CN117209169A - Laser sealing method for glass and titanium alloy by adding foam copper as transition layer - Google Patents

Laser sealing method for glass and titanium alloy by adding foam copper as transition layer Download PDF

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Publication number
CN117209169A
CN117209169A CN202311074425.2A CN202311074425A CN117209169A CN 117209169 A CN117209169 A CN 117209169A CN 202311074425 A CN202311074425 A CN 202311074425A CN 117209169 A CN117209169 A CN 117209169A
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China
Prior art keywords
glass
titanium alloy
solder
laser
copper
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CN202311074425.2A
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Inventor
陈长军
陆奕楷
张敏
徐梦璇
邵嘉琪
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Suzhou University
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Suzhou University
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Abstract

The invention relates to a laser sealing method for realizing glass and titanium alloy by adding foam copper as a transition layer, belonging to the technical field of sealing of heterogeneous materials. The invention takes TiZrNiCu as solder, and adds foam copper as intermediate transition layer to make laser sealing, and the glass-titanium alloy sealing body is prepared. In the sealing process, the foam copper is introduced as a functional gradient material while the solder is introduced into the glass and the titanium alloy, so that the problems of mismatching caused by overlarge difference of thermal expansion coefficients between the glass and the titanium alloy and the initiation sensitivity of cracks caused by difference of physical properties are effectively reduced, the thermal stress and the interface pressure between the glass and the titanium alloy are reduced, and the tolerance limits of thermal shock resistance and thermal circulation of the titanium alloy and a glass sealing body are improved.

Description

Laser sealing method for glass and titanium alloy by adding foam copper as transition layer
Technical Field
The invention relates to the technical field of sealing of heterogeneous materials, in particular to a laser sealing method for glass and titanium alloy by adding foam copper as a transition layer.
Background
The sealing of glass and metal is realized by bonding and sealing glass with sealing strips and glass strips. Or oxidizing the metal surface to form an oxide film, and then preserving heat for a long time in a heat preserving furnace under the high temperature condition to realize the sealing of glass and metal. Because of high temperature and long heat preservation time during sealing, the glass and metal performances are damaged, and the production efficiency and quality are very inconvenient to control. Compared with the traditional metal material for sealing, the titanium and titanium alloy material has the strength similar to that of high-quality steel, has the advantages of small density, light weight, high specific strength and the like, has the advantages of wide working range, corrosion resistance and the like, is known as 'twenty-first century metal', and is widely applied to the fields of aerospace, navigation, chemical industry, metallurgy, medical treatment, instruments and the like. However, the titanium alloy material has the problems of poor wettability, high-temperature phase change and the like in the process of sealing with glass, so that the existing sealing interface between the glass body and the titanium alloy has certain defects, such as a large number of microcracks generated at the defect of the sealing interface when the sealing interface is interfered by external environment changes, thereby causing the problems of poor air tightness, poor insulation resistance and the like. Meanwhile, titanium alloy is extremely easy to oxidize at high temperature, and different types of oxide layers are formed at different temperatures, so that the difficulty of subsequent surface treatment is increased. Therefore, there is still a need for a convenient and reliable sealing means for sealing glass to titanium alloy.
At present, the stability of the glass and titanium alloy sealing body under the thermal cycle load is improved, and an interlayer is adopted to release stress and reduce the formation of brittle intermetallic compounds, so that the glass and titanium alloy sealing body is an effective solution. Clearly, optimizing solder chemistry, forming gradient materials, and reducing or preventing the formation of brittle intermetallic compounds is an excellent solution.
Copper foam is a compound which is very easy to form with glass and has metal characteristics, and copper foam is also very easy to form brittle intermetallic compounds with Fe, ni and the like in metal, so that the conventional brazing solder forms brittle intermetallic compounds in a glass-metal sealing body. In order to prevent the formation of brittle intermetallic compounds, a brazing filler metal layer is added between the copper foam and the metal to form a barrier layer, so that brittle intermetallic compounds are not easy or can not be formed between the copper foam and the base metal due to the existence of the barrier layer, and the heat-resistant cyclic load resistance of the glass-metal sealing body can be further improved. Since the conventional brazing filler metal is directly composed of Ag-Cu or Ag-Cu-Ti, and this brazing filler metal is a compound having metallic characteristics, and has an advantage in that it can be combined with glass or ceramics, but forms brittle intermetallic compounds with Ti, al, ni in the base metal inevitably, it is necessary to develop a new material system instead of the existing material system.
