CN103934594A - Ultralow hydrogen ceramic welding flux for chrome molybdenum heat resistant steel and preparation method thereof - Google Patents
Ultralow hydrogen ceramic welding flux for chrome molybdenum heat resistant steel and preparation method thereof Download PDFInfo
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- CN103934594A CN103934594A CN201410124297.2A CN201410124297A CN103934594A CN 103934594 A CN103934594 A CN 103934594A CN 201410124297 A CN201410124297 A CN 201410124297A CN 103934594 A CN103934594 A CN 103934594A
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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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
- B23K35/3602—Carbonates, basic oxides or hydroxides
-
- 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
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/362—Selection of compositions of fluxes
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- Nonmetallic Welding Materials (AREA)
Abstract
Ultralow hydrogen ceramic welding flux for chrome molybdenum heat resistant steel comprises the following components, by mass percent, 28%-35% of MgO, 6%-15% of CaO, 17%-22% of CaF2, 13%-20% of Al2O3, 5%-10% of SiO2, 1%-5% of K2O + NaO, 0.5%-3.5% of ferromanganese, 0.5%-2% of ferrosilicon, and 6%-8% of MgCO3. The ultralow hydrogen ceramic welding flux for the chrome molybdenum heat resistant steel contains magnesia, fluoride, silicate, carbonate, the ferromanganese and the ferrosilicon serving as reducing agents and quartz which improves slag detachability and appearance of welding seams. When the ultralow hydrogen ceramic welding flux for the chrome molybdenum heat resistant steel is used for welding, the electric arc is stable, the slag detachability in the welding seams is good, the appearance of the welding seams is attractive, and the surfaces of the welding seams are free of cracks, air holes, indentations and other welding defects.
Description
Technical field
The invention belongs to technical field of welding materials, especially relate to a kind of chrome molybdenum heat resisting steel ultralow-hydrogen low bonded flux.
Background technology
Known, chrome-molybdenum steel has special high-quality performance, usually be used to manufacture some high temperature resistant, high voltage bearing valve and pressure vessels, the Mayari using on pressure vessel is mainly taking Cr-Mo as main, this class steel not only has resistant to elevated temperatures performance, also has good anti-hydrogen-type corrosion ability, but how to ensure after welding, welding point has and similarly performance of mother metal under high temperature, high pressure, various corrosive medium condition, is the test to welding material.Along with the application of Cr-Mo series heat resisting steel is more and more extensive, safety, the economical operation of steels for pressure vessel use and welding point will be played crucial effect to national industry-by-industry, for this reason, corresponding welding material has been proposed to acid test, and Cr-Mo steel easily causes hot and cold defects i.e.cracks in welding, conventional heat resisting steel is applicable to normal temperature and large gap welding condition with welding material; And in the narrow gap of groove and the welding of special heat resisting steel, require under low-temperature impact toughness (40 DEG C) environment, corresponding submerged arc welding flux is also in the blank stage.
Heat resisting steel is usually used in manufacturing the parts of at high temperature working in the industrial departments such as boiler, steam turbine, industrial furnace, dynamic power machine and aviation, petrochemical industry, nuclear power.At present, the serviceability temperature scope of heat resisting steel is 200～1300 DEG C, operating pressure be several MPas to tens MPas, working environment is very complicated.So present heat resisting steel welding material is except requiring elevated temperature strength, also require enough toughness, good machinability and weldability according to purposes difference, and certain structure stability.
The manufacture of large pressurized vessel is taking Lincoln weld as main, and especially narrow-clearance submerged arc welding connects.Domesticly exist larger unstability in heat-resistant steel submerged arc welding wire, solder flux and welding procedure, hot tearing problem etc. happens occasionally, be badly in need of improving conventional in the market high-strength heat-resistant steel submerged arc welding wire and solder flux, on market, supporting solder flux is difficult to meet and under different heat-treat conditions, in the time of high temperature, all has good mechanical property.
Current domestic heat resisting steel solder flux mostly is high temperature sintering solder flux, and the remaining diffusible hydrogen of weld seam is higher.The basicity that improves submerged arc welding flux is considered to obtain the effective measures of high tenacity weld seam, but can make diffusible hydrogen in weld seam increase thereupon, causes the cold crack tendency being caused by hydrogen to increase.The neutrality of domestic current research and production and caustic fusion solder flux, can not meet the performance requirement of quenching and tempering type high strength steel, so develop the needs that the new non-smelting type welding flux of the low hydrogen content of high alkalinity is high strength steel welding development.
