CN104276837A - Metal vitrification sealing method - Google Patents
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- CN104276837A CN104276837A CN201310292361.3A CN201310292361A CN104276837A CN 104276837 A CN104276837 A CN 104276837A CN 201310292361 A CN201310292361 A CN 201310292361A CN 104276837 A CN104276837 A CN 104276837A
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Abstract
The invention relates to a metal vitrification sealing method which comprises the following steps: pretreating a sealing part of a metal sealing piece; performing chemical treatment on the metal surface at the sealing part of the metal sealing piece so as to form a metal oxide pretreatment layer on the surface of the sealing part of the metal sealing piece; preparing glass sealing paste, namely preparing glass of which the thermal expansion coefficient is matched with that of a metal matrix of the metal sealing piece and of which the components and the pretreatment layer can be mutually diffused and permeated into glass powder, mixing the glass powder with an adhesive and a solvent, and blending to prepare the paste; performing vitrification on the metal sealing piece, namely uniformly coating the paste on the surface of the sealing part of the metal sealing piece so as to form a glass coating layer, and performing heat treatment in a protective atmosphere to form a vitrification layer; and sealing the metal sealing piece and ceramics, namely matching the metal sealing piece on which the vitrification layer is formed with a sealing part of a to-be-sealed ceramic part, and sealing in an inert atmosphere.
Description
Technical field
The present invention relates to metal-ceramic sealing technology field, be specifically related to a kind of by metallic glass, and then carry out the method for sealing-in with pottery.
Background technology
Metal has very important meaning with the application of sealing process in modern industrial technology of pottery.Be not only the critical process in vacuum electron device, and its range of application is more and more wider, is also widely used in the fields such as integrated antenna package, nuclear power, high energy physics, the energy, medical facilities, chemical industry, automotive industry, science and techniques of defence at present.Metal doubles to grow up along with multi-disciplinary the intersection with ceramic seal technology, and it is the extension of materials application, is the basic technology that a manufacturability and practicality are all very strong.Along with vacuum electron device is to the expansion day by day in high-power future development and metal and ceramic seal process application field, to the quality of seal interface, as reliability, resistance to air loss, intensity, stability etc. are had higher requirement.
Traditional metal and ceramic seal, all first metallize ceramic seal face, then carry out sealing-in by solder and metal.Ceramic metallization technology is exactly the paste be made up of specific refractory metal (molybdenum, tungsten etc.) and metal oxide (aluminum oxide, calcium oxide, silicon oxide etc.) in the surface-coated that ceramic member and metalwork carry out being connected, and in reducing atmosphere high temperature (1300 ~ 1600 DEG C) sintering curing, ceramic member surface attachment one deck is made to have the coating of metalline, to weld with metal parts, form Ceramic-to-metal seal part.First, ceramic metalizing process needs high temperature sintering solidification in reducing atmosphere, and have certain requirement to the control of atmosphere, this adds cost and the difficulty of operation undoubtedly; Secondly, when the closure utilizing ceramic metalizing process to obtain is for having certain corrosive environment to metal molybdenum or tungsten, the resistance to air loss of seal interface, stability and reliability will be difficult to be guaranteed; In addition, the closure utilizing ceramic metalizing process to obtain contains multiple interfacial layer (as the interface between ceramic component and metal layer in sealing-in place, interface between metal layer and solder, interface between solder and metal parts), and the interfacial layer place that to be whole closure the weakest, thus the control of ceramic metallization sealing technology to sealing process process is had higher requirement.
Summary of the invention
The object of this invention is to provide the new approaches of a kind of metal and ceramic seal, to overcome the deficiencies in the prior art.The present inventor finds after deliberation, first by the sealing-in position vitrifying of metal sealing part, namely first pre-treatment is carried out at the sealing-in position of metal sealing part, comprise oxidation, sulfuration, phosphatization, boronation, nitrogenize etc., one deck pretreatment layer can be formed at sealing-in portion faces, the paste of one deck by glass powder furnishing is applied again on pretreatment layer, carry out high-temperature heat treatment under an inert atmosphere, utilize the phase mutual diffusion of pretreatment layer and glass ingredient, merge, the combination firmly vitrifying layer that component has Gradient distribution can be formed at the sealing-in position of metal sealing part, then directly sealing-in is carried out with pottery by vitrifying layer, this purpose can be realized.
