CN107214434B - LNG structure and the nickel-base welding rod and preparation method thereof of 9Ni steel peculiar to vessel welding - Google Patents
LNG structure and the nickel-base welding rod and preparation method thereof of 9Ni steel peculiar to vessel welding Download PDFInfo
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- CN107214434B CN107214434B CN201710263345.XA CN201710263345A CN107214434B CN 107214434 B CN107214434 B CN 107214434B CN 201710263345 A CN201710263345 A CN 201710263345A CN 107214434 B CN107214434 B CN 107214434B
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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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- 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
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Abstract
LNG structure and the nickel-base welding rod and preparation method thereof of 9Ni steel peculiar to vessel welding, the welding rod includes Ni-based core wire and the coating for being coated on core wire surface, form the chemical component and degree of Ni-based core wire are as follows: C :≤0.10%, Si :≤0.10%, Mn :≤0.10%, Cu :≤0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤0.40%, Ni+Co: >=99.5%, each ingredient total amount is 100%；Usability of electrode of the present invention is good, in production process can smooth extrusion, electrode coating intensity and surface quality are preferable, and welding rod core shift is controllable；Deposited metal composition meets standard, weld metal pore-free and crackle, and there is the stretching of preferable room temperature and low-temperature flexibility, good mechanical properties can be widely applied.
Description
Technical field
The present invention relates to field of welding material, and in particular to a kind of LNG structure and 9Ni steel peculiar to vessel welding nickel-base welding rod and
Preparation method.
Background technique
With the rapid economic development in our country, liquefied natural gas (LNG) dosage is increased every year with 10% speed, it is contemplated that
In the near future, natural gas will become the third-largest energy of the China after coal and petroleum.Store and transport low temperature used in LNG
9Ni steel has become another focus of steel industry production.Since 2008, in the case where the departments such as National Development and Reform Committee support, saddle
The domestic iron and steel enterprises such as steel, Nangang and Taiyuan Iron and Steel Co. successfully develop domestic low temperature 9Ni steel successively, and it is existing to have broken the long-term import of 9Ni steel
As accelerating China's LNG industrial expansion.Expect the year two thousand twenty, Chinese LNG import volume is up to 44,000,000 tons, even more.
In recent years, domestic LNG technology development is very fast, and 9Ni steel replaces Ni-Cr stainless steel to have become the main material for building LNG low-temperature storage tank
Material, realizes production domesticization substantially and technology is increasingly mature, LNG storage tank has realized autonomous Design and construction, but matches with 9Ni steel
The wlding of set also needs long import, consistent from designing institute to the side of undertaking the construction of to require to accelerate the domestic of the mating wlding of 9Ni steel
Change progress.The production domesticization of the mating wlding of 9Ni steel can not only reduce LNG project cost, shorten procurement cycle, improve construction efficiency,
More importantly push comprehensive production domesticization of LNG storage tank technology and entire industry.
The country carries out the mating wlding development research of 9Ni steel, is concentrated mainly on the development of ENiCrMo-6 welding rod, but all exist
Different degrees of disadvantage, using seldom on Practical Project.In order to comply with the trend of domestic 9Ni steel production domesticization and meet LNG storage
Foreign technology and market foreclosure are broken to wlding urgent need in tank market, develop a kind of craftsmanship and well mould with low temperature
The LNG structure and shipbuilding electrode that property, toughness have both are very necessary.
Summary of the invention
The object of the present invention is to provide the nickel-base welding rod and preparation method thereof that a kind of LNG structure and 9Ni steel peculiar to vessel are welded, systems
Standby welding rod appearance of weld is good, can preferably adapt to the applying working condition of LNG structure and build on-site peculiar to vessel.
Present invention technical solution used for the above purpose are as follows: the Ni-based weldering of LNG structure and 9Ni steel peculiar to vessel welding
Item, the welding rod include Ni-based core wire and the coating for being coated on core wire surface, and the chemical component and percentage for forming Ni-based core wire contain
Amount are as follows: C :≤0.10%, Si :≤0.10%, Mn :≤0.10%, Cu :≤0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤
0.40%, Ni+Co: >=99.5%, each ingredient total amount is 100%.