Flux basicity improves, and its oxidation susceptibility reduces, but and the minimizing of hydrogen content has been subject to inhibition, this is general rule.In order to obtain the solder flux of the low hydrogen content of high alkalinity, take high temperature sintering, it can make the at high temperature whole or large portion removal of moisture (comprising the crystallization water) in solder flux, can improve again the intensity of solder flux, reduce its fragmentation, absorb the surface of moisture thereby also just reduced solder flux, that is reduced the moisture in solder flux, but the solder flux moisture absorption is serious after high temperature sintering, in welding process, diffusible hydrogen content is difficult to be controlled at lower level.
Summary of the invention
The object of this patent is a kind of chrome molybdenum heat resisting steel ultralow-hydrogen low bonded flux proposing, and the design concept of this solder flux is to adopt gas-slag-alloy discharge protection to obtain the even welding point of ultralow-hydrogen low of low hydrogen, and traditional submerged arc welding flux is taking slag protection as main.Bonded flux has the feature simple, energy resource consumption is low, processing performance is good of manufacturing.After high temperature sintering solder flux high temperature sintering, how to prevent the oxide water suction of alkali and alkaline earth metal ions, because inorganic binder burns after certain temperature, lost the crystallization water, also lost viscosity.And there are not these problems in low temperature bonded flux, therefore exploitation high alkalinity, ultralow-hydrogen low new type low temperature sintered flux have certain meaning.Manufacturing technology and technological requirement to container are more and more higher, not only require weld metal to have good obdurability coupling, and the narrow-clearance submerged arc welding of thick-walled vessel require solder flux to have good deslag performance and extremely good cracking resistance.
In order to realize described goal of the invention, the present invention adopts following technical scheme:
A kind of chrome molybdenum heat resisting steel ultralow-hydrogen low bonded flux, the each component of described solder flux and mass percentage content thereof are as follows: MgO:28～35%, CaO:6～15%, CaF
2: 17～22%, Al2O
3: 13～20%, SiO
2: 5～10%, K
2o+NaO:1～5%, ferromanganese: 0.5～3.5%, ferrosilicon: 0.5～2%, MgCO
3: 6～8%.
MgCO of the present invention
3remaining CO
2equivalent is 4%～8%.
A preparation method for ultralow-hydrogen low bonded flux for chrome molybdenum heat resisting steel, after formula batching, crosses 30 mesh sieves, and after mixing, modulation 42～45Be(20 DEG C adds water) potassium-sodium water glass; Cure 3h through 300 DEG C of low temperature, 500 DEG C of high temperature cure 60min, then cooling with stove, cross 12～60 mesh sieves, bonded flux.
Owing to having adopted technique scheme, the present invention has following beneficial effect: this sintered flux divides low temperature bonding solder flux, and domestic sintered flux, taking high temperature sintering solder flux as main, is widely used in every field.And bonded flux is because its manufacturability is difficult to hold, especially load mould problem is not resolved, this bonded flux greatly at 400～600 DEG C baking make, the hydrogen content of therefore containing in bonded flux is higher than melt flux and sintered flux.The design concept of this welding is that low-temperature sintering is to keep the carbonate of q.s, when baking, never degenerate, hydrogen content own is higher, by controlling the manufacturing process of solder flux, the hydrogen content of welding machine itself is declined, reduce the effect of hydrogen dividing potential drop and decompose a large amount of gas in the electric arc of remaining carbonate, thereby make diffusible hydrogen content very low.
Make solder flux gas in the process of curing and in welding process, be easy to discharge by modulation waterglass component.Sintering temperature is at 400 DEG C～700 DEG C sintering 60min, and at this temperature, marble can not decompose.This solder flux has higher basicity, can produce again appropriate CO simultaneously in welding process
2gas, the mechanism with the formation such as slag, alloying element gas-slag-metal Combined Protection, is down to below 3.0ml/100g diffusible hydrogen.This welding basicity is higher in addition, and a little less than oxidisability, oxygen content is down to below 270ppm～300ppm, makes weld seam not increase not rephosphorization of silicon, has good anti-hydrogen embrittlement, anti-temper brittleness, the crisp ability that ageing resistance heat treatment causes.Be down to≤3.0ml/100g of weld metal diffusible hydrogen, basicity is: 2.7～3.2, the weld metal that obtains not only oxygen, hydrogen content are low, and do not increase silicon, not rephosphorization, make weld seam there is good obdurability, excellent anti-hydrogen embrittlement, the ability of anti-temper brittleness.
