CN115780940A - Zirconium alloy welding method - Google Patents

Abstract

The present disclosure relates to the field of welding technology, and discloses a zirconium alloy welding method, including: using zirconium alloy as a base material, performing electrochemical hydrogen charging treatment on at least one side surface of the base material to form at least one hydrogen charging surface correspondingly, The first base material to be welded is obtained; the first base material to be welded is brazed on the hydrogen-filled surface of the first base material to be welded. In the present disclosure, at least one side of the zirconium alloy is electrochemically charged with hydrogen to obtain a first base material to be welded with at least one hydrogen-filled surface, and then the hydrogen-charged surface of the first base material to be welded is subjected to the first base material to be welded. The brazing of the base material at least achieves the effect of being able to weld the zirconium alloy at a lower temperature, and can enhance the bonding strength of the welding interface of the zirconium alloy, thereby improving the mechanical properties of the welded joint.

Description

Zirconium alloy welding method

technical field

The present disclosure relates to the field of welding technology, for example, relates to a zirconium alloy welding method.

Background technique

In recent years, global nuclear energy has developed rapidly. Nuclear power is both high-efficiency and clean, and it is the clean energy with the greatest development potential in the future. As the "first metal in the atomic energy age", zirconium alloys are widely used in common structural components in the nuclear industry, such as fuel elements for water-cooled nuclear reactors, due to their small thermal neutron absorption cross-section, good processability and excellent corrosion resistance. cladding materials, core structural materials and pressure tubes, etc. Therefore, realizing the reliable connection of zirconium alloy and giving full play to its high-quality performance has become a key area of nuclear power technology development.

However, there are still several problems in the welding of zirconium alloys:

1. The atomic diffusion and solubility of zirconium alloys are poor, so the mechanical properties of zirconium alloys at welded joints are poor;

2. The high thermal processing temperature makes the zirconium alloy prone to phase transformation during thermal processing, resulting in reduced strength and grain growth;

3. The hardness of the weld is small, and the performance difference between the weld and the base material is large.

To sum up, there is an urgent need for a zirconium alloy welding method to achieve welding of zirconium alloys at a lower temperature, and to enhance the bonding strength of the zirconium alloy welding interface, thereby improving the mechanical properties of the welded joint Effect.

Contents of the invention

The purpose of the present disclosure is to overcome the deficiencies of the prior art, to provide a welding method for zirconium alloys, to at least achieve the welding of zirconium alloys at a lower temperature, and to enhance the bonding strength of the welding interface of zirconium alloys, thereby The effect of improving the mechanical properties of welded joints.

The purpose of this disclosure is achieved through the following technical solutions:

In one aspect, a zirconium alloy welding method is provided. The welding method includes: using zirconium alloy as the base material, performing electrochemical hydrogen charging treatment on at least one side surface of the base material, so as to form at least one hydrogen charging surface correspondingly, and obtain the first base material to be welded; The hydrogen-filled surface of the first base material to be welded is brazed to the first base material to be welded.

In the above embodiment, by performing the electrochemical hydrogen charging treatment on at least one side surface of the substrate (that is, the zirconium alloy), hydrogen can be added to the substrate (that is, the zirconium alloy). alloy), thereby correspondingly obtaining the first base material to be welded with at least one hydrogen-filled surface; at this time, the hydrogen-filled surface has a certain content of hydride, so it can be seen that on the hydrogen-filled surface , the hydrogen element changes the phase composition and microstructure of the zirconium alloy. Therefore, when the hydrogen-charged surface of the first substrate to be welded is brazed to the first substrate to be welded, on the one hand, the diffusion ability of the hydrogen element to improve the diffusion of the liquid solder and the zirconium alloy in the zirconium alloy are utilized. The role of the solubility of the element makes the interface reaction more fully, thereby enhancing the bonding strength of the welding interface, and finally improving the mechanical properties of the welded joint; on the other hand, the principle of induced diffusion and dissolution of hydrogen can also be used , to achieve the purpose of high-performance brazing of zirconium alloys at lower temperatures. In addition, the method of adding hydrogen element to at least one surface of the substrate (ie, the zirconium alloy) by using the electrochemical hydrogen charging treatment has the advantages of being stable and easy to implement.