At this, the invention provides a kind of method for sealing of metallic glass, described method comprises:
(1) pre-treatment at metal sealing part sealing-in position: by carrying out chemical treatment to the metallic surface at metal sealing part sealing-in position to form metallic compound pretreatment layer at metal sealing part sealing-in portion faces;
(2) preparation of seal glass paste: by the matched coefficients of thermal expansion of the metallic matrix with metal sealing part and between glass ingredient and pretreatment layer can the glass of phase mutual diffusion and infiltration make glass powder after be modulated into paste with binding agent, solvent;
(3) vitrifying of metal sealing part: the surface described paste being evenly coated on described metal sealing part sealing-in position forms vitreous coating layer and heat-treats to form vitrifying layer under protective atmosphere; And
(4) metal sealing part and ceramic sealing-in: the metal sealing part of vitrifying layer will be formed and carry out sealing-in under inert atmosphere after working good in the sealing-in position of the ceramic component sealed.
The present invention forms at the metal sealing part sealing-in position of having carried out surface preparation the combination firmly vitrifying layer that component has Gradient distribution; Then directly sealing-in is carried out with pottery by vitrifying layer.Compared with the method for sealing of traditional ceramic metallization, in the method for sealing of metallic glass of the present invention, by the phase mutual diffusion of component, fusion between metal with glass, define the interfacial layer of compositional gradient change, by the effect of chemical bond, metal and glass are combined, make both combinations very firm, interface stability is high, and resistance to air loss is good.Again, because metallic surface treatment process is comparatively ripe, the seal glass that therefore can match with it according to the different choice thermal expansivity of metal surface treatment process, has expanded the range of application of metallic glass method for sealing greatly.And, after metallic glass can directly and pottery carry out sealing-in, do not need additionally to add solder, simplify sealing process, decrease seal interface simultaneously, improve the reliability and stability of sealing process.
In the present invention, described metal can comprise stainless steel, kovar alloy, Ni, Ti, Mo, Mn, Al, W and alloy thereof.
In the present invention, described chemical treatment can be oxidation, sulfuration, phosphatization, boronation, nitrogenize or halogenation.By described chemical treatment, the pretreatment layer of containing metal oxide, metallic sulfide, metal phosphide, metal boride, metal nitride or metal halide can be formed at metal sealing part sealing-in portion faces.Again, the thickness of the pretreatment layer of formation can be 1 ~ 10 μm.
According to difference and the described chemically treated difference of metallic matrix, different glass systems can be selected as sealing-in medium, make the matched coefficients of thermal expansion of glass and metallic matrix, and between glass ingredient with pretreatment layer can phase mutual diffusion, infiltration, thus form fine and close vitrifying layer.On the contrary, due to metallic surface, to carry out chemically treated technique comparatively ripe again, therefore according to treating that the thermal expansivity of sealing-in pottery selects the seal glass of suitable ingredients, then can carry out corresponding surface treatment according to the component of seal glass to metal.This has expanded the range of application of metallic glass sealing technology greatly.
In a preferred example, described chemical treatment is oxidation, and described glass is silicate glass and/or borosilicate glass.
In another preferred example, described chemical treatment is sulfuration, and described glass is chalcogenide glass.
In another preferred example, described chemical treatment is phosphatization, and described glass is phosphate glass.
In another preferred example, described chemical treatment is boronation, and described glass is borosilicate glass.
In another preferred example, described chemical treatment is nitrogenize, and described glass is Nitrogen Containing Glass.
In another preferred example, described chemical treatment is halogenation, and described glass is halide glass.
In described step (2), the particle diameter of described glass powder can be 2 ~ 200 μm.
Described binding agent can be polyvinyl butyral acetal, ethyl cellulose, rosin and/or nitrocotton.
Described solvent can be ethanol, acetone, Terpineol 350, N-BUTYL ACETATE, propyl carbinol and/or pimelinketone.