The present invention adopts a kind of novel bonded flux, reduce as far as possible the harmful field trash such as S, P, O in weld seam by controlling the formula etc. of raw material grades, solder flux manufacturing process, optimization, improve its degree of purity, making has lower oxygen content in slag, ensure that in welding process, alloying component reaches effective transition, guarantee that it has good obdurability, adjust other component of solder flux simultaneously, realize optimization and the high-speed welding of welding procedure.
The solder type that this patent proposes contains magnesia, fluoride, silicate, carbonate, the ferromanganese that is used as reducing agent, ferrosilicon and improves the removability of slag and the quartz of appearance of weld.The weld defect such as good, appearance of weld is attractive in appearance, face of weld flawless, pore, load mould of the removability of slag in arc stability, seam while using sintered flux of the present invention welding.
In this sintered flux, the Main Function of each composition is summarized as follows:
Fused magnesite MgO:28～35%
Main Function is slag making, regulates fusing point, viscosity, surface tension and the mobility of slag, improves appearance of weld, and minimizing is splashed.In the time that fused magnesite content exceedes 35%, the viscosity of slag increases, and slag fluidity is poor, and spreadability reduces; When fused magnesite content is lower than 20% time, slag fluidity variation, causes appearance of weld variation.Thereby fused magnesite content in solder flux is controlled to 28～35%.
Fluorite CaF
2: 14～22%
Appropriate fluorite can reduce the surface tension of liquid metal, improves its mobility, makes appearance of weld attractive in appearance, reduces weld porosity sensitiveness, and can reduce the diffusible hydrogen content of deposited metal.Fluorite content lower than 14% time, makes appearance of weld bad, easy venthole in weld seam.In the time that fluorite content exceedes 22%, make arc stability variation, the content of therefore controlling fluorite in solder flux is 10～20%.
Corundum Al
2o
3: 13～20%
Main Function is slag making, regulates fusing point and the viscosity of slag.When corundum content is lower than 13% time, fusing point and the viscosity of slag are lower, and spreadability is poor; When corundum content is higher than 20% time, slag fusing point is too high, and when welding, the spreadability of liquid slag is poor, and the spreadability of slag is significantly reduced.Arc stability variation when welding.Thereby in control solder flux, corundum content is 13～20%.
Calcium oxide CaO:6～15%
Calcium oxide CaO adds with the form of wollastonite, mainly, as slag making, improves arc stability and droplet transfer performance.When CaO content in wollastonite is lower than 6% time, slag making amount is less, and butt welded seam protection effect is poor, and droplet transfer particle is larger, and ripple is thicker, and when CaO content in wollastonite is higher than 15% time, the siliconising that can increase butt welded seam, affects the performance of weld seam.Thereby should to control in solder flux CaO content in wollastonite be 6～15%.
Quartz SiO
2: 5～10%
The main improved effect appearance of weld of using.When silica flour content is lower than 5% time, appearance of weld is poor, and weld metal is sprawled not opened, and appearance of weld coefficient is less, and when silica flour content is higher than 10% time, the siliconising that can increase butt welded seam, affects the performance of weld seam.Thereby should to control quartz content in solder flux be 5～10%.
Ferrosilicon: 0.5～2%
Add the effect of mainly playing deoxidation.Ferrosilicon addition lower than 0.5% time, can not arrive the effect of deoxidation, and ferrosilicon addition higher than 2% time, can increase silicone content in weld seam.Thereby control ferrosilicon addition is 0.5～2%.
Ferromanganese: 0.5～3.5%
Adding of ferromanganese mainly played deoxidation and the effect that regulates viscosity coefficient of dross.Ferromanganese addition lower than 0.5% time, can not arrive the effect of deoxidation, and ferromanganese addition higher than 2% time, can increase the viscosity of slag.Thereby control ferromanganese addition is 0.5～3%.
MgCO
3：6～8％
MgCO
3add the effect of mainly playing gas making and slag making.MgCO
3addition lower than 6% time, can not arrive the effect of deoxidation, and protection is not enough, can produce pore, MgCO
3addition higher than 8% time, can increase the viscosity of slag, equally also can produce its fear.Thereby MgCO
3controlling addition is 6～8%.
The CO of metal carbonate remnants
2equivalent is: 4%～8%
As CO remaining in component
2when equivalent is greater than 8%, gas, flue dust that welding process produces are larger, and aggravating working environment, produces a large amount of load moulds, and simultaneous oxidation gas increases weld metal residual oxygen; As the CO when remaining in component
2when equivalent is greater than 4%, the partial pressure of generation is lower, is not enough to make diffusible hydrogen to be down to ultralow-hydrogen low level.