In some embodiments, the electrolytic solution used in the electrochemical hydrogen charging treatment is a sulfuric acid solution added with thiourea; wherein, the concentration of the sulfuric acid is 0.5-1 mol/L, and the concentration of the thiourea is 0.02- 0.04mol/L.

In the above embodiment, the preparation method of the sulfuric acid solution added with thiourea has the advantages of simple operation and low cost. In some embodiments, the conditions of the electrochemical hydrogen charging treatment include: a temperature of 25-35° C., a time of 1-720 min, and a current density of 80-120 mA/cm ² .

It should be noted that, the embodiment of the present disclosure does not limit the conditions of the electrochemical hydrogen charging treatment, which can be selected and set according to needs.

In some embodiments, before performing the electrochemical hydrogen charging treatment, a step of pre-treating the substrate is also included. Wherein, the pretreatment includes: sequentially polishing, disinfecting and drying the base material to obtain a sample; performing sample sealing treatment on the sample to obtain the base material to be charged with hydrogen.

In some examples, the sample sealing treatment includes: wrapping the sample with conductive glue, connecting wires to the wrapped sample, and performing the electrochemical hydrogen charging treatment on the sample after connecting the wires. Seal other parts than the surface.

In some embodiments, brazing the first base material to be welded on the hydrogen-filled surface of the first base material to be welded includes: using the brazing filler metal foil to braze the second base material to be welded One side of the surface and the hydrogen-filled surface of the first substrate to be welded are brazed.

It should be noted that, in this case, the time for the electrochemical hydrogen charging treatment may be, for example, 1-240 min.

In some embodiments, at least one side surface of the second base material to be welded is a hydrogen-filled surface, and the preparation method of the second base material to be welded is the same as that of the first base material to be welded. On this basis, brazing one side surface of the second base material to be welded and the hydrogen-filled surface of the first base material to be welded includes: brazing the hydrogen-charged surface of the second base material to be welded and the hydrogen-filled surface The hydrogen-filled surface of the first substrate to be welded is brazed.

In the above embodiment, by providing two substrates to be welded with hydrogen-filled surfaces (that is, a first substrate to be welded with a hydrogen-charged surface and a second substrate to be welded with a hydrogen-charged surface), and the two Brazing on the hydrogen-filled surface of the former can simultaneously improve the dissolving ability of the elements in the two zirconium alloys to be welded, and further improve the diffusion ability of the liquid solder, so that the interface reaction occurs more fully, thereby further enhancing the welding interface. The bond strength, and ultimately further improve the mechanical properties of welded joints. At the same time, since the diffusion ability of the liquid solder and the dissolution ability of the elements in the zirconium alloy have been further improved, it is more conducive to the high-performance brazing of the zirconium alloy at a lower temperature.

In some embodiments, the second substrate to be welded is a zirconium alloy.

It should be noted that, in this case, the time for the electrochemical hydrogen charging treatment may be, for example, 1-720 min.

In some embodiments, the solder foil is an Ag-Cu-Ti ternary active solder foil; wherein, the copper content of the Ag-Cu-Ti ternary active solder foil is 26.7% to 27% %, the titanium content of the Ag-Cu-Ti ternary active solder foil is 2%-4.5%.

In the above embodiments, by selecting the Ag-Cu-Ti ternary active solder foil, the activity and wettability of the welding interface can be enhanced by using Ti as an active component, thereby improving the mechanical properties of the welding joint.

It should be noted that there are many types of the above-mentioned Ag-Cu-Ti ternary active solder foil, which can be selected according to actual needs, as long as the requirements of the above-mentioned embodiments can be guaranteed. For example, the above-mentioned Ag-Cu-Ti ternary active solder foil may be an AgCuTi3.3 solder foil.

In some embodiments, the liquidus of the solder foil is in the range of 770-810°C.

In some embodiments, the thickness of the solder foil is 20-500 μm.

In the above embodiments, by controlling the thickness of the solder foil, the mechanical properties of the welded joint can be guaranteed.

In some embodiments, the brazing is vacuum brazing; the vacuum brazing conditions include: a temperature of 790-850° C., a holding time of 10-30 minutes, and a vacuum degree higher than 2×10 ^-3 .

In the above embodiments, by limiting the conditions of the vacuum brazing, the completion of the brazing and the mechanical properties of the welded joint can be guaranteed.

It should be noted that the conditions of the above vacuum brazing can be selected according to actual needs, as long as the requirements of the above embodiments can be ensured.

