CN103025677A - Sealing glass and sealing composite material - Google Patents

Sealing glass and sealing composite material Download PDF

Info

Publication number
CN103025677A
CN103025677A CN2011800366402A CN201180036640A CN103025677A CN 103025677 A CN103025677 A CN 103025677A CN 2011800366402 A CN2011800366402 A CN 2011800366402A CN 201180036640 A CN201180036640 A CN 201180036640A CN 103025677 A CN103025677 A CN 103025677A
Authority
CN
China
Prior art keywords
sealing
glass
metal
content
volume
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.)
Pending
Application number
CN2011800366402A
Other languages
Chinese (zh)
Inventor
菊谷武民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Electric Glass Co Ltd
Original Assignee
Nippon Electric Glass Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Publication of CN103025677A publication Critical patent/CN103025677A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders

Abstract

This sealing glass is for sealing a metal object to be sealed, characterized by comprising, by mol%, 15 to (but not including) 30% SnO, 20 to 40% P2O5, 5 (but not including 5) to 20% WO3, and 3.4 to (but not including) 30% ZnO, as a glass composition, wherein the mol ratio SnO/ZnO is 1 to 4.5.

Description

Glass for sealing and sealing matrix material
Technical field
The present invention relates to the glass for sealing for the sealed thing of sealing metal system.Need to prove that in the following description, " sealing " comprises the member concept of airtight joint " envelope " each other, in addition, " glass for sealing " comprises the concept of " sealing and using glass ".
Background technology
As shown in Figure 1, grill pans etc. have the metal-made double container 10 of heat insulation function, has following structure: under the state that outer container 1 and inner jar 2 dispose in the mode that overlaps, be sealed in the structure of the interconnecting part of the hollow bulb 4 of formation between outer container 1 and the inner jar 2 and outside atmosphere with sealing material 3.In addition, so by the hollow bulb 4 of the metal-made double container 10 of sealing material 3 sealings, be retained vacuum state (for example, with reference to patent documentation 1).
Hollow bulb 4 is retained vacuum state through operation as follows.That is, at first, as shown in Figure 2, before sealing, sealing material 3 is contained in the recess 5 that forms at metal-made double container 10.In addition, interior with sealing material 3 meltings at recess 5 after hollow bulb 4 vacuumized by the venting port 6 that arranges in the bottom of recess 5, venting port 6 is sealed.The sealing (comprising sealing of metal and metal, metal and pottery, metal and glass etc.) of so sealed thing such as metal-made double container 10 metal-mades such as grade is carried out under the nonoxidizing atmospheres such as reduced atmosphere, inert atmosphere for the oxidation that prevents metal usually.
Here, the metal material that uses in the metal-made double container, selected according to the weather resistance (thermotolerance, acid resistance) of the thermal treatment in the manufacturing process, acid treatment etc., price of steel product etc. are come.Consider these items, the metal material that has the metal-made double container does not use the SUS304 of common austenite (18%Cr8%Ni) and uses the SUS436 of ferritic series (18%Cr), the situation of SUS403.
On the other hand, about sealing material 3, except using the metallic substance such as aluminium, tin, nickel, use in addition the situation of glass.When using glass (hereinafter referred to as sealing glass) as sealing material 3, because the low temperature of seal temperature, can realize the saving of the material cost due to the minimizing of shortening, thickness of steel product of activity time, its result can make cheap for manufacturing costization of metal-made double container.
Specifically, as sealing glass, be widely used the PbO-B that contains a large amount of lead 2O 3Be glass (for example with reference to patent documentation 2～5).But, for the consideration of environment aspect etc., also propose to use Bi 2O 3-B 2O 3Be glass, SnO-P 2O 5Be that the lead-free glass such as glass are as sealing glass (for example with reference to patent documentation 6～10).
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2000-166777 communique
[patent documentation 2] TOHKEMY 2002-345655 communique
The real fair 6-16897 communique of [patent documentation 3] Japan
[patent documentation 4] Japanese kokai publication sho 62-209712 communique
[patent documentation 5] Japanese kokai publication hei 5-47322 communique
[patent documentation 6] TOHKEMY 2005-350314 communique
No. 2628007 communique of [patent documentation 7] patent
[patent documentation 8] TOHKEMY 2000-72479 communique
[patent documentation 9] TOHKEMY 2001-139344 communique
[patent documentation 10] TOHKEMY 2008-30972 communique
Summary of the invention
The problem that invention will solve
Yet, in the situation of metal-made double container, for example grill pan, for example seal 500 ℃～800 ℃ mesophilic range.In addition, sealing glass also is used for the sealing etc. in the aperture of sheath well heater, in this situation also the mesophilic range (for example 450 ℃～800 ℃) in equal extent seal.
But, in such mesophilic range, use above-mentioned SnO-P 2O 5Be that the sealed thing of metal-made of Glass On Metals double container processed, sheath well heater etc. is when sealing, because above-mentioned SnO-P 2O 5Be that glass is low melting glass, produce easily bubble so become in the glass.Its result, gas can occur from the leakage of bubble in life-time service, and the resistance to air loss of hermetic unit is impaired, or the possibility that hermetic unit is peeled off raises.
On the other hand, Bi 2O 3-B 2O 3The problem that is glass is that the bismuth composition is reduced easily in the sealing process that carries out under nonoxidizing atmosphere, be difficult to guarantee stable state (for example with reference to patent documentation 10).
Therefore, technical task of the present invention is, even if provide a kind of by nonoxidizing atmosphere also can mesophilic range well the sealed thing of sealing metal system, and can guarantee for a long time the bubble-tight by SnO-P of hermetic unit 2O 5It is the glass for sealing that glass forms.
Be used for solving the means of problem
