide arsenoxide (As 2O 3) 0.1 0.1 0.2 0.3 0.2
Cerium oxide (CeO 2) 0.2 0.3 0.2 0.1 0.1
Arsenic oxide arsenoxide+cerium oxide (As 2O 3+CeO 2) 0.3 0.4 0.4 0.4 0.3
The coefficient of expansion (* 10 -7/℃) (30～400℃) 38.2 39.1 37.4 40.3 36.8
Bubble generation number (individual/kg) ＜10 ＜10 ＜10 ＜10 ＜10
The glass liquidus temperature (℃) 990 1000 990 1000 990
Learn that from table one be made up of example 1 to 5 disclosed glass for sealing, its coefficient of expansion is 36-41 * 10 -7/ ℃ (30-400 ℃), close with tungsten group Metal and Alloy, so be suitable for and the sealing-in of tungsten group Metal and Alloy.Because its coefficient of expansion is close, do not make component failures so can not produce crack or gas leakage after the sealing-in.In addition, liquidus temperature all is lower than 1010 ℃, can not produce crystallization and transparence is reduced.It is few that bubble produces number, can not cause physical strength to reduce and gas leakage, and objectionable impuritiess such as not leaded and antimony.
Its preferable proportion of composing when below each composition material of this glass for sealing of explanation is used for molybdenum group metal or alloy.
Silicon oxide sio 2Be the main body that glass is formed, preferable content is 70.0% to 76.0%.If silica content is less than 70.0%, produced glass swelling coefficient is too high, is not suitable for and the sealing-in of tungsten group metal or alloy.If silica content more than 76.0%, will cause the too high processing difficulties of melting temperature (Tm) of glass, and the easy devitrification of made glass.
Aluminium oxide Al 2O 3For being used for improving the intensity of glass structure, preferable content is between 0.0% to 4.0%.If alumina content is more than 4.0%, viscosity is too high in the time of will causing glass sealing, and operational difficulty can't fully soak into the metallic surface to form tight sealing-in.
Boron oxide B 2O 3Act as fusing assistant, the viscosity of main system glass cream when reducing fusion cast glass, its preferable content is 13.0% to 19.0%.If boron oxide content is less than 13.0%, its effect of fluxing promptly can't be given full play to.If boron oxide content more than 19.0%, owing to the volatilization of boron oxide, is difficult for making the glass of homogeneous.
Lithium Oxide 98min Li 2O, sodium oxide Na 2O and potassium oxide K 2O act as fusing assistant, the main viscosity of glass cream when reducing fusion cast glass, and adjust the coefficient of expansion of glass.Preferable content is respectively Lithium Oxide 98min Li 2O 0.0% to 4.0%, sodium oxide Na 2O 0.0% to 4.0% and potassium oxide K 2O0.0% to 8.0%, and total content is between 5.0% to 11.0%.If total content is less than 5.0%, will cause the glass swelling coefficient too low.If total content more than 11.0%, will cause the glass swelling coefficient too high.
In addition, if Lithium Oxide 98min Li 2The content of O will cause glass swelling coefficient and liquidus temperature too high more than 4.0%.If sodium oxide Na 2The content of O will cause the glass swelling coefficient too high more than 4.0%, and in addition, the free sodium ion will pollute electronic package, make its electrical deterioration.If potassium oxide K 2O content also will cause the glass swelling coefficient too high more than 8.0%.
Magnesium oxide MgO, calcium oxide CaO, strontium oxide SrO and barium oxide BaO act as fusing assistant and reinforcing glass plasticity.Preferable content is respectively magnesium oxide MgO 0.0% to 1.0%, calcium oxide CaO 0.0% to 1.0%, strontium oxide SrO 0.0% to 1.0% and barium oxide BaO 0.0% to 1.0%, and its total content is between 0.0% to 2.0%.If total content more than 2.0%, will cause glass devitrification and plasticity bad.
In addition, if the content of magnesium oxide MgO more than 1.0%, will cause the glass chemical resistant properties to worsen.If calcium oxide CaO content more than 1.0%, will cause glass devitrification and plasticity bad.If strontium oxide SrO content more than 1.0%, will cause forming of glass bad.If barium oxide BaO content more than 1.0%, will cause forming of glass bad.
Zinc oxide ZnO is intensity and the chemical resistant properties that is used for improving glass structure, and preferable content is at 0.0% to 2.0%.If the zinc oxide ZnO content more than 2.0%, will cause the glass devitrification.
Arsenic oxide arsenoxide As 2O 3With cerium oxide CeO 2Effect be the glass finings and the defrother in when fusion.Preferable content is respectively arsenic oxide arsenoxide As 2O 30.0% to 1.0% with cerium oxide CeO 20.0% to 1.0%, its total content is 0.05% to 1.0%.If total content is less than 0.05%, its clarification and de-bubble effect promptly can't be given full play to.If total content, will cause glass blackout in the sealing-in process more than 1.0%, influence transparence.