In some examples, in the vacuum brazing condition, the temperature is 790°C.

In some examples, in the vacuum brazing condition, the holding time is 10 minutes.

In some examples, in the vacuum brazing conditions, the degree of vacuum is 3×10 ^-3˜5 ×10 ^-3 .

In some embodiments, the zirconium alloy is Zr-4 alloy.

To sum up, the embodiment of the present disclosure performs the electrochemical hydrogen charging treatment on at least one side surface of the substrate (that is, the zirconium alloy) to obtain the first hydrogen charging surface. The base material to be welded, and then brazing the first base material to be welded on the hydrogen charging surface of the first base material to be welded can promote the diffusion of solder elements and the formation of elements in the zirconium alloy at a lower temperature. Dissolving, changing the distribution form and state of intermetallic compounds, thereby enhancing the bonding strength of the welding interface, and ultimately improving the mechanical properties of the welded joint.

It should be noted that, although there is already a technical solution in the related art that adopts electrochemical hydrogen charging treatment to treat the surface of zirconium alloy, and then performs diffusion welding to improve the interfacial diffusion rate of zirconium alloy, it is different from that provided by the present disclosure. The welding methods are essentially different. Specifically:

The brazing in the embodiments of the present disclosure is to form a connection through the wetting and filling diffusion of liquid brazing material; at the same time, the brazing of the zirconium alloys that have undergone the electrochemical hydrogen charging treatment provided in the embodiments of the present disclosure The technical solution of welding is mainly to use hydrogen to improve the diffusion ability of liquid solder, and to improve the ability of the elements in the two zirconium alloy substrates to be welded to dissolve and diffuse in liquid form, thereby promoting the intermetallic of the welding interface. Compound generation reaction, in this case, a variety of intermetallic compound phases are generated at the welding interface and welded joints, which can enhance the bonding strength of the welding interface and the mechanical properties of the welded joint, and finally play a role in interface strengthening.

However, the diffusion welding in the related art is a kind of solid phase welding. When carrying out diffusion welding to the zirconium alloy base material, the surface and the middle layer of the zirconium alloy base material are all in solid phase. In this case, the The two zirconium alloy substrates are connected through the diffusion of zirconium elements and the bridging of pores. At this time, there is no interfacial reaction at the welding interface, and no intermetallic compounds are generated; The technical scheme of hydrogen-treated zirconium alloy diffusion welding is only to introduce hydrogen element at the welding interface, and use the defect of hydrogen atom vacancy to improve the diffusion efficiency of zirconium element.

It can be seen that the technical solutions provided by the related art are essentially different from the technical solutions provided by the present disclosure in terms of mechanism of action and reaction form. Therefore, the related art does not serve as any reference for the present disclosure.

A zirconium alloy welding method provided by the present disclosure has the following beneficial effects:

1. A method for welding zirconium alloys according to the present disclosure, by performing the electrochemical hydrogen charging treatment on at least one side of the base material (that is, the zirconium alloy), so as to obtain the welding process with at least one hydrogen charging surface. The first base material to be welded, and then brazing the first base material to be welded on the hydrogen-filled surface of the first base material to be welded, the hydrogen element can be used to improve the diffusion ability of the liquid solder and the elements in the zirconium alloy The dissolving ability makes the interface reaction more fully, thereby enhancing the bonding strength of the welding interface, and finally improving the mechanical properties of the welded joint.

2. A zirconium alloy welding method disclosed in the present disclosure achieves the purpose of high-performance brazing of zirconium alloys at a relatively low temperature by improving the diffusion ability of liquid solder and the solubility of elements in the zirconium alloy.

Description of drawings

In order to illustrate the technical solutions in the present disclosure more clearly, the following will briefly introduce the accompanying drawings used in some embodiments of the present disclosure. Apparently, the accompanying drawings in the following description are only appendices to some embodiments of the present disclosure. Figures, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings. In addition, the drawings in the following description can be regarded as schematic diagrams, and are not intended to limit the actual size of the product involved in the embodiment of the present disclosure, the actual flow of the method, and the like.

