CN106077997A - A kind of solder for anti-fused salt corrosion nickel base superalloy melting - Google Patents
A kind of solder for anti-fused salt corrosion nickel base superalloy melting Download PDFInfo
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- CN106077997A CN106077997A CN201610556350.5A CN201610556350A CN106077997A CN 106077997 A CN106077997 A CN 106077997A CN 201610556350 A CN201610556350 A CN 201610556350A CN 106077997 A CN106077997 A CN 106077997A
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- solder
- fused salt
- salt corrosion
- base superalloy
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- 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
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- Nonmetallic Welding Materials (AREA)
Abstract
The invention discloses a kind of solder for anti-fused salt corrosion nickel base superalloy melting, belong to technical field of welding materials.The component of described solder is by weight percentage: C:0.03 ~ 0.06%, Mn:0.04 ~ 0.10%, Si:0.3 ~ 0.5%, Cu≤0.10%, Co≤0.20%, P≤0.015%, S≤0.015%, rare earth element: 0.01 ~ 0.05%, Fe:1.0 ~ 5.0%, Cr:6.0 ~ 8.0%, Mo:12.0 ~ 18.0%, Al≤0.3%, Ti≤0.2%, Nb:1.0 ~ 2.0%, wherein: Ti+Nb+Al≤2%, surplus is Ni.The invention also discloses a kind of wlding for anti-fused salt corrosion nickel base superalloy melting, a kind of anti-fused salt corrosion nickel base superalloy method of attachment, and a kind of anti-fused salt corrosion nickel base superalloy structural member.The present invention can be effectively improved toughness and the antioxygenic property of weld seam, and can guarantee that excellent anti-fused salt corrosion performance and mechanical behavior under high temperature, can meet and have the fused salt of relatively operation at high temperature and performance requirement, radiation environment to use needs, it is adaptable to the welding of MSR structural material.
Description
Technical field
The present invention relates to technical field of welding materials, be specifically related to a kind of for the fusing of anti-fused salt corrosion nickel base superalloy
The solder of weldering.
Background technology
MSR belongs to the 4th generation of technology such as nuclear energy system, the advantage with a series of uniqueness, high including inherent safety, flexibly
Fuel recycle characteristic, thorium base fuel available and preventing nuclear proliferation etc..But it is owing to have employed fused salt as coolant, molten
Salt pile structure material must have resistance to fused salt corrosion, high temperature resistant and irradiation reciprocal action.The alloy of external anti-fused salt corrosion is main
Being Hastelloy N alloy, China also studied the domestic high-temperature nickel-base alloy GH3535 of correspondence.In order to ensure welding knot
Structure has reliable elevated temperature strength, has high temperature resistant molten salt corrosive nature simultaneously, and the solder that research and development match is imperative.
Generally for ensureing that high-temperature nickel-base alloy has the resistance to fused salt corrosion performance identical with mother metal, mainly comprising of solder
Element must and mother metal holding identical, but due in anti-fused salt corrosion nickel base superalloy elements Mo and Cr content higher, weld seam
Toughness can be less than mother metal, cause bead crack sensitivity to increase.How to ensure the most resistance to fused salt corrosion of weld seam, and preferably high temperature
While intensity, having again higher toughness is to improve the vital factor of weldquality.Therefore, for anti-fused salt corrosion nickel
Based high-temperature alloy, needs badly and provides a kind of solder meeting the use requirement of MSR work condition environment, to ensure MSR structural member
Security reliability.
Summary of the invention
The technical problem to be solved is to overcome prior art not enough, it is provided that a kind of for anti-fused salt corrosion nickel
The solder of based high-temperature alloy melting, can be effectively improved toughness and the antioxygenic property of weld seam, and can guarantee that excellent anti-fused salt
Corrosive nature and mechanical behavior under high temperature, can meet and have the fused salt of relatively operation at high temperature and performance requirement, radiation environment to use need
Want, it is adaptable to the welding of MSR structural material.
The present invention solves above-mentioned technical problem the most by the following technical solutions:
A kind of solder for anti-fused salt corrosion nickel base superalloy melting, the component of described solder is by weight percentage
It is calculated as: C:0.03～0.06%, Mn:0.04～0.10%, Si:0.3～0.5%, Cu≤0.10%, Co≤0.20%, P≤
0.015%, S≤0.015%, rare earth element: 0.01～0.05%, Fe:1.0～5.0%, Cr:6.0～8.0%, Mo:12.0
～18.0%, Al≤0.3%, Ti≤0.2%, Nb:1.0～2.0%, wherein: Ti+Nb+Al≤2%, surplus is Ni.
