CN108098186A - High corrosion resistance nickel-based solder foil and preparation method thereof - Google Patents
High corrosion resistance nickel-based solder foil and preparation method thereof Download PDFInfo
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- CN108098186A CN108098186A CN201711361760.5A CN201711361760A CN108098186A CN 108098186 A CN108098186 A CN 108098186A CN 201711361760 A CN201711361760 A CN 201711361760A CN 108098186 A CN108098186 A CN 108098186A
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- Prior art keywords
- solder
- foil
- corrosion resistance
- present
- solder foil
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
- B23K35/304—Ni as the principal constituent with Cr as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0227—Rods, wires
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/023—Alloys based on nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of high corrosion resistance nickel-based solder foil and preparation method thereof, and solder is laminated band, suitable for the assembling of large-area brazing part, can also overcome the problems, such as using soldering paste vacuum drying oven and vacuum system to be caused to pollute；Solder foil alloy chrome content of the present invention is high, and corrosion resistance is good；The brazing temperature of solder foil of the present invention is less than 1100 DEG C, and stainless crystalline grain of steel will not be made to grow up；It is brazed using solder foil of the present invention, soldering joint strength does not change with joint clearance of brazing size, is conducive to the assembling of complicated brazing member；Soldering of the solder of the present invention especially suitable for stainless steel cooler for recycled exhaust gas, is also applied for the soldering of other heat exchangers.
Description
Technical field
The present invention relates to a kind of high corrosion resistance nickel-based solder foil for stainless steel soldering, especially suitable for EGR
（Exhaust gas recycles）The soldering of cooler and other heat exchangers, belongs to welding field.
Background technology
With raising of the people to environmental consciousness, country increasingly payes attention to the pollution of environment for vehicle exhaust, to vapour
Tail gas discharge standard also increasingly improves.Exhaust gas recycles（EGR）Cooler just comes into being.The action principle of cooler for recycled exhaust gas
It is to cool down a part of exhaust gas in cooler for recycled exhaust gas, and cycles and also return in cylinder, reaches the burning temperature for reducing cylinder
Degree and oxygen content；This device can save oil consumption, and can obviously reduce the discharge of nitrogen oxides and flue dust, it has also become automobile making
In indispensable component.
The working environment of cooler for recycled exhaust gas is severe, its requirement can bear high temperature, the corrosion of some strength and various strong acid.EGR
Cooler generally using such as 304,304L, 316,316L austenitic stainless steels, is manufactured by vacuum brazing method.
Powdery is all first made in the solder of soldering cooler for recycled exhaust gas at present, and paste use is then tuned into organic matter.Use cream
During shape solder, organic binder bond and solvent in soldering paste generate explosion due to volatilization when heated, influence the wetting characteristics of solder；
And vacuum degree of these volatile matters when can influence vacuum brazing, make soldering extending heating time, reduce production efficiency, it is more important
Be that vacuum drying oven and vacuum system can be caused to pollute.
The content of the invention
It is an object of the invention to provide a kind of high corrosion resistance nickel-based solder foils and preparation method thereof, and solder is made
Foil suitable for the assembling of large-area brazing part, can also overcome and cause vacuum drying oven using soldering paste and what vacuum system polluted asks
Topic；Solder foil alloy chrome content of the present invention is high, and corrosion resistance is good；The brazing temperature of solder foil of the present invention is less than 1100
DEG C, stainless crystalline grain of steel will not be made to grow up；Using solder foil of the present invention be brazed, soldering joint strength not with joint clearance of brazing size and
Variation, is conducive to the assembling of complicated brazing member；Soldering of the solder of the present invention especially suitable for stainless steel cooler for recycled exhaust gas, is also suitable
In the soldering of other heat exchangers.
To achieve the above object, the present invention provides a kind of high corrosion resistance nickel-based solder foil, ingredient percentage by weight
It is than proportioning：Cr 27~31%, P 5~7%, Si 3~5%, Zr 0.5~1%, surplus are nickel.
Preferably, total content≤10wt% of P and Si.
Preferably, foil is made up of cooling mode, and foil thickness is 0.025~0.04mm.