The inventor has carried out various experiments, found that by strict restriction SnO-P 2O 5It is the glass compositing range of glass, even if nonoxidizing atmosphere, also can be at mesophilic range (500 ℃～800 ℃ temperature range, preferred 450 ℃～800 ℃ temperature range) the sealed thing of sealing metal system well, and can when sealing, the reaction of glass and the sealed thing of metal-made appropriately be changed, thereby propose the present invention.That is, glass for sealing of the present invention is the glass for sealing for the sealed thing of sealing metal system, forms as glass, contains SnO 15%～30% (but not comprising 30%), P with a % by mole expression 2O 520%～40%, WO 35%～20% (but not comprising 5%), ZnO 3.4%～30% (but not comprising 30%), mol ratio SnO/ZnO are more than 1 below 4.5.
Glass for sealing of the present invention limits the glass compositing range as described above.So, can suitably flow in mesophilic range, can prevent from producing in the glass a large amount of bubbles simultaneously.In addition, the sealed thing appropriate reaction of glass for sealing and metal-made can be guaranteed firmly cementability.And then, even if in the situation about under nonoxidizing atmosphere, being sealed, also can prevent the surperficial devitrification of hermetic unit, the rotten state of affairs.Therefore, owing to can realize these advantages, the result can guarantee the resistance to air loss of hermetic unit for a long time, even if mesophilic range also can realize good sealed state.
The second, glass for sealing of the present invention does not preferably contain in fact PbO.So, can satisfy in recent years environmental requirement." do not contain in fact PbO " here, and refer to that the PbO content in the glass composition is the following situation of 1000ppm (quality).
The 3rd, glass for sealing of the present invention, the preferred glass transition temperature is 350 ℃～500 ℃.Need to prove that second-order transition temperature can be measured with push-down dilatometer etc.
The 4th, glass for sealing of the present invention is preferred for 1.0 * 10 -2Sealing in the reduced atmosphere below the Torr.
The 5th, glass for sealing of the present invention is preferred for oxygen concn and is the sealing in the following atmosphere of 5 volume %.
The 6th, sealing glass of the present invention is particularly suitable for the sealing of metal-made double container.
The 7th, sealing glass of the present invention, preferred seal temperature is 450 ℃～800 ℃.
The 8th, sealing glass of the present invention is by utilizing the moulding of drip shaping method to form.
The 9th, sealing glass of the present invention is preferably implemented cutting and is processed after moulding.
The tenth, sealing matrix material of the present invention is the sealing matrix material that contains glass powder and resistivity against fire filler, it is characterized in that glass powder contains above-mentioned glass for sealing.
The 11, sealing matrix material of the present invention, the content of preferred glass powder are 45 volume %～100 volume %, and the content of resistivity against fire filler is 0 volume %～55 volume %.
[effect of invention]
According to aforesaid the present invention, can strictly adjust by SnO-P 2O 5Be the glass compositing range of the sealing glass that forms of glass, so even if nonoxidizing atmosphere, also can be at the mesophilic range sealed thing of sealing metal system well, and guarantee for a long time the resistance to air loss of hermetic unit.
Description of drawings
Fig. 1 is the cross section sketch chart of the structure of expression metal-made double container.
Fig. 2 is the amplification cross section sketch chart before the sealing process in the zone shown in the X of Fig. 1.
Embodiment
The glass for sealing that an embodiment of the invention relate to forms as glass, contains SnO 15%～30% (but not comprising 30%), P with a % by mole expression 2O 520%～40%, WO 35%～20% (but not comprising 5%), ZnO 3.4%～30% (but not comprising 30%), mol ratio SnO/ZnO are more than 1 below 4.5.
As mentioned above, below illustrate SnO-P 2O 5The glass compositing range that is glass has carried out the reason that limits.Need to prove that in the explanation that contains scope of each composition, % represents to refer to % by mole.
SnO is the composition that reduces the fusing point of glass, and its content was 15%～30% (but not comprising 30%), preferred 20%～28%.When the content of SnO lacked than 15%, the viscosity of glass raise, and flowability descends in mesophilic range easily.Need to prove that the content of SnO is 20% when above, raise in that mesophilic range is mobile, so guarantee easily high-air-tightness.On the other hand, than more than 30% the time, the low temperature lower-glass occurs softening at the content of SnO, so processing temperature excessively reduces, and becoming is difficult to use in mesophilic range.That is, in the situation of the sealing that is used for the metal-made double container, glass excess flow during sealing is difficult to the venting port at mesophilic range sealing metal double container processed.
P 2O 5Be network former, its content is 20%～40%, preferred 25%～35%.At P 2O 5Content when lacking than 20%, it is unstable that glass becomes.On the other hand, at P 2O 5Content than more than 40% the time, wet fastness descends.Need to prove, as long as P 2O 5Content be more than 25%, then the further stabilization of glass as long as be below 35%, then can improve weathering resistance.
WO 3Be so that with reactive appropriateization of the sealed thing of metal-made and raising bonding strength, bubble-tight composition.In addition, adding WO 3The time, weathering resistance raises, and therefore can improve the long-term reliability of hermetic unit.WO 3Content be 5%～20% (not comprising 5%), preferred 10%～15%.At WO 3Content be 5% when following, can't obtain above-mentioned effect.On the other hand, at WO 3Content than more than 20% the time, the phase-splitting tendency strengthens when melting, it is unstable that glass becomes.Need to prove, at WO 3Content when being 10%～15%, mobile mesophilic range is improving.In addition, at WO 3Content than more than 5% the time, can produce above-mentioned effect, but in the situation of air atmosphere lower seal, glass is devitrification when sealing easily.For this reason, the glass for sealing of present embodiment is preferred for 1.0 * 10 -2Sealing in the reduced atmosphere below the Torr or oxygen concn are the sealing in the following atmosphere of 5 volume %.