Preferably, the percentage by weight of C is 0.05～0.06%.
Preferably, the percentage by weight of Mn is 0.5～0.8%.
Preferably, the percentage by weight of Mo is 16.0～18.0%.
Preferably, percentage by weight sum >=23% of Cr and Mo.
Preferably, the ratio and≤0.02% of the weight percent of S and P.
Preferably, described rare earth element is lanthanum or cerium or yttrium or a combination thereof.In view of rare earth ferrosilicon price than pure rare earth just
The most a lot, in order to reduce manufacturing cost further, described rare earth element uses rare earth ferrosilicon form to add.
The wlding of the multi-forms such as solid core welding wire, flux-cored wire, welding, welding rod can be prepared based on above-mentioned solder,
Melting for anti-fused salt corrosion nickel base superalloy.Therefore techniques below side can also be obtained according to identical invention thinking
Case:
A kind of wlding for anti-fused salt corrosion nickel base superalloy melting, its used solder is any of the above technology
Solder described in scheme.
A kind of anti-fused salt corrosion nickel base superalloy method of attachment, utilizes above-mentioned wlding to carry out melting.
A kind of anti-fused salt corrosion nickel base superalloy structural member is by least two anti-fused salt corrosion nickel base superalloy parts
It is formed by connecting by said method.
Compared to existing technology, technical solution of the present invention has the advantages that
The present invention is added by the Si element of certain content, can form stable M in weld seam6C-type carbide；Pass through Nb
The addition of element, the preparation adding the resistance to austenite recrystallization, beneficially wlding controls, and the compound of formation is all right
Seam organization is refined, it addition, the Nb element of certain content can strengthen weld seam opposing fission product tellurium embrittlement energy as forming core particle
Power；By the interpolation of rare earth element, aluminium alloy can be purified, suppress and remove harmful element segregation, crystal grain thinning, improvement folder
Miscellaneous.
Utilizing wlding of the present invention to carry out the welding of anti-fused salt corrosion nickel base superalloy, appearance of weld is attractive in appearance, crack-sensitivity
Property low, the room temperature of deposited metal, the tensile strength average of high temperature and yield strength average are above mother metal performance requirement, and keep
Higher fracture elongation, deposited metal can reach more than 0.92 with the creep rupture strength ratio of mother metal, the high temperature resistance of deposited metal
Oxidation susceptibility, high temperature resistant molten salt corrosive nature is basic and mother metal is suitable.
The present invention can realize mating with the mechanical property of anti-fused salt corrosion nickel base superalloy, has good resisting simultaneously and melts
Salt corrosion performance, it is adaptable to the high-temperature structural material welding of MSR.
Accompanying drawing explanation
Fig. 1 a is the deposited metal of embodiment 1 Cross Section Morphology schematic diagram after 700 DEG C/400h fused salt corrosion；
Fig. 1 b is the deposited metal of embodiment 1 cross section Cr distribution diagram of element after 700 DEG C/400h fused salt corrosion；
Fig. 2 a is GH3535 alloy Cross Section Morphology schematic diagram after 700 DEG C/400h fused salt corrosion；
Fig. 2 b is GH3535 alloy cross section Cr distribution diagram of element after 700 DEG C/400h fused salt corrosion；
Fig. 3 is the deposited metal according to embodiments of the invention 1 and GH3535 alloy creep rupture strength and rupture life relation
Figure.
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is described in detail:
In order to meet the security reliability of MSR welding structural element, the present invention proposes a kind of for anti-fused salt corrosion
The solder of nickel base superalloy melting, its component (percentage by weight) is specific as follows:
The content of C controls between 0.03～0.06%, is preferably controlled between 0.05～0.06%, within the range
C makes weld seam have preferable tough coupling.C content is the highest, can increase the intensity of weld seam, but plasticity can decrease, it addition, such as
Really C content is too big, can make to be formed in weld seam substantial amounts of carbide, reduces seam organization stability, and carbon content is too low, can make weld seam
Low strength.
The content of Mn controls between 0.04～0.10%, is preferably controlled between 0.5～0.8%, and Mn is mainly as de-
Oxygen agent and desulfurizing agent, can smelt at wlding and carry out deoxidation and desulfurization in welding process, make the impurity element in weld seam reduce；
It addition, Mn element is readily collected in dendrite circle, the effect of strengthening dendrite circle can be played.