Preferably, the ingredient of raw material and its weight percent content be successively in coating are as follows: CaCO3: 18 ~ 20%, CaF2: 10 ~
12%, TiO2: 4 ~ 6%, Al2O3: 4 ~ 6%, zircon sand: 1 ~ 2%, CMC:0.5 ~ 1%, K2CO3: 0.5 ~ 1%, Cr:28 ~ 30%, Mo:8 ~
11%, Mn:5 ~ 7%, ferrosilicon: 4 ~ 6%, molybdenum-iron: 3 ~ 5%, ferro-niobium: 2 ~ 3%, each ingredient total amount is 100%；Wherein, it is also added in coating
There is binder, the additive amount of binder is 20 ~ 25% of raw material gross weight in coating.
Wherein, the binder uses pure potassium water glass, chemical component are as follows: K2O >=12, SiO2>=25, S≤0.
005, P≤0.005.
In the present invention, CaCO3In the form of marmorean, CaF2In the form of fluorite, TiO2It is added in the rutile form,
Al2O3With α-Al2O3Form.
The preparation method of LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, comprising the following steps:
Step 1: carrying out ingredient: C :≤0.10%, Si :≤0.10%, Mn according to following elemental constituent and degree:
≤ 0.10%, Cu :≤0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤0.40%, Ni+Co: >=99.5%, all components are melted
It after refining, forged, rolled, drawing, chopping, Ni-based core wire is made, it is spare；
Step 2: being target proportion: CaCO according to following components and degree3: 18 ~ 20%, CaF2: 10 ~ 12%,
TiO2: 4 ~ 6%, Al2O3: 4 ~ 6%, ZrSiO4: 1 ~ 2%, CMC:0.5 ~ 1%, K2CO3: 0.5 ~ 1%, Cr:28 ~ 30%, Mo:8 ~ 11%, Mn:
5 ~ 7%, ferrosilicon: 4 ~ 6%, molybdenum-iron: 3 ~ 5%, ferro-niobium: 2 ~ 3%, calculate calcite and fluorite, rutile, the α-Al to be added2O3, zirconium
The amount of sand, carboxymethyl cellulose, potassium carbonate, hafnium metal powfer, metal molybdenum powder, manganese metal, ferrosilicon, molybdenum-iron, ferro-niobium, and according to meter
It calculates result and weighs each material；Be mixed it is dry-mixed uniformly after, first be added material total weight 2.5% water, pre- 2 ~ 3min of wet mixing
Afterwards, add weight and account for the binder of material total weight 20 ~ 25% and carry out wet mixing, after beat group feeding extrusion press it is interior wrapped in
On Ni-based core wire, nickel-base welding rod is made after baking.
In the present invention, fluorite, rutile and α-Al2O3As slag former, fluorite can generate in Welding Metallurgy reaction
HF reduces the hydrogen content in weld seam；CaF2It can reduce slag surface tension, make slag thinning, viscosity reduces, and improves the stream of slag
Dynamic property.In addition, fluorite also has the function of desulfurization；Rutile can improve the basicity of slag system, TiO2Slag system can be made by short elongated,
To inhibit " dropping down slag " phenomenon when vertical position welding；Al2O3Fusing point is high, oxidisability is low, can change fusing point, viscosity and the flowing of welding rod
Property.
In the present invention, not only as slag former but also as gas-forming agent, CaO can improve the basicity of slag system, increase smelting marble
Golden desulfuration ability, reduces the infiltration of silicon, is conducive to the improvement of the physicochemical property of slag；Generate CO2Hydrogen partial pressure can be reduced, substantially
The hydrogen content in weld metal is reduced, the tendency that postwelding generates cold crack is weakened.Meanwhile basic coating of the invention is when in use
It can chemically react, decomposite CO2Gas etc. forms the gas of protective atmosphere in arc region, protects electrode tip and place
In the weld seam of high temperature, prevent weld seam from generating stomata.
In the present invention, zircon sand can reduce slag entirety thermal expansion coefficient, improve the removability of slag；CMC is main forming
Agent, make electrode coating have certain plasticity, elasticity and mobility, convenient for the compacting of welding rod, keep electrode surface smooth without
Cracking；Potassium carbonate can stabilising arc, improve extrusion.
In the present invention, crome metal, metal molybdenum, manganese metal compounding can transition alloy elements, guarantee must into weld metal
The chemical component wanted participates in deoxidation, improves the intensity of weld seam；And alloyed powder ferrosilicon and molybdenum-iron, ferro-niobium, the addition of alloy can mend
The scaling loss for repaying welding process beneficial element guarantees reasonable chemical component, resistance to high temperature oxidation and the corrosion resistance of weld metal.