Preferably, the weight ratio of described glass powder, binding agent, solvent can be (40wt% ~ 80wt%): (2wt% ~ 10wt%): (15wt% ~ 55%).
In described step (3), described coating can be dip-coating, spraying, silk screen printing, machinery coating etc.
Described thermal treatment can be 600 ~ 1100 DEG C of insulations 10 ~ 50 minutes.Through this thermal treatment, by the phase mutual diffusion of component, fusion between described pretreatment layer with glass, define the interfacial layer of compositional gradient change, by the effect of chemical bond, metal and glass are combined, make both combinations very firm, interface stability is high, and resistance to air loss is good.
Described protective atmosphere can be wet N
2/ H
2gas mixture or wet Ar/H
2gas mixture, wherein, steam H in described protective atmosphere
2the content of O can be 0.3 ~ 3vol%, H
2content can be 0.1 ~ 1.5vol%.
The thickness of described vitrifying layer can be 0.5 ~ 3mm.
In described step (4), described sealing-in can be at Ar or N
2in 600 ~ 1200 DEG C of sealing-ins 30 ~ 120 minutes under atmosphere.Due to be after metallic glass directly and pottery carry out sealing-in, not needing additionally to add solder, because this simplify sealing process, decreasing seal interface simultaneously, improve the reliability and stability of sealing process.
Accompanying drawing explanation
Fig. 1 is the principle schematic of metallic glass of the present invention.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment is only for illustration of the present invention, and unrestricted the present invention.
The object of this invention is to provide the new approaches of a kind of metal and ceramic seal, to overcome the deficiencies in the prior art.The invention discloses a kind of method for sealing of metallic glass, first by the sealing-in position vitrifying of metal sealing part, then directly carry out sealing-in with pottery by vitrifying layer.Fig. 1 is the principle schematic of metallic glass of the present invention, see Fig. 1, metallic glass is exactly first pre-treatment is carried out at the sealing-in position of metal sealing part, comprise oxidation, sulfuration, phosphatization, boronation, nitrogenize etc., thus form one deck pretreatment layer at sealing-in portion faces, the paste of one deck by glass powder furnishing is applied again on pretreatment layer, carry out high-temperature heat treatment under an inert atmosphere, utilize the phase mutual diffusion of pretreatment layer and glass ingredient, merge, the combination firmly vitrifying layer that component has Gradient distribution is formed at the sealing-in position of metal sealing part, for example, see Fig. 1, diffusion layer comprises the product of glass coating component and pretreatment of metal surface.
Particularly, exemplarily, the method for sealing of metallic glass of the present invention can comprise the following steps.
(1) pre-treatment at metal sealing part sealing-in position
Described pre-treatment includes but not limited to oxidation, sulfuration, phosphatization, boronation, nitrogenize, halogenation etc.; Described metal includes but not limited to stainless steel, kovar alloy, Ni, Ti, Mo, Mn, Al, W etc. and alloy thereof.See following reaction formula, by described pre-treatment, metallic compound (MXn) pretreatment layer can be formed on the surface at metal sealing part sealing-in position,
（X=O、S、P、B、N、F）
The thickness of the pretreatment layer formed can be 1 ~ 10 μm.
(2) the choosing of seal glass
According to the difference of metallic matrix and the difference of pretreatment technology, select different glass systems as sealing-in medium, make the matched coefficients of thermal expansion of glass and metallic matrix, and between glass ingredient with pretreatment layer can phase mutual diffusion, infiltration, thus form fine and close vitrifying layer, particularly
A, during () metal sealing part sealing-in position oxide treatment, corresponding glass is silicate glass or borosilicate glass, as SiO
2-Al
2o
3-B
2o
3-Na
2o-K
2o-Li
2o-Bi
2o
3deng;
B, during () metal sealing part sealing-in position sulfidizing, corresponding glass is chalcogenide glass, as Li
2s-P
2s
5-GeS
2, Ge-Sb-S-Se glass etc.;
C, during () metal sealing part sealing-in position bonderizing, corresponding glass is phosphate glass, as ZnO-Al
2o
3-P
2o
5system glass etc.;
D, during () metal sealing part sealing-in position borax treatment, corresponding glass is borosilicate glass, as B
2o
3-Bi
2o
3-SiO
2-Na
2o-K
2o-Li
2o etc.;
E, during () metal sealing part sealing-in position nitriding treatment, corresponding glass is Nitrogen Containing Glass, as oxynitride glass etc.;
F, during () metal sealing part sealing-in position halogenation treatment, corresponding glass is halide glass, as fluoride glass etc.;
Should be understood that to carry out chemically treated technique comparatively ripe due to metallic surface, therefore according to treating that the thermal expansivity of sealing-in pottery selects the seal glass of suitable ingredients, then can carry out corresponding surface treatment according to the component of seal glass to metal.This has expanded the range of application of metallic glass sealing technology greatly.