ZnO is intermidate oxide, is the composition that makes the effect increase of stabilization in addition, and its content was 3.4%～30% (but not comprising 30%), preferred 5%～28%.If consider the stability (devitrification resistance, minute phasic property etc.) of whole glass, the content of ZnO is preferably more than 5%.But, be 30% when above at the content of ZnO, the one-tenth balance-dividing that glass forms is impaired, and devitrification occurs in surface at glass during sealing easily.Need to prove, be 28% when following at the content of ZnO, and the stable mesophilic range of glass improves.
Mol ratio SnO/ZnO is more than 1 below 4.5, and is preferred more than 1 below 4.Mol ratio SnO/ZnO was less than 1 o'clock, and it is unstable that glass becomes easily.On the other hand, mol ratio SnO/ZnO was greater than 4.5 o'clock, and glass is excess flow when sealing, and becoming is difficult to the sealed thing of sealing metal system, and produces easily bubble in glass.
As any composition, can add following composition.
MgO is that mesh is modified oxide compound, is the composition that makes stabilization in addition.The content of MgO is 0%～20%, particularly preferably 0%～5%.At the content of MgO than more than 20% the time, during sealing easily the surface at glass devitrification occurs.
Al 2O 3Being intermidate oxide, is the composition that makes stabilization in addition, and then is the composition that thermal expansivity is descended.Al 2O 3Content be 0%～10%, particularly when considering the stability of glass, thermal expansivity, flowability etc., preferred 0.5%～5%.At Al 2O 3Content than more than 10% the time, softening temperature rises, flowability descends in mesophilic range easily.
SiO 2Being network former, is the composition that suppresses devitrification in addition.SiO 2Content be 0%～15%, particularly preferably 0%～8%.At SiO 2Content than more than 15% the time, softening temperature rises, flowability descends in mesophilic range easily.
B 2O 3Being network former, is the composition that makes stabilization in addition.B 2O 3Content be 0%～25%.At B 2O 3Content than more than 25% the time, the viscosity of glass excessively raises, and mobilely during sealing significantly descends, the resistance to air loss of hermetic unit might be impaired.Particularly in the glass compositional system that present embodiment relates to, B 2O 3Content than more than 25% the time, the glass easy phase-splitting that becomes.Need to prove B 2O 3The tendency that the viscosity of glass is raise is stronger.For this reason, in the situation that softening temperature is significantly descended, preferably do not contain in fact B 2O 3, that is to say to be preferably below 0.1%.
With regard to R 2O (R is any among Li, Na, K, the Cs) is adding R 2During in the O composition at least a kind, improve with the cementability of the sealed thing of metal-made such as stainless steel.R 2The content of O is 0%～20%, particularly preferably 0.1%～10%.At R 2The content of O is than more than 20% the time, and glass is devitrification when sealing easily.In addition, about Li 2O, Na 2O, K 2O, Cs 2The content of O is respectively 0～12%, and particularly preferably 0.1～10%.Need to prove, at R 2In the O composition, Li 2The O raising is large with the effect of the cementability of the sealed thing of metal-made.
Lanthanide oxide is that mesh is modified oxide compound, and its content is 0%～25%, and is preferred 0.1～20%, particularly preferably 0.5%～15%.Than more than 25% the time, seal temperature raises at the content of lanthanide oxide, and flowability descends in mesophilic range easily.Need to prove, as lanthanide oxide, can use La 2O 3, CeO 2, Nd 2O 3Deng.In addition, be more than 0.1% as long as make the content of lanthanide oxide, just can improve weathering resistance.
Except lanthanide oxide, add other rare-earth oxides, for example Y 2O 3The time, can further improve weathering resistance.The content of the rare-earth oxide except lanthanide oxide counts 0%～5% with total amount.
And then, for glass makes stabilization, can add MoO 3, Nb 2O 5, TiO 2, ZrO 2, CuO, MnO, In 2O 3, R ' O (R ' be among Mg, Ca, Sr, the Ba any) etc. and addition reach 35% in total amount.Need to prove that than more than 35% the time, the one-tenth balance-dividing that glass forms is impaired in total amount for the content of these compositions, glass becomes unstable on the contrary, becomes to be difficult to make glass for sealing.Need to prove that as long as the content of these compositions is counted below 25% with total amount, then glass just is difficult to become unstable.
MoO 3Content be 0%～20%, particularly preferably 0%～10%.At MoO 3Content than more than 20% the time, the viscosity of glass raises, glass becomes and is difficult to flow in mesophilic range.
Nb 2O 5, TiO 2, ZrO 2Content be respectively 0%～15%, particularly preferably 0%～10%.Than more than 15% the time, the one-tenth balance-dividing that glass forms is impaired respectively for these compositions, and glass becomes unstable on the contrary.
The content of CuO, MnO is respectively 0%～10%, and particularly preferably 0%～5%.Than more than 10% the time, the one-tenth balance-dividing that glass forms is impaired respectively for these compositions, and glass becomes unstable on the contrary.
About In 2O 3, ignoring in the situation of cost, be the composition that can use for the weathering resistance that obtains height.In 2O 3Content be preferably 0%～5%.
The content of R ' O counts 0%～15% with total amount, and particularly preferably 0%～5%.The content of R ' O in total amount than more than 15% the time, the one-tenth balance-dividing that glass forms is impaired, glass becomes unstable on the contrary.
Need to prove, except mentioned component, can also add other compositions and make its addition for example reach 5%.In addition, as mentioned above, from the viewpoint of environment, preferably do not contain in fact PbO.
Has the SnO-P that above glass forms 2O 5Be glass, second-order transition temperature is about 350 ℃～500 ℃, and yield-point is about 380 ℃～530 ℃, and the thermal expansivity of 30 ℃～300 ℃ temperature range is about 60 * 10 -7/ ℃～110 * 10 -7/ ℃.In addition, this glass is 1.0 * 10 -2In the reduced atmosphere below the Torr, the sealed thing of sealing metal system well in 500 ℃～800 ℃ temperature range, and then in the atmosphere below remaining oxygen concentration is 5 volume %, inert atmospheres such as nitrogen, argon, at 450 ℃～650 ℃ the temperature ranges sealed thing of sealing metal system well.