Wherein, molybdenum is not oxidizable, subsequent can be added in the molten steel of scrap melting, reduces oxidization burning loss；Ferrosilicon can be used as deoxidation
Agent, while crystal grain can be refined.
The present invention uses pure potassium water glass as binder, due to containing K+So there are also stabilising arcs to act on, but excessive mistake
Dense to will cause that weldering speed is slow, it is big to splash, the viscosity of slag improves, and influences mechanical performance, and secondly modulus is excessively high promotes coating quick-drying to add
By force, keep electrode coating easily eccentric, used time coating intensity after high temperature is dried can also reduce, and therefore, the present invention uses modulus 3.0,
The pure potassium water glass of 40 ~ 44 ° of Be ' of Baume degrees (20 DEG C).
The utility model has the advantages that 1, present invention employs CaO-CaF2-SiO2Basic slag system cooperates rutile, a small amount of zircon sand and has
Welding rod is made in machine object, metal powder, alloy part powder and pure potassium water glass, has good welding usability, and electric arc is steady when welding
Fixed, diamagnetic blow ability is strong, easy to operate；Appearance of weld is good, and welding bead is smooth, and covering comprehensively, takes off slag and is easy；Molten bath clarity is good
It is good, it splashes in welding process small, powder amount is few；Welding rod adapts to wider welding current range, with alloy core wire technology path phase
Than core wire melting cost is greatly reduced, and coating is not rubescent in welding process, and sleeve protecting effect is good, and welding rod utilization rate is high, can be compared with
The applying working condition of LNG structure and build on-site peculiar to vessel is adapted to well.The other defects such as weld metal pore-free and crackle, to reach
Deposited metal is set to have the effect of preferable low-temperature impact toughness, higher tensile strength and yield strength at -196 DEG C.
2, usability of electrode of the present invention is good, can smooth extrusion, electrode coating intensity and surface quality in production process
Preferably, welding rod core shift is controllable；Deposited metal composition meets standard, weld metal pore-free and crackle, has preferable normal
Temperature stretches and low-temperature flexibility, good mechanical properties can be widely applied.
Specific embodiment
The present invention is further explained in the light of specific embodiments, so that those skilled in the art can be better
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, the welding rod include Ni-based core wire and are coated on core wire surface
Coating forms the chemical component and degree of Ni-based core wire are as follows: C :≤0.10%, Si :≤0.10%, Mn :≤0.10%, Cu:
≤ 0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤0.40%, Ni+Co: >=99.5%, each ingredient total amount is 100%.
Key problem in technology of the invention is to reasonably adjust slag system, and the correct ratio for controlling various medicinal powder in welding rod, each component is pressed
Weight proportion is as follows: CaCO3: 18 ~ 20%, CaF2: 10 ~ 12%, TiO2: 4 ~ 6%, Al2O3: 4 ~ 6%, zircon sand: 1 ~ 2%, CMC:0.5 ~
1%, potassium carbonate: 0.5 ~ 1%, hafnium metal powfer: 28 ~ 30%, metal molybdenum powder: 8 ~ 11%, manganese metal: 5 ~ 7%, ferrosilicon: 4 ~ 6%, molybdenum-iron: 3 ~
5%, ferro-niobium: 2 ~ 3%, each component total amount is 100%.Wherein CaCO3In the form of marmorean, CaF2In the form of fluorite, TiO2With
Rutile form is added, Al2O3In the form of Alpha-alumina, waterglass is added in the form of pure potassium water glass, wherein in coating
It is also added with binder, the additive amount of binder is 20 ~ 25% of raw material gross weight in coating.The chemical component of main raw material(s)
It is shown in Table 1.
The chemical component requirement of 1 main raw material(s) of table
The following are three embodiments of powder different weight percentage content in the present invention, in three embodiments, core wire rule
Lattice are 3.2 × 350mm of Ф, and other than the weight percent content of coating powder is different, remaining technical characteristic is all the same.It is specific real
It applies for example shown in table 2.