The content of Si is preferably controlled between 0.3～0.5%, and silicon is in order to prevent the oxidation of weld seam, and stable base guarantees weldering
Seam intensity, moreover it is possible to improve the pattern of Carbide Precipitation phase, quantity and distribution situation in weld seam.As silicone content ＜ 0.3%, weld seam
The M of more instability can be formed2C-type carbide, stable M6C-type carbide is less, M2C-type carbide at high temperature can occur
Decompose, affect the elevated temperature strength of weld seam；When silicone content is 0.5～1.0%, the welding performance of steel can be reduced, easy when welding
Generate low melting point silicate, increase slag and the mobility of fusion, affect welding quality；By optimal control silicone content it is
0.3～0.5%, weld seam can be formed with stable M6C-type carbide is main, is less likely to occur to decompose under high-temperature service, it is ensured that its
High-temperature service intensity.
Cu can be with improving welding property, but under neutron irradiation, be easily caused rich Cu cluster and separate out, infringement weld seam anti-in
Sub-irradiation behaviour；Co is as solution strengthening element, it is possible to significantly improve creep strength and the plasticity of alloy.But owing to solder is molten
In the welding application of salt pile structure part, can stand high neutron irradiation, decaying is60Co, the radioactive material long half-lift that this being a kind of
Matter, is attended by gamma-rays simultaneously, bigger to environmental hazard.Comprehensive information above, should strictly control the copper coin in solder of the present invention
Element, Co element should control content that rationally may be low in regulation.Cu element weight percent in solder of the present invention is defined to≤
0.10%, Co element weight percent is defined to≤0.20%.
P and S is impurity element, makes weldability be deteriorated, and reduces plastic property of weld bead, it addition, easily form segregation in weld seam, damages
Evil weld seam anti-neutron irradiation performance.P and S fully belongs to harmful element, the most preferably occurs without in solder of the present invention, but
The control crossing low content can cause cost to increase.Through comprehensive consideration, in solder of the present invention, P and S element requires that control is: P≤
0.015%, S≤0.015%, S+P≤0.02%.
Rare earth element (Re) can be the most permissible with low melting point harmful element phase separations such as phosphorus, arsenic, stannum, antimony, bismuth, lead in steel
Form, with these impurity, the compound that low melting point is higher, also can suppress these segregations being mixed on crystal boundary, play purification,
The impurity in weld seam is made to reduce.Rare earth easily generates the oxysulfide of rare earth, forms complex inclusion or rare earth silicate
Compound, their fusing point is high and highly stable, can control the pattern of field trash.Rare earth element can improve weld seam intensity and
Toughness, improves the creep rupture strength of weld seam, when rare earth element content controls 0.01～0.05%, it is also possible to improve the anti-height of weld seam
Temperature oxidation susceptibility, but when rare earth element content is more than 0.05%, and oxidation resistance reduces on the contrary, and rare earth element price is relatively
High.Rare earth element percentage by weight in solder the most of the present invention is defined to 0.01～0.05%.
The content of Fe controls between 1.0～5.0%, and Fe element adds mainly as accompanying element, can be with replacing section
Nickel is to reduce cost and to improve waste utilization rate.
The content of Cr controls between 6.0～8.0%, and Cr within the range is to be effectively improved at oxidizing corrosion medium
In the key element of decay resistance, and high temperature oxidation resistance can be improved.But in MSR Service Environment, weld seam is at height
Corrosion mechanism in temperature molten salt, mainly Cr element diffuses in fused salt in large quantities.In order to reduce fused salt corrosion, preferably control
Cr element is 6.0%.
The content of Mo controls between 12.0～18.0%, preferably between 16.0～18.0%, and molybdenum within the range
Mainly as strong solution strengthening element, its atomic radius is relatively big, makes lattice that big distortion, notable strengthening γ base occur after solid solution
Body, puies forward heavy alloyed elevated temperature strength.
Al, Ti are controlled elements in solder of the present invention, and when both constituent contents increase, weld seam tends to form γ '
Precipitated phase, inefficacy of growing up the most under the high temperature conditions due to γ ' precipitated phase, unfavorable to alloy property.Nb is shape in weld seam
Become tiny carbide, austenite recrystallization can be stoped in heating process with pinning crystal boundary, delay the crystalline substance of recrystallization austenite
Grain length is big, the beneficially control in wlding (the especially real core of small diameter or flux-cored wire) preparation process, and the change formed
Compound as forming core particle, can refine the tissue of weld seam, improves the intensity of weld seam, it addition, add Nb element in solder, and can
To strengthen the embrittling effect of weld seam opposing fission product tellurium.In solder of the present invention, Al and Ti element requires that control is: Al≤
0.3%, Ti≤0.2%, and the content of Nb controls between 1.0～2.0%, and Ti+Nb+Al≤2%.