In the glass for sealing of present embodiment, second-order transition temperature is 350 ℃～500 ℃, particularly preferably 400 ℃～450 ℃.When second-order transition temperature was lower than 350 ℃, glass was in the mesophilic range excess flow, and becoming is difficult to the sealed thing of sealing metal system, and produces easily bubble in glass.On the other hand, when second-order transition temperature was higher than 500 ℃, softening temperature rose, and flowability descends in mesophilic range easily.
In the glass for sealing of present embodiment, yield-point is 380 ℃～530 ℃, particularly preferably 440 ℃～480 ℃.When yield-point was lower than 380 ℃, glass was in the mesophilic range excess flow, and becoming is difficult to the sealed thing of sealing metal system, and produces easily bubble in glass.On the other hand, when yield-point was higher than 530 ℃, softening temperature rose, and becoming is difficult to seal in mesophilic range.Need to prove that yield-point can use push-down dilatometer etc. to be measured.
In the glass for sealing of present embodiment, the thermal expansivity of 30 ℃～300 ℃ temperature range is 60 * 10 -7/ ℃～110 * 10 -7/ ℃, particularly preferably 70 * 10 -7～85 * 10 -7/ ℃.So, become easily and the matched coefficients of thermal expansion of the sealed thing of metal-made, so can reduce the stress that hermetic unit is applied.Need to prove that the thermal expansivity of 30 ℃～300 ℃ temperature range can use push-down dilatometer etc. to be measured.
The glass for sealing of present embodiment can carry out good sealing to the sealed thing of various metal-mades.In addition, the glass for sealing of present embodiment in order to prevent the oxidation of metal when sealing, is preferred for 1.0 * 10 -2Seal in the reduced atmosphere below the Torr, or be used for the sealing that oxygen concn is the following atmosphere of 5 volume %.
The glass for sealing of present embodiment for thermal expansivity is regulated, uses after can adding resistivity against fire filler and Composite.In the situation of mixing the resistivity against fire filler, its combined amount is glass for sealing (glass powder) 45 volume %～100 volume %, resistivity against fire filler 0 volume %～55 volume %.When the content of resistivity against fire filler manyed than 55 volume %, relatively the ratio of glass powder reduced, and becoming is difficult to guarantee needed flowability.
As the resistivity against fire filler, can use various materials, such as using quartz, trichroite, zircon, stannic oxide, niobium oxides, zirconium phosphate, phosphoric acid wolframic acid zirconium, willemite, mullite etc.In addition, with regard to NbZr (PO 4) 3Be ceramic powder, contain phosphoric acid in the composition, so and SnO-P 2O 5The adaptability that is glass is good.Need to prove NbZr (PO 4) 3Be that ceramic powder preferably adds on a small quantity (for example 0.1～2 quality %) MgO as sintering aid.
Below, the manufacture method of the glass for sealing of present embodiment is described in detail.
At the glass for sealing of present embodiment and use in its making of matrix material, at first, according to becoming after mode that above-mentioned glass forms concocted frit, carry out melting at 850 ℃～1000 ℃, make melten glass.In the situation of the glass compositing range that present embodiment relates to, even if melting is also no problem in atmosphere, but the SnO during glass forms when should be noted that melting is not oxidized to SnO 2In order to prevent that the SnO in the glass composition is oxidized to SnO 2, preferably at N 2Middle melting or in melten glass, carry out N 2Bubbling etc., under non-oxidizing atmosphere, carry out melting.In addition, in the situation of the melting of laboratory level, from the viewpoint of workability, preferably after on the melting crucible cover, carry out melting.
Be in the situation of metal at sealed thing, in most cases do not mix the resistivity against fire filler and use separately glass.In this case, pull out melten glass (1) with bar-shaped, and cutting becomes specified length, and (2) drippage melten glass also is shaped to the chip form with prescribed level, and (3) are cured after being shaped to bulk, can make glass for sealing thus.Need to prove, about the glass for sealing of bulk, cut out regulation the size after in.The glass for sealing of present embodiment is using separately in the situation of glass the shapes such as preferred rectangular parallelepiped, cylinder, ball, Elliptical ball, hemisphere, ovum type, marble shape.In addition, in this case, do not need the binding agent etc. that takes off described later, and can realize the simplification of sealing process, but can't paste, therefore preferably in the part that should seal of the sealed thing of metal-made, be provided for arranging the recess of glass for sealing.Specifically, in the situation of metal-made double container, preferably at venting port recess is set.
The glass for sealing of present embodiment preferably adopts drip shaping method (methods of above-mentioned (2)) moulding.When using the method, can omit or simplify the mechanical workouts such as cutting, so can make at a low price glass for sealing.Need to prove, after the drippage melten glass, as long as with forming mould etc. melten glass is pressurizeed, just the height of sealing glass etc. can be adjusted to desirable scope.
In the situation of drip shaping method, need to drip the nozzle of usefulness, need to be with melting furnace and nozzle welding.If consider the weldability of melting furnace and nozzle, as melting furnace material and nozzle material, be fit to use platinum and alloy, zirconium and alloy thereof etc.
In the situation of drip shaping method, as long as regulate the viscosity of nozzle od and melten glass, just can control the volume of glass for sealing.In the situation that the venting port to the metal-made double container seals, the volume of glass for sealing preferably equates with the volume of the recess that forms at the periphery of venting port or below it.Compare with the volume of recess when excessive at the volume of glass for sealing, because the differential expansion of glass for sealing and metal (for example SUS430 system), be full of cracks becomes and enters easily glass part, and becoming is difficult to keep the resistance to air loss of hollow bulb.In addition, during for the volume of the irreducible minimum that arrives venting port, might seal venting port at the volume of glass for sealing infalliblely.If consider above aspect, the volume of glass for sealing is preferably at 50%～120% of the volume of the recess of the periphery formation of venting port.