K
2O+Na
2O：1%～5%
The mixture of potassium sodium oxidation, owing to being easy to ionization in potassium sodium electric arc, mainly plays the effect of stable arc, and in the time that the two content sum is less than 1%, arc stability is poor, and appearance of weld is poor; In the time that the two content sum is greater than 5%, slag is rarer, and weld seam covers incomplete, is shaped poor.
Detailed description of the invention
Explanation the present invention that can be detailed by the following examples, discloses object of the present invention and is intended to protect all technological improvements in the scope of the invention.
The concrete proportioning of bonded flux composition is as shown in table 1.
Table 1 embodiment composition proportion (wt%)
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| MgO | 28% | 35% | 32% |
| CaF 2 | 22% | 17% | 20% |
| Al 2O 3 | 20% | 13% | 19% |
| CaO | 11% | 8% | 10% |
| SiO 2 | 10% | 9% | 5% |
| K 2O+NaO | 1% | 5% | 3.5% |
| Si-Fe | 0.5% | 1.5% | 2% |
| Mn-Fe | 0.5% | 3.5% | 2.5% |
| MgCO 3 | 7% | 8% | 6% |
This solder flux weld seam processing performance is good, and when welding, in arc stability, the white bright non-oxidation look of face of weld, groove, the removability of slag is good, and after vibration, the de-slag rate of bottom reaches more than 75%, and the automatic perk of slag in groove is touched de-.Appearance of weld is attractive in appearance, and bead height is moderate, and aspect ratio of weld is 1.6, and it is moderate that weld seam infiltrates angle.Can coordinate multiple welding wire to use, adopt three kinds of solder flux of embodiment 1 to 3 to match with corresponding welding wire, 1.25%Cr-0.5Mo, 2.25%Cr-1Mo, 2.25Cr-1Mo-0.3V steel that welding thickness of slab is 80mm, the chemical composition of welding wire is as table 2.
The chemical composition of embodiment main raw material(s) requires as shown in table 2.
The chemical composition of table 2 embodiment welding wire
O, H content in chemical composition, mechanical property and the weld seam of embodiment 1～3 postwelding measurement weld seam, result is as table 3, table 4, table 5.Comprehensive mechanical property is good, and diffusible hydrogen and residual oxygen are lower:
Table 3 welding rod deposited metal composition of the present invention
Table 4 weld metal mechanical property
The oxygen content of table 5 weld metal, diffusible hydrogen content
In embodiment, in weld seam, averaged oxygen content is≤270ppm, and in weld seam, diffusible hydrogen is all less than 3ml/100g(IIW mercury process).
Part not in the detailed description of the invention is prior art.
Claims (3)
1. a chrome molybdenum heat resisting steel ultralow-hydrogen low bonded flux, is characterized in that: the each component of described solder flux and mass percentage content thereof are as follows: MgO:28 ~ 35%, CaO:6～15%, CaF
2: 17～22%, Al
2o
3: 13～20%, SiO
2: 5～10%, K
2o+NaO:1～5%, ferromanganese: 0.5～3.5%, ferrosilicon: 0.5 ~ 2%, MgCO
3: 6～8%.
2. chrome molybdenum heat resisting steel ultralow-hydrogen low bonded flux as claimed in claim 1, is characterized in that: described MgCO
3remaining CO
2equivalent is 4% ~ 8%.
3. a preparation method for ultralow-hydrogen low bonded flux for chrome molybdenum heat resisting steel as claimed in claim 1, is characterized in that: after formula batching, cross 30 mesh sieves, after mixing, modulation 42 ~ 45Be(20 DEG C adds water) potassium-sodium water glass; Cure 3h through 300 DEG C of low temperature, 500 DEG C of high temperature cure 60min, then cooling with stove, cross 12～60 mesh sieves, bonded flux.