The type and ingredient contrast table of 2 embodiment chinese raw materials of table
Embodiment 1
The preparation method of LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, comprising the following steps:
Step 1: carrying out ingredient: C :≤0.10%, Si :≤0.10%, Mn according to following components and degree :≤
0.10%, Cu :≤0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤0.40%, Ni+Co: >=99.5%, by all components melting
Afterwards, it forged, rolled, drawing, chopping, Ni-based core wire is made, it is spare；
Step 2: being target proportion according to component in table 2 and degree, the Dali to be added of embodiment 1 is calculated
Stone, fluorite, rutile, α-Al2O3, zircon sand, carboxymethyl cellulose, potassium carbonate, hafnium metal powfer, metal molybdenum powder, manganese metal, silicon
The amount of iron, molybdenum-iron, ferro-niobium, and each material is weighed according to calculated result；Be mixed it is dry-mixed uniformly after, first be added material total weight
2.5% water, after pre- 2 ~ 3min of wet mixing, add weight and account for the binder of material total weight 20 ~ 25% and carry out wet mixing, after the group of beating
It is sent into extrusion press and is wrapped on Ni-based core wire, after low temperature bakes and high temperature bakes, the temperature that low temperature bakes
Degree is at 150 DEG C, and the temperature that high temperature bakes is 300 DEG C, and the time that low temperature bakes and high temperature bakes is 1.5h.
Embodiment 2
The preparation method of LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, in step 1 the preparation of core wire and chemistry at
Divide with embodiment 1, the weight percent content of coating powder is as shown in table 2；Remaining feature is the same as embodiment 1.
Embodiment 3
The preparation method of LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, in step 1 the preparation of core wire and chemistry at
Divide with embodiment 1 and embodiment 2, the weight percent content of coating powder is as shown in table 2；Remaining feature is the same as embodiment 1.
Test process is carried out to three types welding rod obtained above, wherein the 1 welding rod starting the arc of embodiment is slightly difficult, and welding bead covers
Gai Buquan, the slight dry slag in surface, the clarity in molten bath is inadequate, the poor operability of upward welding in the vertical position；2 welding bead of embodiment takes off slag and covers
Lid, appearance of weld, arc stability is best, and the operability of especially vertical position welding is good；Electric arc is unstable in embodiment 3, welds
It splashes in journey larger, flue dust is more, the poor operability of upward welding in the vertical position.Welding rod is used in view of what LNG structure and 9Ni steel peculiar to vessel were welded
Actual use operating condition, Comprehensive Correlation, choose embodiment 2 make a series of performance test.
According to the requirement of GB/T 13814-2008 and GB/T 25774.1-2010, using carbon steel test plate (panel) heap side.Welding rule
Model: AC welding, preceding two layers of single layer single track, rear several layers of every layer of twice, 70 ~ 130A of welding current, 25 ~ 30V of voltage, speed of welding
It for 5 ~ 10cm/min, is not required to preheat before weldering, between road temperature≤100 DEG C, without being heat-treated after the completion of welding.To embodiment 2
After the completion of carrying out the welding of deposition test plate (panel), a series of Physicochemical test is carried out.
As shown in table 3 and table 4, table 5,2 welding rod deposited metal chemical component of embodiment, room temperature mechanical stretch are listed respectively
The test result of performance and -196 DEG C of low-temperature impact works and lateral expansion.According to 13814 ENi6620 of AWSA5.11 and GB/T
The requirement of standard, chemical component, room temperature stretching and -196 DEG C of low-temperature impact works and lateral expansion of welding rod deposited metal are equal
Meet indices.
The deposited metal composition contrast table (mass percent, %) of 3 embodiment welding rod of table and standard requirements
4 embodiment welding rod of table and standard requirements deposited metal tensile property contrast table
5 embodiment welding rod of table and -196 DEG C of low-temperature impact works of standard requirements deposited metal and lateral expansion contrast table
Usability of electrode is good in the present invention, and stable mechanical property, manufacturing cost is low, and added value is big, the five-year, domestic
The demand of 9Ni steel at 100,000 tons or more, dive in 2000 tons or more even more, good market prospects by matched wlding
In Benefit.Low in cost, craftsmanship is excellent, arc stability, and arc stiffness is good, splash it is small, molten iron flow is good, weld seam at
Shape is beautiful, takes off slag and is easy, the chemical component of deposited metal, the indices such as mechanical property can meet standard requirements well.
Claims (4)
1.LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, which includes Ni-based core wire and the medicine for being coated on core wire surface
Skin, it is characterised in that: form the chemical component and degree of Ni-based core wire are as follows: C :≤0.10%, Si :≤0.10%, Mn :≤
0.10%, Cu :≤0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤0.40%, Ni+Co: >=99.5%, each ingredient total amount is
100%；The ingredient of raw material and its weight percent content be successively in coating are as follows: CaCO3: 18 ~ 20%, CaF2: 10 ~ 12%, TiO2: 4 ~
6%, Al2O3: 4 ~ 6%, ZrSiO4: 1 ~ 2%, CMC:0.5 ~ 1%, K2CO3: 0.5 ~ 1%, Cr:28 ~ 30%, Mo:8 ~ 11%, Mn:5 ~ 7%, silicon
Iron: 4 ~ 6%, molybdenum-iron: 3 ~ 5%, ferro-niobium: 2 ~ 3%, each ingredient total amount is 100%；Wherein, binder, binder are also added in coating
Additive amount be coating in raw material gross weight 20 ~ 25%.