Disclosure of Invention
In order to solve the technical problems, the invention provides a laser sealing method for realizing glass and titanium alloy by adding foam copper as a transition layer, in particular to a laser sealing method for realizing glass and titanium alloy by adding foam copper as a transition layer, which can effectively improve the strength of a sealing joint between glass and titanium alloy.
The invention is realized by the following technical scheme:
the first object of the invention is to provide a laser sealing method for glass and titanium alloy by adding foamy copper as a transition layer, which comprises the following steps,
s1: setting a processing track according to the size and shape of glass and titanium alloy to be sealed;
s2: uniformly spraying or placing solder on one side of the titanium alloy to be sealed, and placing foam copper on the solder; spraying or placing solder on the foamy copper;
the solder is TiZrNiCu powder or a TiZrNiCu foil, and the TiZrNiCu powder or the TiZrNiCu foil comprises the following components in percentage by atom: ti-5Zr-15Ni-15Cu;
the foam copper is foam copper powder or foam copper foil;
s3: placing the glass to be sealed on the titanium alloy provided with the foam copper and the solder, and ensuring that the glass to be sealed is in close contact with the titanium alloy to form a body to be sealed;
s4: and (3) clamping the to-be-sealed body obtained in the step (S3), and carrying out laser irradiation on the welding flux at the junction of the glass and the titanium alloy according to the processing track set in the step (S1) to obtain the glass-titanium alloy sealing body.
In one embodiment of the present invention, in step S1, the glass to be sealed and the titanium alloy to be sealed are obtained through the following pretreatment:
degreasing and deoiling the titanium alloy to be sealed, and then oxidizing;
and cleaning the glass to be sealed with clear water, and then cooling and air-drying.
In one embodiment of the present invention, in step S1, the titanium alloy is titanium alloy Ti6Al4V.
In one embodiment of the present invention, in step S1, the glass is high purity silica glass.
In one embodiment of the present invention, in step S2, the solder has a thickness of 20 μm to 100 μm.
In one embodiment of the present invention, in step S2, the particle size of the TiZrNiCu powder is 5 μm to 50. Mu.m.
In one embodiment of the present invention, in step S2, when the solder is TiZrNiCu powder, a copper foam foil is placed on the solder;
when the solder is TiZrNiCu foil, placing a foam copper foil or spraying foam copper powder on the solder.
Namely TiZrNiCu and copper foam can be foil at the same time, but cannot be powder at the same time when placed.
Specifically, the TiZrNiCu powder or the TiZrNiCu foil and the copper foam foil have metallic luster, and do not need oxidation treatment.
In one embodiment of the invention, in step S2, the copper foam foil has a thickness of 10 μm to 30 μm.
In one embodiment of the present invention, in step S2, the copper foam powder has a particle size of less than 10 μm and a purity of greater than 99.7%.
In one embodiment of the present invention, in step S4, the wavelength of the laser is 800nm to 1100nm.
In one embodiment of the present invention, in step S4, the parameters of the laser irradiation are: the laser scanning speed is 80mm min -1 -160mm·min -1 The method comprises the steps of carrying out a first treatment on the surface of the The laser power is 80W-160W; the pulse width is 1.5ms-3.0ms; the frequency is 5Hz-10 Hz; the scanning times are 1-3.
In one embodiment of the present invention, in step S4, the laser irradiation is performed in a protective atmosphere; specifically, the protective atmosphere is helium or argon, preferably argon.
The second object of the invention is to provide a glass-titanium alloy sealing body prepared by the laser sealing method. The glass-titanium alloy sealing body comprises glass, titanium alloy and welding flux and foam copper which are arranged between the edges of the glass and the titanium alloy and used for sealing, and the specific structural schematic diagram is shown in figure 1.