In addition, if arsenic oxide arsenoxide As 2O 3Content will cause glass blackout in the sealing-in process more than 1.0%.If cerium oxide CeO 2Content will make the glass flavescence more than 1.0%, influence transparence.
Proportion of composing and characteristic when table two (example 6 is to example 10) is applied to molybdenum group Metal and Alloy for the present invention.
The proportion of composing of table two glass for sealing and characteristic (when being applied to molybdenum group Metal and Alloy).
Below consist of molar percentage (mol%) Embodiment
Example 6 Example 7 Example 8 Example 9 Example 10
Silicon oxide (SiO 2) 72.9 74.3 71.8 74.9 73.6
Aluminum oxide (Al 2O 3) 1.6 1.8 2.6 0.9 2.2
Boron oxide (B 2O 3) 16.2 15.7 17.1 14.6 17.8
Lithium Oxide 98min (Li 2O) 0.5 0.3 0.1 1.2 1.6
Sodium oxide (Na 2O) 1.4 0.7 2.6 2.8 3.1
Potassium oxide (K 2O) 5.8 6.2 5.4 3.6 1.1
Lithium Oxide 98min+sodium oxide+potassium oxide (Li 2O+Na 2O+K 2O) 7.7 7.2 8.1 7.6 5.8
Magnesium oxide (MgO) 0.2 0.4 0 0.1 0
Calcium oxide (CaO) 0.4 0.1 0 0.1 0
Strontium oxide (SrO) 0 0 0 0.3 0
Barium oxide (BaO) 0 0 0.1 0.3 0.2
Magnesium oxide+calcium oxide+strontium oxide+barium oxide (MgO+CaO+SrO+ BaO) 0.6 0.5 0.1 0.8 0.2
Zinc oxide (ZnO) 0.6 0.2 0 0.8 0
Arsenic oxide arsenoxide (As 2O 3) 0.1 0.1 0.2 0.3 0.2
Cerium oxide (CeO 2) 0.3 0.2 0.1 0.1 0.2
Arsenic oxide arsenoxide+cerium oxide (As 2O 3+CeO 2) 0.4 0.3 0.3 0.4 0.4
The coefficient of expansion (* 10 -7/℃) (30～400℃) 50.1 48.6 51.2 49.1 47.4
Bubble generation number (individual/kg) ＜10 ＜10 ＜10 ＜10 ＜10
The glass liquidus temperature (℃) 910 900 910 890 900
Learn by example 6 to 10 disclosed seal glasses from table two and to form that its coefficient of expansion is 46-52 * 10 -7/ ℃ (30～400 ℃), close with molybdenum group Metal and Alloy, so be suitable for and the sealing-in of molybdenum group Metal and Alloy.Because its coefficient of expansion is close, do not make component failures so can not produce crack or gas leakage after the sealing-in.In addition, liquidus temperature all is lower than 920 ℃, can not produce crystallization and transparence is reduced.It is few that bubble produces number, can not cause physical strength to reduce and gas leakage.And objectionable impuritiess such as not leaded and antimony.
Table three is the control group of table one, and example 11 to 13 is formed for being different from glass of the present invention.
The proportion of composing of table three glass for sealing and characteristic (when being applied to tungsten group Metal and Alloy).
Below consist of molar percentage (mol%) Comparative example
Example 11 Example 12 Example 13
Silicon oxide (SiO 2) 74.9 73.4 76.3
Aluminum oxide (Al 2O 3) 1.1 0.9 2.1
Boron oxide (B 2O 3) 13.2 15.1 14.1
Lithium Oxide 98min (Li 2O) 1.2 0 0.2
Sodium oxide (Na 2O) 4.6 2.9 1
Potassium oxide (K 2O) 3.3 1.1 1.5
Lithium Oxide 98min+sodium oxide+potassium oxide (Li 2O+Na 2O+K 2O) 9.1 4 2.7
Magnesium oxide (MgO) 0.6 3.5 0.4
Calcium oxide (CaO) 0.2 3.1 0.8
Strontium oxide (SrO) 0.3 0 1.1
Barium oxide (BaO) 0.3 0 0.9
Magnesium oxide+calcium oxide+strontium oxide+barium oxide (MgO+CaO+SrO+ BaO) 1.4 6.6 3.2
Zinc oxide (ZnO) 0.2 0 1.2
Arsenic oxide arsenoxide (As 2O 3) 0.1 0 0.2
Cerium oxide (CeO 2) 0 0 0.2
Arsenic oxide arsenoxide+cerium oxide (As 2O 3+CeO 2) 0.1 0 0
The coefficient of expansion (* 10 -7/℃) (30～400℃) 42.1 37.2 35.1
Bubble generation number (individual/kg) 10～50 ＞50 ＜10
The glass liquidus temperature (℃) 1020 1040 1030
Table three points out to be different from the characteristic that disclosed glass during with tungsten group metal and alloy sealing is formed.In example 11, its coefficient of expansion is higher than tungsten group Metal and Alloy and glass liquidus temperature height, can cause crack or gas leakage and devitrification.In example 12, its bubble produces the too much and glass liquidus temperature height of number, can cause physical strength reduction, gas leakage and light transmission poor.In example 13, its coefficient of expansion is lower than tungsten group Metal and Alloy and glass liquidus temperature height, can cause crack or gas leakage and devitrification.