2. LNG structure as described in claim 1 and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, it is characterised in that: the bonding
Agent uses modulus 3.0, the pure potassium water glass of 40 ~ 44 ° of Be ' of Baume degrees, chemical component are as follows: K2O >=12%, SiO2>=25%, S≤
0. 005%, P≤0.005%.
3. LNG structure as described in claim 1 and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, it is characterised in that: CaCO3With Dali
The form of stone is added, CaF2It is added in the form of fluorite, TiO2It is added in the rutile form, Al2O3With α-Al2O3Form add
Enter.
The preparation method of 4.LNG structure and the nickel-base welding rod of 9Ni steel peculiar to vessel welding, which comprises the following steps:
Step 1: carrying out ingredient: C :≤0.10%, Si :≤0.10%, Mn according to following elemental constituent and degree :≤
0.10%, Cu :≤0.10%, Mg :≤0.10%, S≤0.005%, Fe :≤0.40%, Ni+Co: >=99.5%, by all components melting
Afterwards, it forged, rolled, drawing, chopping, Ni-based core wire is made, it is spare；
Step 2: being target proportion: CaCO according to following components and weight percent content3: 18 ~ 20%, CaF2: 10 ~ 12%,
TiO2: 4 ~ 6%, Al2O3: 4 ~ 6%, ZrSiO4: 1 ~ 2%, CMC:0.5 ~ 1%, K2CO3: 0.5 ~ 1%, Cr:28 ~ 30%, Mo:8 ~ 11%, Mn:
5 ~ 7%, ferrosilicon: 4 ~ 6%, molybdenum-iron: 3 ~ 5%, ferro-niobium: 2 ~ 3%, calculate calcite and fluorite, rutile, the α-Al to be added2O3, zirconium
The amount of sand, carboxymethyl cellulose, potassium carbonate, hafnium metal powfer, metal molybdenum powder, manganese metal, ferrosilicon, molybdenum-iron, ferro-niobium, and according to meter
It calculates result and weighs each material；Be mixed it is dry-mixed uniformly after, first be added material total weight 2.5% water, pre- 2 ~ 3min of wet mixing
Afterwards, add weight and account for the binder of material total weight 20 ~ 25% and carry out wet mixing, after beat group feeding extrusion press it is interior wrapped in
On Ni-based core wire, nickel-base welding rod is made after baking.
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| CN108568614B (en) * | 2018-04-17 | 2020-11-06 | 南京工程学院 | Anti-coated red cracking nickel-based alloy welding rod and preparation method thereof |
| CN113579558B (en) * | 2020-04-30 | 2024-02-09 | 宝武特种冶金有限公司 | Nuclear grade nickel-chromium-iron alloy core wire and manufacturing method thereof |
| CN111843278A (en) * | 2020-06-23 | 2020-10-30 | 磐固合金(常州)有限公司 | Nickel-based welding rod for argon arc backing welding and preparation method thereof |
| CN114346380B (en) * | 2022-02-18 | 2022-10-28 | 上海绿地建设(集团)有限公司 | Welding process of high-strength steel structure |
| CN115502605B (en) * | 2022-09-26 | 2023-09-12 | 苏州思萃熔接技术研究所有限公司 | Welding rod for welding 9Ni steel for LNG low-temperature storage tank and preparation method of welding rod |
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| JP2000117488A (en) * | 1998-08-10 | 2000-04-25 | Kobe Steel Ltd | Ni-BASED ALLOY FLUX-CORED WIRE |
| CN103753051A (en) * | 2014-01-09 | 2014-04-30 | 上海交通大学 | Electric welding rod with novel slag system for welding 9Ni steel for storage tanks of LNG (liquefied natural gas) ships |
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| CN105108379A (en) * | 2015-09-30 | 2015-12-02 | 四川大西洋焊接材料股份有限公司 | Welding electrode compatible with Ni9 steel and capable of being used in cryogenic environment and preparation method thereof |
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