In order to verify effect of the present invention, the solder of four kinds of different components is used to prepareSolid core welding wire, and utilize institute
The solid core welding wire of preparation carries out the welding of anti-fused salt corrosion nickel base superalloy (all using GH3535 alloy in four embodiments),
Finally welding effect is measured evaluation.Solder compositions (percentage by weight) in four embodiments is as shown in table 1:
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| C | 0.06 | 0.053 | 0.046 | 0.036 |
| Mn | 0.65 | 0.69 | 0.45 | 0.71 |
| Fe | 4.06 | 4.25 | 4.2 | 4.3 |
| Si | 0.44 | 0.35 | 0.46 | 0.41 |
| P | 0.0028 | 0.002 | 0.001 | 0.002 |
| S | 0.001 | 0.003 | 0.006 | 0.008 |
| Cu | 0.002 | 0.0022 | 0.0047 | 0.002 |
| Co | 0.14 | 0.12 | 0.10 | 0.05 |
| Cr | 6.89 | 6.50 | 6.96 | 7.05 |
| Mo | 17.2 | 16.7 | 16.5 | 16.8 |
| Re | 0.05 | 0.045 | 0.041 | 0.035 |
| Al | 0.03 | 0.003 | 0.002 | 0.05 |
| Ti | 0.01 | 0.02 | 0.03 | 0.01 |
| Nb | 1.5 | 1.5 | 1.7 | 2.0 |
| Ni | Surplus | Surplus | Surplus | Surplus |
Use above-mentionedWelding wire, with 99.99% pure argon protection, uses GTAW to close at GH3535
Carrying out deposited metal mechanical property test on gold, welding conditions are: welding current 140～155A, weldingvoltage 10～14V, weldering
Connecing speed 60～80mm/min, gas flow 10～12L/min, between road, temperature controls at≤90 DEG C.Above parameter is used to utilize
Prepared by various embodiments above, solid core welding wire welds, and appearance of weld is attractive in appearance, and crack sensitivity is extremely low.Each embodiment is melted
Metallisation carries out chemical composition analysis, does not substantially have the scaling loss of important alloying element, and test result is the most identical with table 1 and right
Each deposited metal tensile property carries out room temperature test, and its deposited metal tensile strength average is 758MPa, and yield strength average is
525MPa, higher than the mother metal performance requirement of GH3535 alloy, but the elongation percentage average of deposited metal is 33.8%, wants less than mother metal
Evaluation, can recover the plasticity of weld seam by post weld heat treatment.Deposited metal performance (the strain as shown in table 2 that each embodiment is concrete
Speed is 0.05/s, elongation percentage marker field length 40mm).
Table 2
Table 3 is that (strain rate is 0.05/s, elongation percentage labelling segment length for 650 DEG C of tensile properties of embodiment 1～embodiment 4
Degree 40mm).Deposited metal is 519MPa the tensile strength average of 650 DEG C, and yield strength average is 349MPa, higher than GH3535
The mother metal performance requirement of alloy.Standard not yet specifies the elongation percentage at 650 DEG C of mother metals, and deposited metal the most averagely extends
Rate remains at 18.2%.