The sealing glass of present embodiment in the situation of sealing metal double container processed, preferably is accommodated in the recess that forms at the metal-made double container, carries out on this basis sealing process.So, can stablize the mounting sealing glass, and can efficient sealed venting port.
The sealing glass of present embodiment is preferred for the sealing of grill pan, incubation canteen, insulation cooker, is particularly preferred for the sealing of grill pan.These metal-made double containers can be sealed 500 ℃～700 ℃ mesophilic range, so the sealing glass of present embodiment is fit to.
The sealing glass of present embodiment, being preferred for metal material is SUS430 or martensitic (the metal-made double container of 12%～14%Cr) SUS436, SUS403 of ferritic series (18%Cr).These metal materials in most cases are sealed 500 ℃～700 ℃ mesophilic range, so the sealing glass of present embodiment is fit to.
In addition, after melten glass is shaped to the film shape, pulverize, classification, can be processed into powder shape thus.For the glass powder that obtains, when mixing the resistivity against fire filler, can make composite powder.Then, the glass powder that obtains or composite powder (situation that comprises tinting material is many) and vehicle are being carried out to make the paste material when mixing.
As the resin in the vehicle, preferably can aliphatic poly ethylene series carbonic ether, particularly preferably polymerized thylene carbonate ethyl ester, poly (propylene carbonate).These resins are difficult to make SnO-P when having sealing 2O 5Be the rotten character of glass.On the other hand, when using general ethyl cellulose as resin, SnO-P 2O 5Be that rotten possibility height occurs glass.About the solvent in the vehicle, preferably from N, it is a kind of or more than two kinds that N '-dimethyl formamide, ethylene glycol, methyl-sulphoxide, methylcarbonate, Texacar PC, butyrolactone, caprolactone, METHYLPYRROLIDONE select.These solvents make SnO-P when having sealing 2O 5Be the character that glass is difficult to go bad.
Next, the surface coated paste material to the sealed thing of metal-made carries out drying.About the coating of paste material, use divider, screen process press etc. to get final product.Then, as required, carrying out burning till (once-firing) afterwards in order to take off binding agent, the limit makes itself and the opposing party's sealed thing contact edge burn till (twice firing), and sealed thing is sealed.Need under being enough to the condition of gluing of surfaces of wetting sealed thing, glass powder or matrix material carry out twice firing.
About once-firing, in order to prevent SnO-P 2O 5Be the rotten of glass, preferably under the inert atmospheres such as nitrogen, argon, particularly nitrogen atmosphere, carry out.
The glass for sealing of present embodiment is preferred for 1.0 * 10 -2Sealing in the reduced atmosphere below the Torr.So long as 1.0 * 10 -2The reduced atmosphere that Torr is following just can prevent the oxidation of the sealed thing of metal-made.In addition, in order to prevent the oxidation of the sealed thing of metal-made infalliblely, further preferably 1.0 * 10 -3Seal under the reduced atmosphere below the Torr.On the other hand, in pressure ratio 1.0 * 10 -2When Torr was large, glass is devitrification, rotten when sealing easily.Need to prove, so long as 1.0 * 10 -2The decompression that Torr is following then can realize with normally used rotor pump.
In the actual production of metal-made double container etc., for the vacuum tightness that improves in the container in most cases uses oil diffusion pump (diffusion pump) that sealing atmosphere is reduced pressure.In this case, the vacuum tightness of sealing atmosphere is 1.0 * 10 -3Below the Torr.The upper limit of vacuum tightness to sealing atmosphere is not particularly limited.Need to prove, with rotor pump and turbo-molecular pump, reduce pressure into 1.0 * 10 by also -6Torr has carried out seal test, and the result can confirm that devitrification, rotten does not occur the glass for sealing of present embodiment.But, in actual production, about the vacuum tightness of sealing atmosphere, because from the impact of the release gas of glass for sealing, the sealed thing of metal-made, being difficult to is 1.0 * 10 -6Below the Torr.
The glass for sealing of present embodiment, being preferred for oxygen concn is the following atmosphere of 5 volume %, the sealing in the inert atmospheres such as nitrogen, argon.So, the glass devitrification, rotten when sealing that becomes easily, and can prevent the oxidation of the sealed thing of metal-made.On the other hand, at the oxygen concn of sealing atmosphere when manying than 5 volume %, glass become easy devitrification, go bad and the sealed thing of the metal-made easy oxidation that becomes.Need to prove, even if do not use vacuum pump etc., only make the rare gas elementes such as nitrogen, argon flow into the blanket gas atmosphere, the gas concentration that makes rare gas element is 95 volume % when above, and can make the remaining oxygen concentration in the blanket gas atmosphere is below the 5 volume %.
[embodiment 1]
Below, the embodiment of glass for sealing of the present invention is described in detail.Need to prove that following embodiment is simple illustration.The present invention is not limited to following embodiment.
Table 1,2 illustrates embodiments of the invention (No.1～11), and table 3 illustrates comparative example (No.12～16).
Figure BDA00002777899100121
[table 2]
Figure BDA00002777899100131
[table 3]
Figure BDA00002777899100141