The brazing filler metal used in the invention is composed of TiZrNiCu, and the copper foam is used as a single brazing filler metal welding layer, so that a barrier layer is formed between a metal matrix and the copper foam, and brittle intermetallic compounds are prevented from being formed between the copper foam and the matrix. Therefore, the TiZrNiCu is used as the brazing filler metal and the foam copper is used as the transition layer to seal the glass and the titanium alloy, so that the performance of the titanium alloy and the glass sealing body, particularly the performance of heat shock resistance, can be further improved.
Compared with the prior art, the technical scheme of the invention has the following advantages:
in the sealing process, the foam copper is introduced as a functional gradient material while the solder is introduced into the glass and the titanium alloy, so that the problems of mismatching caused by overlarge difference of thermal expansion coefficients between the glass and the titanium alloy and the initiation sensitivity of cracks caused by difference of physical properties are effectively reduced, the thermal stress and the interface pressure between the glass and the titanium alloy are reduced, and the tolerance limits of thermal shock resistance and thermal circulation of the titanium alloy and a glass sealing body are improved.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings, in which
FIG. 1 is a schematic view of a material combination of the closure of the present invention;
description of the specification reference numerals: 1. a titanium alloy steel sheet; 2. solder; 3. foam Ni; 4. glass.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
The embodiment provides a laser sealing method for realizing glass and titanium alloy by adding foam copper as a transition layer, which comprises the following specific steps:
s1: taking a window glass sample with the thickness of 8mm multiplied by 20mm multiplied by 4mm as glass to be sealed, taking a titanium alloy Ti6Al4V steel plate with the thickness of 10mm multiplied by 25mm multiplied by 1.5mm as the titanium alloy Ti6Al4V to be sealed, setting a processing track, and preparing a welding fixture;
s2: degreasing and deoiling the titanium alloy Ti6Al4V to be sealed, and then oxidizing; cleaning the glass to be sealed with clear water, and then cooling and air-drying;
s3: taking a TiZrNiCu foil with the thickness of about 20 mu m as solder, placing the solder on one side of Ti6Al4V of the titanium alloy to be sealed, and spraying foam copper powder with the thickness of 11 mu m on the solder; wherein the TiZrNiCu foil comprises the following components in atom percent: ag-42.44at% Cu-7.56at% Sn, and has metallic luster, and no special treatment is needed; the purity of the foam copper powder is more than 99.7%;
s4: placing the glass to be sealed on titanium alloy Ti6Al4V provided with foam copper and solder, and ensuring that the glass to be sealed is in close contact with the titanium alloy Ti6Al4V to form a body to be sealed; a layer of TiZrNiCu foil with the thickness of about 20 mu m is placed on the foam copper powder;
s5, performing S5; the welding fixture clamps the body to be sealed in the step S4 according to the requirement, and laser sealing preparation is carried out;
S6:adopting a fiber laser with the wavelength of 1064nm, and setting laser processing parameters of the fiber laser as follows: laser scanning speed 100mm min -1 The laser power is 110W, the pulse width is 1.5ms, the frequency is 7Hz, and the scanning times are 1-3 tracks;
the laser device sets a processing track according to the step S1: scanning the solder with the scanning length of 78mm (X direction) and 18mm (Y direction), and irradiating the solder at the junction of the glass and the titanium alloy Ti6Al4V at the position 2mm away from the solder in the argon atmosphere, wherein the solder plays a role of glue, so that a glass-titanium alloy Ti6Al4V sealing body is prepared;
s7: and (5) dismantling the welding clamp to finish the whole laser sealing operation flow.
The test shows that the shear strength of the glass-titanium alloy Ti6Al4V sealing body obtained by the laser sealing method of the embodiment can reach 30MPa.
And (3) carrying out a thermal fatigue experiment by taking the sealing body without the foam copper layer as a comparison, wherein the experimental method is that the sealing body with and without the foam copper layer is simultaneously put into a heat preservation furnace for heat preservation, after 12min of heat preservation, the sealing body is taken out and placed at normal temperature, and is blown to cool by a fan for 20 min, and after the temperature of the sealing body becomes the room temperature, the sealing body is put into the furnace for heat preservation for 12min, and the process is repeated. Wherein after each 5 times of the process, the sealing body at room temperature is subjected to one-time coloring inspection to check whether cracks exist.