1 is a schematic diagram of an electrochemical hydrogen charging process according to some embodiments of the present disclosure;

2 is a schematic diagram of a welding process according to some embodiments of the present disclosure;

Fig. 3 is the test result figure in the 4th part of the test effect of the present disclosure; Wherein, (a) is the test result figure of comparative example 1, (b) is the test result figure of embodiment 3, (c) is embodiment The test result figure of 4, (d) is the test result figure of comparative example 3, (e) is the test result figure of embodiment 1, (f) is the test result figure of embodiment 2;

Fig. 4 is the test result figure in the 5th part of the test effect of the present disclosure; Wherein, (a) is the zirconium alloy surface morphology that has not been treated with electrochemical hydrogenation, (b) is the electrochemical hydrogenation treatment through 1h The surface morphology of the zirconium alloy, (c) is the surface morphology of the zirconium alloy after 4h electrochemical hydrogen charging treatment, (d) is the surface morphology of the zirconium alloy after 24h electrochemical hydrogen charging treatment.

Detailed ways

The following will clearly and completely describe the technical solutions in some embodiments of the present disclosure. Obviously, the described embodiments are only some of the embodiments of the present disclosure, rather than all the embodiments. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments provided in the present disclosure belong to the protection scope of the present disclosure.

Unless the context requires otherwise, throughout the specification and claims, the term "comprising" is interpreted in an open and inclusive sense, ie "including, but not limited to". In the description of the specification, the terms "one embodiment", "some embodiments", "exemplary embodiments", "example", "specific examples" or "some examples" are intended to indicate A particular feature, structure, material, or characteristic is included in at least one embodiment or example of the present disclosure. Schematic representations of the above terms are not necessarily referring to the same embodiment or example. Furthermore, the particular features, structures, materials or characteristics described may be included in any suitable manner in any one or more embodiments or examples.

Hereinafter, the terms "first" and "second" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of indicated technical features. Thus, a feature defined as "first" and "second" may explicitly or implicitly include one or more of these features. In the description of the embodiments of the present disclosure, unless otherwise specified, "plurality" means two or more.

In describing some embodiments, the expression "A and/or B" may be used. It is easy to understand that "A and/or B" includes the following three combinations: only A, only B, and a combination of A and B.

Example 1

A welding method for zirconium alloys, comprising: S1-S2.

S1. The preparation of the first substrate to be welded comprises the following steps:

S11. Preparation of electrolyte: use a glass rod to mix 98% concentrated sulfuric acid and deionized water at a volume ratio of about 27:973 under constant stirring, then add an appropriate amount of thiourea, and continue stirring at room temperature until the thiourea is dissolved , solution clarification, obtains electrolytic solution, this electrolytic solution is the sulfuric acid solution of 1mol/L, and contains 2g thiourea in every liter of electrolytic solution;

S12. Pretreatment: use Zr-4 as the base material, use sandpaper to polish the surface of the base material that needs to be electrochemically charged with hydrogen, and then put it into a beaker filled with alcohol for ultrasonic cleaning for 5 minutes for disinfection. Then wash away the particles and impurities on the surface and dry to obtain the sample; use conductive glue to wrap the sample, and connect the wire on the wrapped sample, and then use semi-flowing silicone rubber to remove the impurities in the sample after connecting the wire. Seal the parts other than the surface that needs to be electrochemically charged with hydrogen, and after it is solidified, the base material to be charged with hydrogen is obtained;

S13. Electrochemical hydrogen charging treatment: as shown in Figure 1, the platinum electrode 2 and the base material 3 to be hydrogen charged are put into the beaker containing the electrolyte solution prepared in S11, and the beaker is put into the water bath 4, Turn on the power supply 1, and turn on the power until the hydrogen charging is completed; wherein, the conditions of the electrochemical hydrogen charging treatment include: the temperature is 30±2°C, the time is 4h, and the current density is 100mA/cm ² ;

S2. Welding: As shown in Figure 2, the hydrogen-filled surface of the first base material 5 to be welded is opposite to one side surface of the second base material 6 to be welded, and a solder foil 7 is added between the two, and the solder The area of the material foil is slightly larger than the area of the hydrogen-filled surface of the first base material to be welded and the surface of the second base material to be welded, and the three are put into the clamping device 8, and finally welded by vacuum brazing ; Wherein, the second base material to be welded is Zr-4 alloy; the brazing filler metal foil is AgCuTi3.3 brazing filler metal foil, and its liquidus line is at 777～778 ℃, and thickness is 50 μ m; The conditions of vacuum brazing include: temperature The temperature is 790°C, the holding time is 10min, and the vacuum degree is 5×10 ^-3 Pa.