(3) by the glass ball milling in step (2), pulverize, sieve after obtain glass powder, and with binding agent, solvent after be modulated into paste.The particle diameter of preferred glass powder is 2 ~ 200 μm.Described binding agent includes but not limited to polyvinyl butyral acetal (PVB), ethyl cellulose (EC), rosin and/or nitrocotton.Described solvent includes but not limited to ethanol, acetone, Terpineol 350, N-BUTYL ACETATE, propyl carbinol and/or pimelinketone.The weight ratio of glass powder, binding agent, solvent can be (40wt% ~ 80wt%): (2wt% ~ 10wt%): (15wt% ~ 55%).
(4) paste in step (3) is evenly coated on the surface at metal sealing part sealing-in position.Described coating method includes but not limited to dip-coating, spraying, silk screen printing, machinery coating.The thickness of the vitreous coating layer formed can be 0.5 ~ 3mm.
(5) metal being coated with glass powder of step (4) gained is placed in heating installation such as retort furnace, heat-treats under protective atmosphere.Described protective atmosphere is wet N
2/ H
2gas mixture or wet Ar/H
2gas mixture, wherein, steam H in described protective atmosphere
2the content of O can be 0.3 ~ 3vol%, H
2content can be 0.1 ~ 1.5vol%.Described thermal treatment temp can be 600 ~ 1100 DEG C, and heat treatment time can be 10 ~ 50 minutes.
(6) by the parts of step (5) gained with after the ceramic component sealed is worked good, under inert atmosphere, carry out sealing-in.Described sealing temperature can be 600 ~ 1200 DEG C, and sealing time can be 30 ~ 120 minutes; Described inert atmosphere can be Ar or N
2.
The method for sealing of metallic glass of the present invention has the following advantages:
1, pass through phase mutual diffusion, the fusion of component between metal with glass, define the interfacial layer of compositional gradient change, metal and glass are combined by the effect of chemical bond, make both combinations very firm, interface stability is high, and resistance to air loss is good;
2, because the process of surface treatment such as burning, sulfuration, phosphatization, boronation, nitrogenize, halogenation are comparatively ripe, according to treating that the thermal expansivity of sealing-in pottery selects the seal glass of suitable ingredients, more corresponding surface treatment can be carried out according to the component of seal glass to metal.This has expanded the range of application of metallic glass sealing technology greatly;
3, after metallic glass can directly and pottery carry out sealing-in, do not need additionally to add solder, simplify sealing process, decrease seal interface simultaneously, improve the reliability and stability of sealing process.
Embodiment of illustrating further is below to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; and limiting the scope of the invention can not be interpreted as, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The temperature of reaction that following example is concrete, time etc. are also only examples in OK range, and namely, those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
A the pre-oxidation treatment of () metallic surface: by kovar alloy, if 4J29(25-300 DEG C of thermal expansivity is 4.7 × 10
-6k
-1) in wet Ar/H
2in gas mixture, be heated to 850 DEG C, and be incubated 30 minutes, carry out preoxidation, make sealed portion position Surface Creation a layer thickness of kovar alloy closure be the zone of oxidation of 2 ~ 5 μm.