Table four is the control group of table two, and example 14 to 16 is formed for being different from glass of the present invention.
The proportion of composing of table four glass for sealing and characteristic (when being applied to molybdenum group Metal and Alloy).
Below consist of molar percentage (mol%) Comparative example
Example 14 Example 15 Example 16
Silicon oxide (SiO 2) 72.2 74.8 75.4
Aluminum oxide (Al 2O 3) 1.4 1.7 2.3
Boron oxide (B 2O 3) 14.1 16.2 16.4
Lithium Oxide 98min (Li 2O) 3.2 0.3 0.4
Sodium oxide (Na 2O) 2.4 0.8 1.7
Potassium oxide (K 2O) 6 5.5 2.4
Lithium Oxide 98min+sodium oxide+potassium oxide (Li 2O+Na 2O+K 2O) 11.6 6.6 4.5
Magnesium oxide (MgO) 0.1 0.2 0.6
Calcium oxide (CaO) 0.1 0.3 0.3
Strontium oxide (SrO) 0 0 0.1
Barium oxide (BaO) 0 0 0.1
Magnesium oxide+calcium oxide+strontium oxide+barium oxide (MgO+CaO+SrO+ BaO) 0.2 0.5 1.1
Zinc oxide (ZnO) 0.1 0.2 0.1
Arsenic oxide arsenoxide (As 2O 3) 0.2 0 0.1
Cerium oxide (CeO 2) 0.2 0 0.1
Arsenic oxide arsenoxide+cerium oxide (As 2O 3+CeO 2) 0.4 0 0.2
The coefficient of expansion (* 10 -7/℃) (30～400℃) 56.3 48.6 45.3
Bubble generation number (individual/kg) ＜10 ＞50 10～50
The glass liquidus temperature (℃) 940 910 920
Table four points out to be different from the characteristic that disclosed glass during with molybdenum group metal and alloy sealing is formed.In example 14, its coefficient of expansion is higher than molybdenum group Metal and Alloy and glass liquidus temperature height, can cause crack or gas leakage and devitrification.In example 15, it is too much that its bubble produces number, can cause physical strength reduction, gas leakage and light transmission poor.In example 16, its coefficient of expansion is lower than molybdenum group Metal and Alloy, can cause crack or gas leakage.
The present invention is when implementing, be with the pairing raw material of aforementioned component, behind the uniform mixing, import glass fusion groove, and under 1500-1600 ℃, fuse into glass cream, with known trombone slide method (such as Danner method, Vello method, glass tube down-drawing and similar method), glass cream is drawn into tubulose, strip or bar-shaped, be cut into required length then.
At the glass sample of table one, table two, table three and table four, all be with following method manufacturing; Each composition is got raw material commonly used, according to corresponding molar percentage uniform mixing in addition, again with 1500-1600 ℃ temperature, fusion is 6 to 8 hours in platinum crucible, in the fusion processes, and stirred 2 hours with the platinum stirring rod, to promote the homogeneity of each composition in the glass, then glass cream is poured into cooling forming is tabular in the metal form.At this moment, detect, can obtain characteristic values such as the coefficient of expansion, bubble generation number and glass liquidus temperature respectively, and the difference tabular is on the corresponding column of table one, table two, table three and table four at each glass sample.
The present invention mainly detects according to following method when detecting the characteristic value of glass sample:
(1) coefficient of expansion (unit: 10 -7/ ℃) detect: with reference to (the American Society for Testing and Materials of American Society for testing and materials, hereinafter to be referred as ASTM) ordered numbering E228-95 examination criteria, with mechanical push rods formula thermal dilatometer and aluminum oxide is reference standard, the elongation of heating and measurement glass sample, temperature range is no longer extended to glass from the room temperature amount, even because of the temperature till softening the contraction, temperature rise rate is 3 ℃ of per minutes.The coefficient of expansion is calculated by 30 to 400 ℃ glass elongation.