As shown below, prepared each test portion.At first, the mode that forms according to the glass that becomes in the table has been concocted frit.In addition, as the importing raw material of phosphorus, do not use the ortho-phosphoric acid (orthophosphoric acid) as liquid starting material and use stannous pyrophosphate and metaphosphoric acid zinc, the importing raw material that makes phosphorus all is solid material.When making the importing raw material of phosphorus all be solid material, having that what is called can use with other glass is the advantage of identical producing apparatus.Need to prove, as the importing raw material of phosphorus, liquid starting material directly put into melting furnace and when carrying out melting, the problem that becomes and overflow easily.In addition, for the problem of avoiding overflowing, must interim dry glass raw material.
Then, with the blending after frit 950 ℃ of meltings 2 hours.Need to prove, when melting, in order to suppress the oxidation of SnO, in melting furnace, flow into nitrogen.Remaining oxygen concentration in the melting furnace when flowing into nitrogen is below 1%.
Next, use the carbon drill jig, melten glass is shaped to the cylindric of diameter 5mm, length 20mm.This moulding test portion is carried out anneal, utilize push-down dilatometer (TMA, regaku system), second-order transition temperature, yield-point, 30 ℃～300 ℃ the thermal expansivity of temperature range are measured.In addition, same columned test portion (having annealed) is processed into length 3mm, is used for the evaluation of cementability.
As follows, to having or not cementability evaluation.Use metal as estimating, do not use the SUS304 of the normally used austenite of low-temperature region, but use the SUS430 of the ferritic series of high heat resistance.Estimate the writing board shape that is shaped as 40mm * 40mm with metal.Then, upload at the sealed thing of this metal-made and to be set up the evaluation test portion of stating, the atmosphere in table is burnt till.
" decompression is burnt till " in the table refers to that the limit constantly burns till by the rotor pump limit of reducing pressure.When decompression is burnt till, the pressure variation due to the foamed gas that occurs from glass for sealing is arranged, confirming its pressure by tensimeter is 1.0 * 10 -2Below the Torr.Need to prove, about firing condition, kept 10 minutes 650 ℃ of firing temperatures, the heat-up rate from room temperature to firing temperature be 20 ℃/minute, to the cooling rate of room temperature be 15 ℃/minute.
" atmosphere is burnt till " in the table refers to that the limit constantly burns till with the gas limit of putting down in writing in the 2.0L/ minute lasting inflow table.With regard to the remaining oxygen concn, confirm as below the 5 volume % by oxymeter when burning till.Need to prove that about firing condition, kept 10 minutes 550 ℃ of firing temperatures, the heat-up rate from room temperature to firing temperature is 15 ℃/minute, to the cooling rate of room temperature be 10 ℃/minute.
As from table 1,2 know, in test portion No.1～11, the thermal expansivity of 30 ℃～300 ℃ temperature range is 69.6 * 10 -7～83.7 * 10 -7/ ℃, second-order transition temperature is 389 ℃～463 ℃, yield-point is 416～472 ℃, in addition, burns till in decompression, during atmosphere burns till, does not all have devitrification, rotten after burning till, the cementability that expression is good with the sealed thing of metal-made.Thus, test portion No.1～11 are suitable as the glass for sealing of mesophilic range.
On the other hand, about test portion No.12,13,16, burn till in decompression, during atmosphere burns till, all after burning till, do not have devitrification, rotten, but do not have cementability with metal, can after sealing, peel off from the sealed thing of metal-made.About test portion No.14, burn till in decompression, during atmosphere burns till, all after burning till, do not have devitrification, rotten, but because mol ratio SnO/ZnO is greater than 5, so superfluous flowing on the sealed thing of metal-made, glass can overflow from the sealed thing of metal-made, can't carry out the evaluation of cementability.Need to prove that about test portion No.14, fusing point is excessively low, thinks and can't use in mesophilic range.About test portion No.15, burn till in decompression, during atmosphere burns till, all after burning till, do not have devitrification, rotten, but on the sealed thing of metal-made, flow hardly, so can't carry out the evaluation of cementability.
[embodiment 2]
Below, the embodiment with matrix material describes in detail to sealing of the present invention.Need to prove that following embodiment only is simple illustration.The present invention is not limited by following embodiment.
Table 4 illustrates embodiments of the invention (No.17～20).
Glass powder and the resistivity against fire filler of record in the table 4 are mixed with requirement ratio, made each test portion.Need to prove, make the median size D of glass powder and resistivity against fire filler 50Be 10 μ m.
Figure BDA00002777899100171
Utilize push-down dilatometer (TMA, regaku system), the thermal expansivity of 30 ℃～300 ℃ temperature ranges is measured.Need to prove, sinter each test portion into fine and close test portion, as measuring test portion.
As shown below, to having or not cementability evaluation.At first, with each test portion sintering, made the sintered compact of diameter 20mm, thick 1mm.Then, this sintered compact is loaded on the metal sheet of the SUS430 of 40mm * 40mm, and then load the alumina plate of 40mm * 40mm at this sintered compact, made to estimate and used test portion.Next, under the atmosphere in table this evaluation is burnt till with test portion.At last, metal sheet and the alumina plate of SUS430 are had or not bonding the evaluation.
As being known by table 4, be 59.2 * 10 about the thermal expansivity of the temperature range of test portion No.17～20,30 ℃～300 ℃ -7/ ℃～64.5 * 10 -7/ ℃, in addition, burning till of the atmosphere in the utilization table do not have devitrification, rotten, shows good cementability.
Utilizability on the industry
Glass for sealing of the present invention can be at the mesophilic range sealed thing of sealing metal system well, so for example be suitable for the sealing of sealing, glass and the Dumet line of diode, the orifice sealing of sheath well heater, the sealing of magnetic head, in addition, add resistivity against fire filler etc., when making the matched coefficients of thermal expansion of itself and the sealed thing of metal-made, can be suitable for the sealing of metal and pottery, such as the sealing that is used for the IC encapsulation etc.