The results show that under the conditions of this example, no cracking of the copper foam layer occurred and the seal failed at 5 cycles. And the copper foam layer is added, so that cracks do not appear at the time of 5 cycles, and only appear at the time of 10 th cycle. Meanwhile, the traditional sealing body without solder needs to oxidize titanium alloy at high temperature, and the sealing body adopting Ag-Cu as the solder fails when more than one cycle is performed.
Example 2
The present embodiment provides a laser sealing method for glass and titanium alloy by adding copper foam as a transition layer, which is similar to the method of embodiment 1, and is different in that:
adopted byThe TiZrNiCu solder has a thickness of 32 μm, the solder is in the form of powder, a foam copper foil is placed on the powder, the foam copper foil has a thickness of 15 μm, an Nd-YAG type laser with a wavelength of 1000nm is adopted, the Nd-YAG type laser is set with a processing track of 78mm (X direction) and 18mm (Y direction) of scanning length, and laser parameters are set as follows: laser scanning speed 40mm min -1 The laser power was 130W, the pulse width was 2.5ms, the frequency was 10Hz, the number of scans was 1-3, and the laser sealing operation was performed on glass and titanium alloy Ti6Al4V at a distance of 1mm from the solder.
The test shows that the shearing strength of the glass-titanium alloy Ti6Al4V sealing body obtained by the laser sealing method of the embodiment can reach 37MPa.
The thermal fatigue test was performed by comparing the sealing body without the copper foam layer, and the result shows that under the condition of the embodiment, no crack appears on the copper foam layer and the sealing body fails when the copper foam layer is added for 10 times of circulation. And the copper foam layer is added, so that cracks do not appear at 15 times of cycles, and only appear at 20 times of cycles. Meanwhile, the traditional sealing body without solder needs to oxidize titanium alloy at high temperature, and the sealing body adopting Ag-Cu as the solder fails when more than one cycle is performed.
Example 3
The present embodiment provides a laser sealing method for glass and titanium alloy by adding copper foam as a transition layer, which is similar to the method of embodiment 1, and is different in that:
the thickness of the TiZrNiCu solder is 45 mu m, the TiZrNiCu is in the form of a foil, and a layer of foam copper foil is covered on the TiZrNiCu, and the thickness is 20 mu m. A semiconductor laser having a wavelength of 940nm was used, the processing track set for the semiconductor laser was 78mm (X direction) and 18mm (Y direction) in scanning length, and the laser parameters were set as: laser scanning speed 160mm min -1 The laser power was 160W, the pulse width was 1.8ms, the frequency was 8Hz, the number of scans was 1-3, and the laser sealing operation was performed on glass and titanium alloy Ti6Al4V at a distance of 3mm from the solder.
The test shows that the shearing strength of the glass-titanium alloy Ti6Al4V sealing body obtained by the laser sealing method of the embodiment can reach 44MPa.
The thermal fatigue test was performed by comparing the sealing body without the copper foam layer, and the result shows that under the condition of the embodiment, no crack appears on the copper foam layer and the sealing body fails when the copper foam layer is added for 20 times of circulation. And the copper foam layer is added, so that cracks do not appear at 25 times of cycles, and only appear at 30 times of cycles. Meanwhile, the traditional sealing body without solder needs to oxidize titanium alloy at high temperature, and the sealing body adopting Ag-Cu as the solder fails when more than one cycle is performed.
Example 4
The present embodiment provides a laser sealing method for glass and titanium alloy by adding copper foam as a transition layer, which is similar to the method of embodiment 1, and is different in that:
the TiZrNiCu component of the solder used was 70 μm thick and the TiZrNiCu was in the form of powder covered with a copper foam foil and 25 μm thick, a semiconductor laser having a wavelength of 810nm was used which was set to a processing track of 78mm (X direction) and 18mm (Y direction) in scanning length, and the laser parameters were set to: laser scanning speed is 163 mm/min -1 Laser power 161W, pulse width 1.9ms, frequency 9Hz, number of scans 1-3, and laser sealing operation of glass and titanium alloy Ti6Al4V at a distance of 3mm from the solder.