Choosing of (b) seal glass: select the borosilicate glass that mates with kovar alloy of thermal expansivity as seal glass, if component is SiO
2: Al
2o
3: B
2o
3: Na
2o:K
2o:Li
2o:Bi
2o
3the glass of=60:3:18:3:3:1:12,25 ~ 300 DEG C of thermal expansivity are 4.7 ~ 4.9 × 10
-6k
-1.
The preparation of (c) glass paste: by the glass ball milling in (b), pulverize, sieve, obtain the glass powder that particle diameter is 10 ~ 20 μm, and make solvent with the mixture (1:4) of ethanol and Terpineol 350, weight ratio be 2.5% EC make binding agent, glass powder is modulated into the uniform paste of component.
D glass paste in (c) is evenly coated on the surface at kovar alloy closure sealing-in position by (), coating method is machinery coating, and thickness is 1.5 ~ 2mm.
The vitrifying of (e) metal: the kovar alloy being coated with glass powder of (d) gained is placed in retort furnace, at wet Ar/H
2gas mixture (steam H
2the content of O is 0.5%, H
2content be 1%, all the other are Ar) in heat-treat, thermal treatment temp is 900 DEG C, and heat treatment time is 30 minutes.
F () is by the kovar alloy closure in (e) and under Ar atmosphere, carry out sealing-in after the ceramic component sealed is worked good, and sealing temperature is 1000 DEG C, and sealing time is 50 minutes.
The detected result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10
-11pam
3s
-1; Mechanical experimental results shows, the sealing strength of closure is about 87MPa.
Embodiment 2
A the borax treatment of () metallic surface: in conjunction with known surface metal vitrifying treatment process, make reductive agent with sodium borohydride, adopts the technique of electroless plating, makes kovar alloy, if 4J44(25 ~ 300 DEG C thermal expansivity is 4.7 × 10
-6k
-1) the sealed portion position surface vitrification of closure, generate the boride layer that a layer thickness is 1 ~ 3 μm.
Choosing of (b) seal glass: with embodiment 1.
The preparation of (c) glass paste: by the glass ball milling in (b), pulverize, sieve, obtain the glass powder that particle diameter is 10 ~ 20 μm, and make solvent with dehydrated alcohol, weight ratio be 3% PVB make binding agent, glass powder is modulated into the uniform paste of component.
D glass paste in (c) is evenly coated on the surface at kovar alloy closure sealing-in position by (), coating method is silk screen printing, and thickness is 1.5 ~ 2mm.
The vitrifying of (e) metal: with embodiment 1.
(f) by the kovar alloy closure in (e) with after the ceramic component sealed is worked good in N
2carry out sealing-in under atmosphere, sealing temperature is 1000 DEG C, and sealing time is 50 minutes.
The detected result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10
-11pam
3s
-1; Mechanical experimental results shows, the sealing strength of closure is about 78MPa.
Embodiment 3
The bonderizing of (a) metallic surface: (25 ~ 300 DEG C of thermal expansivity are 10 ~ 13 × 10 by stainless steel according to the parkerizing method of existing widely used metal material surface
-6k
-1) the sealing-in portion faces of closure carries out bonderizing, thus form a layer thickness and be 2 ~ 5 μm, combine firmly phosphatize phosphate coat.
Choosing of (b) seal glass: select the phosphate glass that mates with stainless steel of thermal expansivity as seal glass, if component is P
2o
5: Na
2o:Al
2o
3the glass of=85:10:5, thermal expansivity is 11 × 10
-6k
-1.
The preparation of (c) glass paste: by the glass ball milling in (b), pulverize, sieve, obtain the glass powder that particle diameter is 5 ~ 10 μm, and with acetone as solvent, weight ratio be 3% nitrocotton make binding agent, glass powder is modulated into the uniform paste of component.
D glass paste in (c) is evenly coated on the surface at stainless steel sealed sealing-in position by (), coating method is manual application, and thickness is 1.5 ~ 2mm.
The vitrifying of (e) metal: the stainless steel being coated with glass powder of (d) gained is placed in retort furnace, at wet Ar/H
2gas mixture (steam H
2the content of O is 0.5%, H
2content be 1%, all the other are Ar) in heat-treat, thermal treatment temp is 750 DEG C, and heat treatment time is 50 minutes.