The present invention also provides the preparation methods of above-mentioned high corrosion resistance nickel-based solder foil, include the following steps：
1）The high-purity N i, Cr, Si, Zr that purity is selected to be not less than 99.5%, P element, wherein P, Si, Zr elements with Ni-P, Ni-Si,
Ni-Zr intermediate alloys form adds in；Using the loss the purpose is to reduce these elements in fusion process of intermediate alloy, it is ensured that
The accuracy of brazing filler metal alloy ingredient；
2）Components by weight percentage weighs；
3）Using protective gas induction heating melting smelting method, each element is melted, and is smelted into brazing filler metal alloy；
4）Make foil solder, a diameter of 300mm of beryllium copper roller with list roller chilling legal system under a shielding gas, rotating speed is controlled 500
~2000rpm, the cooling velocity of molten solder are more than 105/sec。
The advantages of the present invention are：A kind of high corrosion resistance nickel-based solder foil and its preparation side are provided
Solder is laminated band, suitable for the assembling of large-area brazing part, can also overcome and cause vacuum drying oven and vacuum using soldering paste by method
The problem of systemic contamination；Solder foil alloy chrome content of the present invention is high, and corrosion resistance is good；The soldering temperature of solder foil of the present invention
Degree will not make stainless crystalline grain of steel grow up less than 1100 DEG C；It is brazed using solder foil of the present invention, soldering joint strength is not with soldering
Gap size and change, be conducive to the assembling of complicated brazing member；Pricker of the solder of the present invention especially suitable for stainless steel cooler for recycled exhaust gas
Weldering, is also applied for the soldering of other heat exchangers.
Solder foil of the present invention also has following features：
1st, the brazing temperature of solder foil of the present invention is not higher than 1100 DEG C, and stainless crystalline grain of steel will not be long because of crystal grain after soldering is heated
It is big and influence its performance, and energy consumption when can save soldering.
2nd, solder of the present invention can be made into the foil of 0.025~0.04mm thickness.
3rd, it is brazed using solder foil of the present invention, the intensity of soldered fitting is good, and acidresistant property is high.
For this brazing filler metal alloy using Ni-Cr alloy as matrix, Cr can improve the inoxidizability of nickel-base alloy and antiacid corrosive power,
Therefore it is the important alloying element in solder, when chromium additive amount is less than 27%, inoxidizability and antiacid corrosive power are declined；
When chromium additive amount is more than 31%, solder forms the less able of Non Crystalline Foil band.
The fusion temperature of Ni-Cr alloy is very high, it is impossible to meet the requirement of brazing temperature, in order to reduce its fusing point, add in drop
Molten element P and Si, P are strong melting point depressants, according to the state diagram of Ni-P bianry alloys and Ni-Cr-P ternary alloy three-partalloy state diagrams, Ni-
11P forms the eutectic that fusing point is 877 DEG C, and Ni-14Cr-10P forms ternary alloy three-partalloy eutectic, and fusing point is 888 DEG C.Therefore, add
P is added to be to the effect for reducing solder fusing point it will be apparent that but the excessive P of addition substantial amounts of brittleness phosphide will be formed in solder
Phase makes soldering joint strength be deteriorated.
It is similar with addition P to add the effect of Si, but it is apparent not as P to drop molten effect.According to Ni-Si bianry alloy states
Figure and Ni-Cr-Si ternary alloy three-partalloy state diagrams, Ni-11.4Si form the eutectic that fusing point is 1150 DEG C, Ni-20.5Cr-11.8Si
Form the ternary eutectic that fusing point is 1077 DEG C.Substantial amounts of brittleness silicide phase will also be formed in solder by adding excessive Si,
Soldering joint strength is deteriorated.
The present invention is to use while add P and Si, it is made to generate synergistic effect, that is, reduces the fusing point of solder, the property of solder
It can will not become very crisp.The additive amount of P is 5~7wt%, the additive amount of Si be 3~5wt%, P and Si total addition level≤
10wt%。
In order to which amorphous brazing filler metal foil is made, the present invention often adds decrystallized element.Conventional method is addition B, but adds B
Solder B can occur when being brazed stainless steel penetrated into the intergranular of stainless steel, the performance of stainless steel can be influenced.The technology of the present invention
Key is a small amount of strong decrystallized element Zr of addition, Zr not still strong decrystallized elements, and can be with crystal grain thinning.Zr is high-melting-point
Element, but according to Ni-Zr state diagrams, a small amount of Zr will not improve the fusing point of alloy, instead be declined the fusing point of solder, small
Zr in 1% is highly beneficial for manufactured Non Crystalline Foil band.
Description of the drawings
Fig. 1 is that 304 stainless joints of different gap are brazed using 3 solder foil of embodiment, strength of joint with
The relational view of joint clearance of brazing.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is further described.Following embodiment is only
For clearly illustrating technical scheme, and it is not intended to limit the protection scope of the present invention and limits the scope of the invention.