Table 3
As a example by the deposited metal that embodiment 1 is obtained, carry out static FLiNaK (chemical composition LiF-NaF-KF mass
Mark is 29.2%, 11.7%, 59.1%) fused salt corrosion, fused salt corrosion temperature is 700 DEG C, and etching time 400h, by GH3535
Alloy is placed in the graphite crucible of same size and etching condition sample as a comparison.The corrosion of material typically uses weight-loss method to comment
The quality of valency corrosive nature, it is contemplated that the resistance to fused salt corrosion of solder of the present invention is effective, and the mechanism of fused salt corrosion is with Cr element
Be diffused in fused salt, the element such as the Fe in fused salt can diffusional deposition to alloy surface, therefore, weight-loss method is not suitable as evaluating this
The index of the resistance to fused salt corrosion of type alloy, the present invention uses the thickness of alloy surface lean Cr layer after fused salt corrosion to close as characterizing
The criterion of the resistance to fused salt corrosion performance of gold, the lean Cr layer thickness of alloy is the most shallow, and the resistance to fused salt corrosion performance of alloy is the best.Fig. 1 a and figure
1b is respectively the embodiment of the present invention 1 gained deposited metal Cross Section Morphology after 700 DEG C/400h fused salt corrosion and electron probe table
The cross section Cr distribution diagram of element levied, Fig. 2 a and Fig. 2 b is respectively GH3535 alloy cross section shape after 700 DEG C/400h fused salt corrosion
The cross section Cr distribution diagram of element that looks and electron probe characterize.It appeared that embodiment 1 gained deposited metal lean Cr layer is basic and female
Material GH3535 alloy is suitable.The lean Cr layer thickness of the deposited metal of embodiment 1 is 3.75 μm, and contrast GH3535 alloy is 3.40 μ
M, shows that the weld seam resistance to fused salt corrosion performance using solder of the present invention welding is the same with GH3535 alloy excellent.Therefore, can use
Solder of the present invention, wlding carry out MSR nuclear equipment welding.
MSR nuclear equipment is generally on active service at high-temperature molten salt environment, in addition to requiring the resistance to fused salt corrosion of excellence, and high temperature
Creep rupture strength is also important Consideration, as a example by the deposited metal that embodiment 1 and embodiment 2 are obtained, it is carried out height
Temperature enduring quality test.Test temperature is 650 DEG C, and the load of applying is respectively 380MPa, 320MPa, 275MPa and 220MPa.
Use same test condition that GH3535 alloy has been carried out durable creeping test.Fig. 3 shows embodiment 1 and embodiment 2 institute
Obtain deposited metal and the creep rupture life of GH3535 alloy, it appeared that the deposited metal long term rupture strength of solder of the present invention
Linear with creep rupture life, the most identical with the GH3535 alloy regularity of distribution, both are parallel lines distribution relations, according to meter
Calculate, both rupture strength factor R values may remain in 0.92, show use solder of the present invention welding weld seam have with
The high temperature endurance performance that GH3535 alloy is excellent equally.
Claims (11)
1. the solder for anti-fused salt corrosion nickel base superalloy melting, it is characterised in that the component of described solder is pressed
Percentage by weight is calculated as: C:0.03 ~ 0.06%, Mn:0.04 ~ 0.10%, Si:0.3 ~ 0.5%, Cu≤0.10%, Co≤0.20%, and P≤
0.015%, S≤0.015%, rare earth element: 0.01 ~ 0.05%, Fe:1.0 ~ 5.0%, Cr:6.0 ~ 8.0%, Mo:12.0 ~ 18.0%, Al
≤ 0.3%, Ti≤0.2%, Nb:1.0 ~ 2.0%, wherein: Ti+Nb+Al≤2%, surplus is Ni.
2. solder as claimed in claim 1, it is characterised in that the percentage by weight of C is 0.05 ~ 0.06%.
3. solder as claimed in claim 1, it is characterised in that the percentage by weight of Mn is 0.5 ~ 0.8%.
4. solder as claimed in claim 1, it is characterised in that the percentage by weight of Mo is 16.0 ~ 18.0%.
5. solder as claimed in claim 1, it is characterised in that percentage by weight sum >=23% of Cr and Mo.
6. solder as claimed in claim 1, it is characterised in that the ratio and≤0.02% of the weight percent of S and P.
7. as claimed in claim 1 solder, it is characterised in that described rare earth element is lanthanum or cerium or yttrium or a combination thereof.
8. solder as claimed in claim 7, it is characterised in that described rare earth element uses rare earth ferrosilicon form to add.
9. the wlding for anti-fused salt corrosion nickel base superalloy melting, it is characterised in that its used solder is power
Profit requires solder described in 1～8 any one.
10. an anti-fused salt corrosion nickel base superalloy method of attachment, it is characterised in that utilize wlding described in claim 9 to enter
Row melting.
11. 1 kinds of anti-fused salt corrosion nickel base superalloy structural members, it is characterised in that by least two Ni-based height of anti-fused salt corrosion
Temperature alloy parts are formed by connecting by method described in claim 10.
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| CN115255718A (en) * | 2022-09-06 | 2022-11-01 | 兰州理工大学 | Nickel-based alloy welding wire and preparation method and application thereof |
| CN115255718B (en) * | 2022-09-06 | 2023-08-18 | 兰州理工大学 | Nickel-based alloy welding wire and preparation method and application thereof |
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