Example 2

In the welding method provided in this embodiment, other steps and conditions are the same as those in Embodiment 1 except that the electrochemical hydrogen charging treatment is performed for 12 hours.

Example 3

A welding method for zirconium alloys, comprising: S1-S2.

S1. The preparation of the first base material to be welded and the second base material to be welded, wherein the preparation of any one of the first base material to be welded and the second base material to be welded comprises the following steps:

S11. Preparation of electrolyte: use a glass rod to mix 98% concentrated sulfuric acid and deionized water at a volume ratio of about 27:973 under constant stirring, then add an appropriate amount of thiourea, and continue stirring at room temperature until the thiourea is dissolved , solution clarification, obtains electrolytic solution, this electrolytic solution is the sulfuric acid solution of 1mol/L, and contains 2g thiourea in every liter of electrolytic solution;

S12. Pretreatment: use Zr-4 as the base material, use sandpaper to polish the surface of the base material that needs to be electrochemically charged with hydrogen, and then put it into a beaker filled with alcohol for ultrasonic cleaning for 5 minutes for disinfection. Then wash away the particles and impurities on the surface and dry to obtain the sample; use conductive glue to wrap the sample, and connect the wire on the wrapped sample, and then use semi-flowing silicone rubber to remove the impurities in the sample after connecting the wire. Seal the parts other than the surface that needs to be electrochemically charged with hydrogen, and after it is solidified, the base material to be charged with hydrogen is obtained;

S13. Electrochemical hydrogen charging treatment: as shown in Figure 1, the platinum electrode 2 and the base material 3 to be hydrogen charged are put into the beaker containing the electrolyte solution prepared in S11, and the beaker is put into the water bath 4, Turn on the power supply 1, and turn on the electricity until the hydrogen charging is completed; the conditions for the electrochemical hydrogen charging treatment include: the temperature is 30±2°C, the time is 1min, and the current density is 100mA/cm ² ;

S2. Welding: The hydrogen-filled surface of the first base material 5 to be welded is opposite to the hydrogen-filled surface of the second base material 6 to be welded, and a solder foil 7 is added between the two, and the area of the solder foil is approximately Greater than the area of both the hydrogen-filled surface of the first base material to be welded and the hydrogen-filled surface of the second base material to be welded, the three are put into the clamping device 8, and finally the vacuum brazing method is used for welding; wherein, brazing The material foil is AgCuTi3.3 solder foil, the liquidus range is 777-778°C, and the thickness is 50μm; the vacuum brazing conditions include: temperature 790°C, holding time 10min, vacuum degree 3× 10 ^-3 Pa.

Example 4

In the welding method provided in this embodiment, other steps and conditions are the same as in Embodiment 3 except that the electrochemical hydrogen charging treatment time is 4 hours.

Comparative example 1

A zirconium alloy welding method includes S100-S200.

S100. Use Zr-4 as the base material, process the base material into a size of 20mm*10mm*3mm, smooth the surface with sandpaper, then put it into a beaker filled with alcohol and ultrasonically clean it for 5 minutes for disinfection, and then wash it away The particles and impurities on the surface are dried to obtain the base material to be welded;

S200. The surfaces of the two substrates to be welded are opposite, and a solder foil is added between the two, and the area of the solder foil is slightly larger than the surface area of the two substrates to be welded, and finally vacuum brazing is used Welding; among them, the solder foil is AgCuTi3.3 solder foil, its liquidus range is 777-778 ° C, and the thickness is 50 μm; the conditions of vacuum brazing include: the temperature is 790 ° C, the holding time is 10 minutes, The degree of vacuum is 3×10 ^-3 Pa.

Comparative example 2

In the welding method provided in this comparative example, other steps and conditions are the same as in Example 3 except that the electrochemical hydrogen charging treatment time is 12 hours.

Comparative example 3

In the welding method provided in this comparative example, other steps and conditions are the same as in Example 3 except that the electrochemical hydrogen charging treatment time is 24 hours.

Comparative example 4

In the welding method provided in this comparative example, other steps and conditions are the same as in Example 3 except that the electrochemical hydrogen charging treatment time is 8 hours.