F in (e) stainless steel sealed is carried out sealing-in with after the ceramic component sealed is worked good by () under Ar atmosphere, sealing temperature is 900 DEG C, and sealing time is 60 minutes.
The detected result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10
-11pam
3s
-1; Mechanical experimental results shows, the sealing strength of closure is about 81MPa.
Embodiment 4
The pre-oxidation treatment of (a) metallic surface: with embodiment 1;
Choosing of (b) seal glass: with embodiment 1;
The preparation of (c) glass paste: with embodiment 1;
D glass paste in (c) is evenly coated on the surface at kovar alloy closure sealing-in position by (), coating method is manual application, and thickness is 1.5 ~ 2mm;
The vitrifying of (e) metal: the kovar alloy being coated with glass powder of (d) gained is placed in retort furnace, at wet N
2/ H
2gas mixture (steam H
2the content of O is 1%, H
2content be 0.5%, all the other are N
2) in heat-treat, thermal treatment temp is 800 DEG C, and heat treatment time is 50 minutes;
(f) by the kovar alloy closure in (e) with after the ceramic component sealed is worked good in N
2carry out sealing-in under atmosphere, sealing temperature is 900 DEG C, and sealing time is 80 minutes;
The detected result of helium mass spectrometer leak detector shows, the helium leak rate of closure is less than 10
-11pam
3s
-1; Mechanical experimental results shows, the sealing strength of closure is about 87MPa.
Embodiment 5
The pre-oxidation treatment of (a) metallic surface: with embodiment 1;
Choosing of (b) seal glass: with embodiment 1;
The preparation of (c) glass paste: with embodiment 1;
D glass paste in (c) is evenly coated on the surface at kovar alloy closure sealing-in position by (), coating method is manual application, and thickness is 1.5 ~ 2mm;
The vitrifying of (e) metal: the kovar alloy being coated with glass powder of (d) gained is placed in retort furnace, at wet N
2/ H
2gas mixture (steam H
2the content of O is 1%, H
2content be 1%, all the other are N
2) in heat-treat, thermal treatment temp is 1050 DEG C, and heat treatment time is 20 minutes;
F () is by the kovar alloy closure in (e) and under Ar atmosphere, carry out sealing-in after the ceramic component sealed is worked good, and sealing temperature is 800 DEG C, and sealing time is 120 minutes;
The detected result of helium mass spectrometer leak detector shows, the helium leak rate of closure is 1.2 × 10
-10pam
3s
-1; Mechanical experimental results shows, the sealing strength of closure is about 72MPa.
Industrial applicability: the seal glass that can match with it according to the different choice thermal expansivity of metal surface treatment process, has expanded the range of application of metallic glass sealing technology greatly; After metallic glass can directly and pottery carry out sealing-in, do not need additionally to add solder, simplify sealing process, decrease seal interface simultaneously, improve the reliability and stability of sealing process, the fields such as integrated antenna package, nuclear power, high energy physics, the energy, medical facilities, chemical industry, automotive industry, science and techniques of defence can be applied to.
Claims (12)
1. a method for sealing for metallic glass, is characterized in that, described method comprises:
(1) pre-treatment at metal sealing part sealing-in position: by carrying out chemical treatment to the metallic surface at metal sealing part sealing-in position to form metallic compound pretreatment layer at metal sealing part sealing-in portion faces;
(2) preparation of seal glass paste: by the matched coefficients of thermal expansion of the metallic matrix with metal sealing part and between glass ingredient and pretreatment layer can the glass of phase mutual diffusion and infiltration make glass powder after be modulated into paste with binding agent, solvent;
(3) vitrifying of metal sealing part: the surface described paste being evenly coated on described metal sealing part sealing-in position forms vitreous coating layer and heat-treats to form vitrifying layer under protective atmosphere; And
(4) metal sealing part and ceramic sealing-in: the metal sealing part of vitrifying layer will be formed and carry out sealing-in under inert atmosphere after working good in the sealing-in position of the ceramic component sealed.