Claims (11)

1. a glass for sealing is for the glass for sealing of the sealed thing of sealing metal system, it is characterized in that,
Form as glass, contain SnO 15%～30% with a % by mole expression but do not comprise 30%, P 2O 520%～40%, WO 35%～20% but do not comprise 5%, ZnO 3.4%～30% but do not comprise 30%, mol ratio SnO/ZnO is more than 1 below 4.5.
2. glass for sealing as claimed in claim 1 is characterized in that,
Do not contain in fact PbO.
3. such as claim 1 or 2 described glass for sealing, it is characterized in that,
Second-order transition temperature is 350 ℃～500 ℃.
4. such as the described glass for sealing of any one in the claim 1～3, it is characterized in that,
Be used for 1.0 * 10 -2Sealing in the reduced atmosphere below the Torr.
5. such as the described glass for sealing of any one in the claim 1～4, it is characterized in that,
Being used for oxygen concn is the sealing of the following atmosphere of 5 volume %.
6. such as the described glass for sealing of any one in the claim 1～5, it is characterized in that,
The sealed thing of described metal-made is the metal-made double container.
7. such as the described glass for sealing of any one in the claim 1～6, it is characterized in that,
Seal temperature is 450 ℃～800 ℃.
8. such as the described glass for sealing of any one in the claim 1～7, it is characterized in that,
Formed by the moulding of drip shaping method.
9. such as the described glass for sealing of any one in the claim 1～8, it is characterized in that,
Implementing cutting after moulding processes.
10. sealing matrix material, it is the sealing matrix material that contains glass powder and resistivity against fire filler, it is characterized in that,
Glass powder contains the described glass for sealing of any one in the claim 1～9.
11. sealing matrix material as claimed in claim 10 is characterized in that,
The content of glass powder is 45 volume %～100 volume %, and the content of resistivity against fire filler is 0 volume %～55 volume %.
CN2011800366402A 2010-07-28 2011-06-29 Sealing glass and sealing composite material Pending CN103025677A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2010-168820 2010-07-28
JP2010-168811 2010-07-28
JP2010168820 2010-07-28
JP2010168811 2010-07-28
PCT/JP2011/064957 WO2012014619A1 (en) 2010-07-28 2011-06-29 Sealing glass and sealing composite material