Experimental effect

1. In order to verify the influence of the electrochemical hydrogen charging treatment in the welding method of the present disclosure on the mechanical properties of the welded joint, the shearing of the welded joint of the zirconium alloy obtained by welding according to the welding method in Example 3 and Comparative Example 1 respectively Strength was tested. The results are shown in the table below:

group Shear strength MPa Example 3 161 Comparative example 1 152

As can be seen from the above table, under the same experimental conditions, compared to the shear strength of the welded joint of the zirconium alloy obtained by welding according to the welding method of comparative example 1, according to the welding method of embodiment 3 (the time of electrochemical hydrogen charging treatment) The shear strength of the zirconium alloy welded joint obtained by welding for 1 min) increases slightly, which shows that the electrochemical hydrogen charging treatment in the welding method of the present disclosure can improve the shear strength of the welded joint.

2. In order to verify the influence of the time of the electrochemical hydrogen charging treatment on the mechanical properties of the welded joint in the welding method of the present disclosure, the welding of the zirconium alloys obtained by welding according to the welding methods in Example 4 and Comparative Examples 2-4 were carried out respectively. The shear strength of the joints was tested. The results are shown in the table below:

group Shear strength MPa Example 4 182 Comparative example 4 123 Comparative example 2 57 Comparative example 3 26

It can be seen from the above table that as the electrochemical hydrogen charging treatment time prolongs, the shear strength of the welded zirconium alloy welded joints increases first and then decreases, which shows that the electrochemical hydrogen charging treatment time is too long. In the long run, there are too many defects such as pores and cracks at the welded joints of zirconium alloys, and the negative effects of these defects are greater than the promotion of hydrogen for diffusion and dissolution, so it will seriously affect the mechanics of welded joints of zirconium alloys performance. Wherein, the electrochemical hydrogen charging treatment time in Example 4 is 4 hours, and the shear strength of the zirconium alloy welded joint can reach 182 MPa.

3. In order to verify the influence of the time of the electrochemical hydrogen charging treatment in the welding method of the present disclosure and the quantity of the welded hydrogen charging surface on the mechanical properties of the welded joint, according to Examples 1, 2, 4 and Comparative Example 2 respectively The shear strength of the welded joints of zirconium alloys obtained by welding in the welding method was tested. The results are shown in the table below:

group Shear strength MPa Example 1 164 Example 2 167 Example 4 182 Comparative example 2 57

As can be seen from the above table, the shear strength of the welded joint of the zirconium alloy obtained by welding according to the welding method of Example 4 (the time of electrochemical hydrogen charging treatment is 4h, and the number of welded hydrogen charging surfaces is 2) is higher than that according to the implementation The shear strength of the welded joint of the zirconium alloy obtained by welding the welding method of example 1 (the time of electrochemical hydrogen charging treatment is 4h, and the quantity of the welded hydrogen charging surface is 1), while according to the welding method of comparative example 2 (electrochemical hydrogen charging is 1) The time of chemical hydrogen charging treatment is 12h, and the quantity of welded hydrogen charging surface is 2) the shear strength of the welded joint of the zirconium alloy obtained by welding is significantly lower than the welding method according to embodiment 2 (the time of electrochemical hydrogen charging treatment is 12h, and the number of welded hydrogen-filled surfaces is 1) the shear strength of the welded joint of the zirconium alloy obtained by welding. It can be seen that, when the time of electrochemical hydrogen charging treatment is suitable, the improvement of the number of hydrogen charging surfaces can improve the shear strength of the welded joint of zirconium alloy; and when the time of electrochemical hydrogen charging treatment is too long, An increase in the number of hydrogen-filled surfaces will adversely affect the shear strength of the zirconium alloy welded joint.

4. In order to verify the influence of the electrochemical hydrogen charging treatment in the welding method of the present disclosure on the microstructure of the welded joint, the welding of the zirconium alloys obtained by welding according to the welding methods in Examples 1 to 4 and Comparative Examples 1 and 3 were carried out respectively. The microstructure of the joints was tested.

As a result, as shown in Figure 3, observing the weld structures of Examples 1-4 and Comparative Examples 1 and 3, it can be found that the interface structure of the welded joint of the zirconium alloy obtained by welding according to the welding method of Examples 1-4 is continuous and dense, In addition, the solder and the base materials on both sides have achieved good metallurgical bonding, while the interface bonding effect of the zirconium alloy welded joint obtained by welding according to the welding methods of Comparative Examples 1 and 3 is relatively poor.