Table 1 lists the solder ingredient and weight percent content of 6 embodiment solder foils of the invention.
1 solder ingredient of table and weight percent content
The manufacturing method of the various embodiments described above solder foil is as follows：
1）The high-purity N i, Cr, Si, Zr that purity is selected to be not less than 99.5%, P element, wherein P, Si, Zr elements with Ni-P, Ni-Si,
Ni-Zr intermediate alloys form adds in；Using the loss the purpose is to reduce these elements in fusion process of intermediate alloy, it is ensured that
The accuracy of brazing filler metal alloy ingredient；
2）Components by weight percentage weighs；
3）Using protective gas induction heating melting smelting method, each element is melted, and is smelted into brazing filler metal alloy；
4）Make the foil solder that thickness is 0.025~0.04mm with list roller chilling legal system under a shielding gas；The diameter of beryllium copper roller
For 300mm, rotating speed control is more than 10 in 500~2000rpm, the cooling velocity of molten solder5/sec。
Soldering joint strength compares
The various embodiments described above solder foil, they are completely melt at a temperature of 1050~1070 DEG C.With the 304 of these solder brazings
The tensile strength of stainless steel banjo fixing butt jointing is listed in table 2.
The tensile strength of 2 304 stainless steel banjo fixing butt jointing of table
| Solder | Brazing temperature（℃） | （MPa） |
| Embodiment 1 | 1090 | 211.5 |
| Embodiment 2 | 1090 | 214.4 |
| Embodiment 3 | 1090 | 216.2 |
| Embodiment 4 | 1090 | 209.3 |
| Embodiment 5 | 1090 | 213.5 |
| Embodiment 6 | 1090 | 215.4 |
| Comparative example BNi-613 soldering paste | 1090 | 202.3 |
304 stainless steel banjo fixing butt jointings being brazed with each embodiment solder foil, the strength of joint than being brazed with paste solder is high, because
For that can occur some defects within a fitting with paste solder soldering.
304 stainless joints of different gap are brazed with 3 solder foil of embodiment, between strength of joint and soldering
As shown in Figure 1, the chart is bright, strength of joint with gap does not increase and is deteriorated the relation of gap, this carrys out the assembly work of brazing member
Say it is critically important, requirement when can simplify assembling to joint clearance of brazing.
Solder corrosion resistance is tested
By 1 to 6 solder foil of embodiment, comparative example BNi-613 soldering paste（Ni-29Cr-6P-4Si）, 2177 foil solders of VZ
（Ni-25Cr-6P-1.5Si-0.5B）Solder is placed in crucible, is melted, is weighed to each sample, before being denoted as experiment into vacuum drying oven
Weight.Above-mentioned 8 kinds of solders are immersed in the corrosive liquid of boiling again, heat 2h, corrosion liquid formula is 65g NaCl+10mL HCl
+ 1L aqueous solutions.After the test, weigh to each sample, be denoted as weight after experiment.Using of poor quality before and after each specimen test
The corrosion resistance of weight-loss ratio characterization solder is calculated, the results are shown in Table 3.
3 corrosion resistance result of the test of table
Table 3 shows that the corrosion resistance of 1 to 6 solder foil of embodiment is all good, the corrosion resistance phase with BNi-613 soldering paste
When the chrome content of VZ 2117 is low, and corrosion resistance is poor.
In addition, the shaping of solder foil is related with brazing filler metal alloy ingredient and proportioning, brazing filler metal alloy ingredient shapes solder foil
Influence be shown in Table 4.
Table 4
It is very big that table 4 shows that Zr influences the foil shaping of brazing filler metal alloy, and when amount containing Zr is less than 0.5, the shaping of solder foil is poor；
When Cr is too high, the shaping of brazing filler metal alloy foil is also poor.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, several improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (4)
1. high corrosion resistance nickel-based solder foil, which is characterized in that its ingredient components by weight percentage is：Cr 27~31%, P
5~7%, Si 3~5%, Zr 0.5~1%, surplus are nickel.
2. high corrosion resistance nickel-based solder foil according to claim 1, which is characterized in that the total content of P and Si≤
10wt%。
3. high corrosion resistance nickel-based solder foil according to claim 1, which is characterized in that foil passes through cooling mode system
Into foil thickness is 0.025~0.04mm.