The test shows that the shearing strength of the glass-titanium alloy Ti6Al4V sealing body obtained by the laser sealing method of the embodiment can reach 46MPa.
The thermal fatigue test was performed by comparing the sealing body without the copper foam layer, and the result shows that under the condition of the embodiment, no crack appears on the copper foam layer and the sealing body fails when the copper foam layer is added for 25 times of circulation. And the copper foam layer is added, so that cracks do not appear at 30 times of cycles, and only appear at 35 times of cycles. Meanwhile, the traditional sealing body without solder needs to oxidize titanium alloy at high temperature, and the sealing body adopting Ag-Cu as the solder fails when more than one cycle is performed.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.

Claims (10)

1. A method for realizing laser sealing of glass and titanium alloy by adding foamy copper as a transition layer is characterized by comprising the following steps,
s1: setting a processing track according to the size and shape of glass and titanium alloy to be sealed;
s2: uniformly spraying or placing solder on one side of the titanium alloy to be sealed, and placing foam copper on the solder; spraying or placing solder on the foamy copper;
the solder is TiZrNiCu powder or a TiZrNiCu foil, and the TiZrNiCu powder or the TiZrNiCu foil comprises the following components in percentage by atom: ti-5Zr-15Ni-15Cu;
the foam copper is foam copper powder or foam copper foil;
s3: placing the glass to be sealed on the titanium alloy provided with the foam copper and the solder, and ensuring that the glass to be sealed is in close contact with the titanium alloy to form a body to be sealed;
s4: and (3) clamping the to-be-sealed body obtained in the step (S3), and carrying out laser irradiation on the welding flux at the junction of the glass and the titanium alloy according to the processing track set in the step (S1) to obtain the glass-titanium alloy sealing body.
2. The laser sealing method according to claim 1, wherein in step S1, the glass to be sealed and the titanium alloy to be sealed are obtained by the following pretreatment:
degreasing and deoiling the titanium alloy to be sealed, and then oxidizing;
and cleaning the glass to be sealed with clear water, and then cooling and air-drying.
3. The laser sealing method according to claim 1, wherein in step S2, the thickness of the solder is 20 μm to 100 μm.
4. The laser sealing method according to claim 1, wherein in the step S2, the particle size of the TiZrNiCu powder is 5 μm to 50 μm.
5. The laser sealing method according to claim 1, wherein in the step S2, when the solder is TiZrNiCu powder, a copper foam foil is placed on the solder;
when the solder is TiZrNiCu foil, placing a foam copper foil or spraying foam copper powder on the solder.
6. The laser sealing method according to claim 1, wherein in step S2, the thickness of the copper foam foil is 10 μm to 30 μm.
7. A laser sealing method according to claim 1, wherein in step S4, the wavelength of the laser light is 800nm to 1100nm.
8. A laser sealing method according to claim 1, wherein in step S4, the parameters of the laser irradiation are: the laser scanning speed is 80mm min -1 -160mm·min -1 The method comprises the steps of carrying out a first treatment on the surface of the The laser power is 80W-160W; the pulse width is 1.5ms-3.0ms; the frequency is 5Hz-10 Hz; the scanning times are 1-3.
9. The method of claim 1, wherein the laser irradiation is performed in a protective atmosphere in step S4.
10. A glass-titanium alloy seal produced by the laser sealing method of any one of claims 1-9.
CN202311074425.2A 2023-08-24 2023-08-24 Laser sealing method for glass and titanium alloy by adding foam copper as transition layer Pending CN117209169A (en)

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Publication number Priority date Publication date Assignee Title
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Publication number Priority date Publication date Assignee Title
CN110981224A (en) * 2019-12-06 2020-04-10 西安赛尔电子材料科技有限公司 Sealing method of titanium-glass sealing assembly
CN113231706A (en) * 2021-06-25 2021-08-10 哈尔滨工业大学 Method for assisting in brazing dissimilar materials by using three-dimensional negative expansion network composite interlayer material
CN114713926A (en) * 2022-03-04 2022-07-08 湘潭大学 Connecting method for nested split-type assembled special-shaped carbon/carbon and metal composite heat dissipation long pipe
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