5. In order to verify the influence of the electrochemical hydrogen charging treatment on the surface morphology of the hydrogen charging surface in the welding method of the present disclosure, the surface morphology of the zirconium alloy that has not undergone electrochemical hydrogen charging treatment, and after 1h, 4h, and 24h respectively The surface morphology of the electrochemical hydrogen-charged zirconium alloys was tested.

The results are shown in Figure 4. Compared with the zirconium alloy without electrochemical hydrogen charging treatment, as the electrochemical hydrogen charging treatment time prolongs, the block-like protrusions on the surface of the zirconium alloy gradually increase, which proves that there are more and more More hydrogen elements are charged into the surface of the zirconium alloy.

In summary, a zirconium alloy welding method disclosed in the present disclosure can weld zirconium alloy at a lower temperature, and can enhance the bonding strength of the zirconium alloy welding interface, thereby improving the mechanical properties of the welded joint Effect.

The above descriptions are only preferred embodiments of the present disclosure, and it should be understood that the present disclosure is not limited to the forms disclosed herein, and should not be regarded as excluding other embodiments, but can be used in various other combinations, modifications and environments, and Modifications can be made within the scope of the ideas described herein, by virtue of the above teachings or skill or knowledge in the relevant art. However, modifications and changes made by those skilled in the art do not depart from the spirit and scope of the present disclosure, and should be within the protection scope of the appended claims of the present disclosure.

Claims (10)

1. a welding method of zirconium alloy, is characterized in that, comprises: Using zirconium alloy as the base material, performing electrochemical hydrogen charging treatment on at least one side surface of the base material, so as to form at least one hydrogen charging surface correspondingly, and obtain the first base material to be welded; Brazing is performed on the first base material to be welded on the hydrogen-filled surface of the first base material to be welded. 2. The welding method according to claim 1, wherein the electrolyte used in the electrochemical hydrogen charging treatment is a sulfuric acid solution added with thiourea; wherein the concentration of the sulfuric acid is 0.5-1mol/L , the concentration of the thiourea is 0.02～0.04mol/L; and/or, The conditions of the electrochemical hydrogen charging treatment include: the temperature is 25-35° C., the time is 1-720 min, and the current density is 80-120 mA/cm ² . 3. The welding method according to claim 1, characterized in that, before performing the electrochemical hydrogen charging treatment, it also includes the step of pre-treating the base material; wherein the pre-treatment includes: Sanding, disinfecting and drying the base material in sequence to obtain a sample; The sample is sealed to obtain the substrate to be charged with hydrogen. 4. The welding method according to claim 1, characterized in that brazing the first base material to be welded on the hydrogen-filled surface of the first base material to be welded comprises: Using the brazing foil, one side surface of the second base material to be welded and the hydrogen-filled surface of the first base material to be welded are brazed. 5. The welding method according to claim 4, wherein at least one side surface of the second base material to be welded is a hydrogen-filled surface, and the preparation method of the second base material to be welded is the same as that of the first base material to be welded. The preparation method of the substrate to be welded is the same; Brazing one side surface of the second substrate to be welded and the hydrogen-filled surface of the first substrate to be welded includes: brazing the hydrogen-filled surface of the second base material to be welded and the hydrogen-filled surface of the first base material to be welded. 6. The welding method according to claim 4, characterized in that, the second substrate to be welded is a zirconium alloy. 7. welding method according to claim 4 is characterized in that, described solder foil is Ag-Cu-Ti ternary active solder foil; Wherein, described Ag-Cu-Ti ternary active solder foil The copper content in the foil is 26.7%-27%, and the titanium content in the Ag-Cu-Ti ternary active solder foil is 2%-4.5%. 8 . The welding method according to claim 7 , wherein the liquidus range of the solder foil is 770-810° C.; and/or, the thickness of the solder foil is 20-500 μm. 9. The welding method according to claim 1, wherein the brazing is vacuum brazing; the conditions of the vacuum brazing include: the temperature is 790-850°C, the holding time is 10-30min, the vacuum degree higher than 2×10 ^-3 . 10. The welding method according to any one of claims 1-9, characterized in that the zirconium alloy is a Zr-4 alloy.

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