Publications (1)

Publication Number Publication Date
CN103025677A true CN103025677A (en) 2013-04-03

Family

ID=45529838

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2011800366402A Pending CN103025677A (en) 2010-07-28 2011-06-29 Sealing glass and sealing composite material

Country Status (2)

Country Link
CN (1) CN103025677A (en)
WO (1) WO2012014619A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274601A (en) * 2013-06-07 2013-09-04 福州大学 Nb2O5-containing seal glass and its preparation and application methods

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114180843B (en) * 2021-12-28 2023-01-13 海南大学 Sealing glass and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087883A (en) * 1992-08-03 1994-06-15 康宁玻璃公司 Barium crown sealed glass
CN1830856A (en) * 2006-03-17 2006-09-13 东华大学 Leadless phosphate seal glass and its preparation method
CN101484396A (en) * 2006-07-11 2009-07-15 日本电气硝子株式会社 Glass composition for sealing and sealed material
JP2010100485A (en) * 2008-10-24 2010-05-06 Nippon Electric Glass Co Ltd Nozzle for forming droplet

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4061792B2 (en) * 1999-11-05 2008-03-19 旭硝子株式会社 Lead-free low melting glass and glass frit
JP2009001433A (en) * 2007-06-19 2009-01-08 Nippon Electric Glass Co Ltd Sealing material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1087883A (en) * 1992-08-03 1994-06-15 康宁玻璃公司 Barium crown sealed glass
CN1830856A (en) * 2006-03-17 2006-09-13 东华大学 Leadless phosphate seal glass and its preparation method
CN101484396A (en) * 2006-07-11 2009-07-15 日本电气硝子株式会社 Glass composition for sealing and sealed material
JP2010100485A (en) * 2008-10-24 2010-05-06 Nippon Electric Glass Co Ltd Nozzle for forming droplet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103274601A (en) * 2013-06-07 2013-09-04 福州大学 Nb2O5-containing seal glass and its preparation and application methods
CN103274601B (en) * 2013-06-07 2016-01-06 福州大学 A kind of containing Nb 2o 5seal glass and preparation and application thereof

Also Published As

Publication number Publication date
WO2012014619A1 (en) 2012-02-02

Similar Documents

Publication Publication Date Title
JP5384203B2 (en) Sealing glass
CN107112974A (en) The manufacture method of airtight package
CN102245525B (en) Sealing glass, glass member having sealing material layer, and electronic device and method for producing the same
US7399720B1 (en) Glass and glass-ceramic sealant compositions
JP2006342044A (en) Vanadium phosphate base glass
JP6617541B2 (en) Lead-free glass and sealing materials
KR101699121B1 (en) Vitreous or at least partially crystalline joining material and the use thereof
CN105683112A (en) Vanadium-based glass material for local heating and sealing, flat-panel display using the glass material, and method for manufacturing the display
WO2008007504A1 (en) Glass composition for sealing and sealed material
KR102066455B1 (en) Coefficient of thermal expansion filler for vanadium-based frit materials and/or methods of making and/or using the same
CN103748050A (en) Crystalline glass composition and adhesive material using same
JPWO2015087718A1 (en) Insulating member, low melting point glass composition, and sealing material paste
CN106977117A (en) Double glazing and its manufacture method
CN108886026A (en) The manufacturing method and airtight package of airtight package
CN107431045A (en) Airtight package and its manufacture method
Reddy et al. Diopside–Mg orthosilicate and diopside–Ba disilicate glass–ceramics for sealing applications in SOFC: Sintering and chemical interactions studies
CN103025677A (en) Sealing glass and sealing composite material
JP4411648B2 (en) Tin phosphate glass and composite materials
JP5080778B2 (en) Phosphate glass and electronic components using phosphate glass
CN109153597A (en) The low temperature tellurate glass mixture being compacted for the Temperature Vacuum at≤450 DEG C
JP4092936B2 (en) Tin phosphate glass and composite materials
CN104387103A (en) Method for soldering zirconia ceramic and metal material together
JP5831839B2 (en) Glass for sealing
CN111741931A (en) Sealing composition
US20150158755A1 (en) Medium temperature solid fuel cell glass packaging material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C05 Deemed withdrawal (patent law before 1993)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20130403