2. method for sealing according to claim 1, is characterized in that, described metal comprises stainless steel, kovar alloy, Ni, Ti, Mo, Mn, Al, W and alloy thereof.
3. method for sealing according to claim 1 and 2, is characterized in that, described chemical treatment is oxidation, sulfuration, phosphatization, boronation, nitrogenize or halogenation, and the thickness of the pretreatment layer of formation is 1 ~ 10 μm.
4. the method for sealing according to any one in claims 1 to 3, is characterized in that, described chemical treatment is oxidation, and described glass is silicate glass and/or borosilicate glass.
5. the method for sealing according to any one in claims 1 to 3, is characterized in that, described chemical treatment is sulfuration, and described glass is chalcogenide glass.
6. the method for sealing according to any one in claims 1 to 3, is characterized in that, described chemical treatment is phosphatization, and described glass is phosphate glass.
7. the method for sealing according to any one in claims 1 to 3, is characterized in that, described chemical treatment is boronation, and described glass is borosilicate glass.
8. the method for sealing according to any one in claims 1 to 3, is characterized in that, described chemical treatment is nitrogenize, and described glass is Nitrogen Containing Glass.
9. the method for sealing according to any one in claims 1 to 3, is characterized in that, described chemical treatment is halogenation, and described glass is halide glass.
10. the method for sealing according to any one in claim 1 ~ 9, is characterized in that, in described step (2),
The particle diameter of described glass powder is 2 ~ 200mm;
Described binding agent is polyvinyl butyral acetal, ethyl cellulose, rosin and/or nitrocotton;
Described solvent is ethanol, acetone, Terpineol 350, N-BUTYL ACETATE, propyl carbinol and/or pimelinketone;
The weight ratio of described glass powder, binding agent, solvent is (40wt% ~ 80wt%): (2wt% ~ 10wt%): (15wt% ~ 55%).
11. method for sealing according to any one in claim 1 ~ 10, is characterized in that, in described step (3),
Described be applied to dip-coating, spraying, silk screen printing, machinery coating etc.;
Described thermal treatment is 600 ~ 1100 DEG C of insulations 10 ~ 50 minutes;
Described protective atmosphere is wet N
2/ H
2gas mixture or wet Ar/H
2gas mixture, wherein, steam H in described protective atmosphere
2the content of O is 0.3 ~ 3vol%, H
2content be 0.1 ~ 1.5vol%;
The thickness of described vitrifying layer is 0.5 ~ 3mm.
12. method for sealing according to any one in claim 1 ~ 11, it is characterized in that, in described step (4), described sealing-in is at Ar or N
2in 600 ~ 1200 DEG C of sealing-ins 30 ~ 120 minutes under atmosphere.
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| CN106735728A (en) * | 2016-11-29 | 2017-05-31 | 长春工业大学 | A kind of connection method of ceramic-lined composite steel tube |
| CN109020262A (en) * | 2018-09-20 | 2018-12-18 | 西安赛尔电子材料科技有限公司 | A kind of glass-to-metal seal radio frequency connector surface treatment method |
| CN109836056A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of geocomposite layer material and preparation method thereof for glass/metal seal interface |
| CN111850538A (en) * | 2020-08-03 | 2020-10-30 | 广东格斯泰气密元件有限公司 | Method for improving sealing strength of glass and metal |
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| CN106568465A (en) * | 2016-03-04 | 2017-04-19 | 北京玻璃研究院 | Method for packaging metal coated fiber grating |
| CN106735728A (en) * | 2016-11-29 | 2017-05-31 | 长春工业大学 | A kind of connection method of ceramic-lined composite steel tube |
| CN109836056A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of geocomposite layer material and preparation method thereof for glass/metal seal interface |
| CN109020262A (en) * | 2018-09-20 | 2018-12-18 | 西安赛尔电子材料科技有限公司 | A kind of glass-to-metal seal radio frequency connector surface treatment method |
| CN111850538A (en) * | 2020-08-03 | 2020-10-30 | 广东格斯泰气密元件有限公司 | Method for improving sealing strength of glass and metal |
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| CN104276837B (en) | 2016-09-07 |
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