4. the preparation method of the high corrosion resistance nickel-based solder foil any one of claims 1 to 3, which is characterized in that
Include the following steps：
1）The high-purity N i, Cr, Si, Zr that purity is selected to be not less than 99.5%, P element, wherein P, Si, Zr elements with Ni-P, Ni-Si,
Ni-Zr intermediate alloys form adds in；
2）Components by weight percentage weighs；
3）Using protective gas induction heating melting smelting method, each element is melted, and is smelted into brazing filler metal alloy；
4）Make foil solder, a diameter of 300mm of beryllium copper roller with list roller chilling legal system under a shielding gas, rotating speed is controlled 500
~2000rpm, the cooling velocity of molten solder are more than 105/sec。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711361760.5A CN108098186A (en) | 2017-12-18 | 2017-12-18 | High corrosion resistance nickel-based solder foil and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711361760.5A CN108098186A (en) | 2017-12-18 | 2017-12-18 | High corrosion resistance nickel-based solder foil and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
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| CN108098186A true CN108098186A (en) | 2018-06-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711361760.5A Pending CN108098186A (en) | 2017-12-18 | 2017-12-18 | High corrosion resistance nickel-based solder foil and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110315239A (en) * | 2019-07-05 | 2019-10-11 | 浙江省冶金研究院有限公司 | A kind of nickel alloy slurry and the ultra-thin band-like nickel-based solder by nickel alloy slurry preparation |
| CN114669907A (en) * | 2022-04-06 | 2022-06-28 | 安徽工业大学 | Zr-containing multi-element nickel-based brazing filler metal, preparation method and brazing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042602C (en) * | 1994-04-06 | 1999-03-24 | 新日本制铁株式会社 | Alloy foil capable of liquid-phase diffusion welding of heat-resisting material in oxidizing atmosphere |
| US6203754B1 (en) * | 1999-01-27 | 2001-03-20 | Usui Kokusai Sangyo Kaisha Limited | Brazing filler metal superior in corrosion resistance and heat resistance, and EGR cooler brazed with said brazing filler metal |
| CN101670500A (en) * | 2009-09-25 | 2010-03-17 | 广州有色金属研究院 | Aqueous nickel welding paste for stainless steel brazing |
| CN101898283A (en) * | 2009-06-01 | 2010-12-01 | 李昕 | Low-temperature nickel-based solder for soldering |
| CN106975856A (en) * | 2016-01-15 | 2017-07-25 | 德昌电机(深圳)有限公司 | The solder of commutator, the method for welding of commutator and the soldering for commutator |
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2017
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| CN1042602C (en) * | 1994-04-06 | 1999-03-24 | 新日本制铁株式会社 | Alloy foil capable of liquid-phase diffusion welding of heat-resisting material in oxidizing atmosphere |
| US6203754B1 (en) * | 1999-01-27 | 2001-03-20 | Usui Kokusai Sangyo Kaisha Limited | Brazing filler metal superior in corrosion resistance and heat resistance, and EGR cooler brazed with said brazing filler metal |
| CN101898283A (en) * | 2009-06-01 | 2010-12-01 | 李昕 | Low-temperature nickel-based solder for soldering |
| CN101670500A (en) * | 2009-09-25 | 2010-03-17 | 广州有色金属研究院 | Aqueous nickel welding paste for stainless steel brazing |
| CN106975856A (en) * | 2016-01-15 | 2017-07-25 | 德昌电机(深圳)有限公司 | The solder of commutator, the method for welding of commutator and the soldering for commutator |
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| 叶雷等: "Hf和Zr为降熔元素镍基钎料对IC10合金的钎焊", 《焊接学报》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110315239A (en) * | 2019-07-05 | 2019-10-11 | 浙江省冶金研究院有限公司 | A kind of nickel alloy slurry and the ultra-thin band-like nickel-based solder by nickel alloy slurry preparation |
| CN110315239B (en) * | 2019-07-05 | 2022-02-15 | 浙江亚通焊材有限公司 | Nickel alloy slurry and ultrathin strip-shaped nickel-based brazing filler metal prepared from same |
| CN114669907A (en) * | 2022-04-06 | 2022-06-28 | 安徽工业大学 | Zr-containing multi-element nickel-based brazing filler metal, preparation method and brazing method thereof |
| CN114669907B (en) * | 2022-04-06 | 2024-04-09 | 安徽工业大学 | Zr-containing multi-element nickel-based brazing filler metal, preparation method and brazing method thereof |
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Application publication date: 20180601 |