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|---|---|---|---|
| CN201410124297.2A CN103934594B (en) | 2014-03-28 | 2014-03-28 | A kind of chrome molybdenum heat resisting steel ultralow-hydrogen low bonded flux and preparation method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101579927B1 (en) * | 2014-10-28 | 2015-12-29 | 현대종합금속 주식회사 | Agglomerated flux for multi-electrode high-basic submerged arc welding |
| CN109093286A (en) * | 2018-09-29 | 2018-12-28 | 四川西冶新材料股份有限公司 | A kind of 2.25Cr-1Mo steel exchange submerged arc welding welding wire and solder flux |
| CN109093287A (en) * | 2018-09-29 | 2018-12-28 | 四川西冶新材料股份有限公司 | A kind of 2.25Cr-1Mo-0.25V steel exchange submerged arc welding welding wire and solder flux |
| CN111037155A (en) * | 2019-12-31 | 2020-04-21 | 四川西冶新材料股份有限公司 | 850 MPa-grade weather-proof high-strength steel matched submerged-arc welding flux |
| CN113210925A (en) * | 2021-05-10 | 2021-08-06 | 合肥紫金钢管股份有限公司 | Welding flux for submerged-arc welding of 12Cr2Mo1R alloy steel pipe and preparation method thereof |
| CN113305469A (en) * | 2021-05-13 | 2021-08-27 | 中国船舶重工集团公司第七二五研究所 | Smelting flux for submerged-arc welding of austenitic welding wire and preparation method thereof |
| CN114273818A (en) * | 2022-01-24 | 2022-04-05 | 昆山京群焊材科技有限公司 | Submerged arc welding wire and welding flux for 1.25% Cr-0.5% Mo-V steel in coal chemical industry |
| WO2023037920A1 (en) * | 2021-09-07 | 2023-03-16 | 株式会社神戸製鋼所 | Bond flux for submerged arc welding, and weld metal |
| WO2023037921A1 (en) * | 2021-09-07 | 2023-03-16 | 株式会社神戸製鋼所 | Bond flux for submerged arc welding, and weld metal |
| CN115890063A (en) * | 2022-12-30 | 2023-04-04 | 四川西冶新材料股份有限公司 | Welding flux for submerged arc welding of P92 steel |
| JP7566660B2 (en) | 2020-02-27 | 2024-10-15 | 日鉄溶接工業株式会社 | Bond flux for submerged arc welding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101579927B1 (en) * | 2014-10-28 | 2015-12-29 | 현대종합금속 주식회사 | Agglomerated flux for multi-electrode high-basic submerged arc welding |
| CN109093286A (en) * | 2018-09-29 | 2018-12-28 | 四川西冶新材料股份有限公司 | A kind of 2.25Cr-1Mo steel exchange submerged arc welding welding wire and solder flux |
| CN109093287A (en) * | 2018-09-29 | 2018-12-28 | 四川西冶新材料股份有限公司 | A kind of 2.25Cr-1Mo-0.25V steel exchange submerged arc welding welding wire and solder flux |
| CN111037155A (en) * | 2019-12-31 | 2020-04-21 | 四川西冶新材料股份有限公司 | 850 MPa-grade weather-proof high-strength steel matched submerged-arc welding flux |
| JP7566660B2 (en) | 2020-02-27 | 2024-10-15 | 日鉄溶接工業株式会社 | Bond flux for submerged arc welding |
| CN113210925A (en) * | 2021-05-10 | 2021-08-06 | 合肥紫金钢管股份有限公司 | Welding flux for submerged-arc welding of 12Cr2Mo1R alloy steel pipe and preparation method thereof |
| CN113305469A (en) * | 2021-05-13 | 2021-08-27 | 中国船舶重工集团公司第七二五研究所 | Smelting flux for submerged-arc welding of austenitic welding wire and preparation method thereof |
| WO2023037920A1 (en) * | 2021-09-07 | 2023-03-16 | 株式会社神戸製鋼所 | Bond flux for submerged arc welding, and weld metal |
| WO2023037921A1 (en) * | 2021-09-07 | 2023-03-16 | 株式会社神戸製鋼所 | Bond flux for submerged arc welding, and weld metal |
| CN114273818A (en) * | 2022-01-24 | 2022-04-05 | 昆山京群焊材科技有限公司 | Submerged arc welding wire and welding flux for 1.25% Cr-0.5% Mo-V steel in coal chemical industry |
| CN114273818B (en) * | 2022-01-24 | 2023-11-28 | 昆山京群焊材科技有限公司 | Submerged arc welding wire for 1.25% Cr-0.5% Mo-V steel in coal chemical industry and welding flux |
| CN115890063B (en) * | 2022-12-30 | 2024-02-09 | 四川西冶新材料股份有限公司 | Flux for submerged arc welding of P92 steel |
| CN115890063A (en) * | 2022-12-30 | 2023-04-04 | 四川西冶新材料股份有限公司 | Welding flux for submerged arc welding of P92 steel |
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