(2) bubble produces number (unit: individual/kg): the plate glass sample through grinding, after the polishing, examining under a microscope its air entrapment number, is calculated the total number of bubbles that surpasses 20 μ m diameters, be scaled the number of bubbles of per kilogram glass again with glass sample weight.
(3) glass liquidus temperature (unit: ℃) detects: be according to ASTM C829-81, will put into platinum dish less than the cullet of 850 μ m, place gradient furnace after 24 hours, measure the crystallization situation of glass with microscope, judge its liquidus temperature and get.
The above is preferred embodiment of the present invention only, is not in order to the present invention being done any pro forma restriction, and all relevant impartial modifications of doing according to claim of the present invention or change are all claim of the present invention and contain.

Claims (6)

  1. One kind with the metal or alloy glass for sealing, the molar ratio that it is characterized in that composition is: 70.0% to 80.0% silicon oxide, 0.0% to 4.0% aluminum oxide, 12.0% to 19.0% boron oxide, 0.0% to 4.0% Lithium Oxide 98min, 0.0% to 6.0% sodium oxide, 0.0% to 8.0% potassium oxide, Lithium Oxide 98min wherein, the summation of sodium oxide and potassium oxide is between 3.0% to 11.0%, 0.0% to 2.0% magnesium oxide, 0.0% to 2.0% calcium oxide, 0.0% to 2.0% strontium oxide, 0.0% to 2.0% barium oxide, magnesium oxide wherein, calcium oxide, strontium oxide and barytic summation are between 0.0% to 4.0%, 0.0% to 2.0% zinc oxide, 0.0% to 1.0% arsenic oxide arsenoxide, 0.0% to 1.0% cerium oxide, wherein the summation of arsenic oxide arsenoxide and cerium oxide is between 0.05% to 1.0%.
  2. 2. as claimed in claim 1 and metal or alloy glass for sealing, when it is characterized in that this metal or alloy is tungsten group metal or alloy, the molar ratio of glass for sealing composition is: 72.0% to 80.0% silicon oxide, 0.0% to 4.0% aluminum oxide, 12.0% to 19.0% boron oxide, 0.0% to 3.0% Lithium Oxide 98min, 0.0% to 6.0% sodium oxide, 0.0% to 4.0% potassium oxide, Lithium Oxide 98min wherein, the summation of sodium oxide and potassium oxide is between 3.0% to 8.0%, 0.0% to 2.0% magnesium oxide, 0.0% to 2.0% calcium oxide, 0.0% to 2.0% strontium oxide, 0.0% to 2.0% barium oxide, magnesium oxide wherein, calcium oxide, strontium oxide and barytic summation are between 0.0% to 4.0%, 0.0% to 1.0% zinc oxide, 0.0% to 1.0% arsenic oxide arsenoxide, 0.0% to 1.0% cerium oxide, wherein the summation of arsenic oxide arsenoxide and cerium oxide is between 0.05% to 1.0%.
  3. 3. as claimed in claim 1 and metal or alloy glass for sealing, when it is characterized in that this metal or alloy is molybdenum group metal or alloy, the molar ratio of glass for sealing composition is: 70.0% to 76.0% silicon oxide, 0.0% to 4.0% aluminum oxide, 13.0% to 19.0% boron oxide, 0.0% to 4.0% Lithium Oxide 98min, 0.0% to 4.0% sodium oxide, 0.0% to 8.0% potassium oxide, Lithium Oxide 98min wherein, the summation of sodium oxide and potassium oxide is between 5.0% to 11.0%, 0.0% to 1.0% magnesium oxide, 0.0% to 1.0% calcium oxide, 0.0% to 1.0% strontium oxide, 0.0% to 1.0% barium oxide, magnesium oxide wherein, calcium oxide, strontium oxide and barytic summation are between 0.0% to 2.0%, 0.0% to 2.0% zinc oxide, 0.0% to 1.0% arsenic oxide arsenoxide, 0.0% to 1.0% cerium oxide, wherein the summation of arsenic oxide arsenoxide and cerium oxide is between 0.05% to 1.0%.
  4. 4. the application in making fluorescent tube of as claimed in claim 1 and metal or alloy glass for sealing.
  5. 5. the application in making fluorescent tube of as claimed in claim 2 and tungsten group metal or alloy glass for sealing.
  6. 6. the application in making fluorescent tube of as claimed in claim 3 and molybdenum group metal or alloy glass for sealing.
CN 03156720 2003-09-08 2003-09-08 Glass for sealing with metal or alloy Expired - Fee Related CN1241855C (en)

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ES2358656B1 (en) * 2009-10-28 2012-01-13 Abengoa Solar New Technologies, S.A. NEW GLASS COMPOSITIONS AND PROCEDURE TO MAKE A GLASS-METAL UNION.
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