CN1788919A - High alkalinity, low activity, superlow hydrogen sintering type solder - Google Patents

High alkalinity, low activity, superlow hydrogen sintering type solder Download PDF

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Publication number
CN1788919A
CN1788919A CN 200410060339 CN200410060339A CN1788919A CN 1788919 A CN1788919 A CN 1788919A CN 200410060339 CN200410060339 CN 200410060339 CN 200410060339 A CN200410060339 A CN 200410060339A CN 1788919 A CN1788919 A CN 1788919A
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solder flux
welding
flux
low
hydrogen
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CN100374238C (en
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姚润钢
孔红雨
刘刚
周浩
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Luoyang Shuangrui Special Alloy Material Co., Ltd.
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725th Research Institute of CSIC
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Abstract

The sintered welding flux with high alkalinity, low activity and ultralow hydrogen content consists of MgO 28-33 wt%, CaF2 12-20 wt%, Al2O3 16-22 wt%, SiO2 8-15 wt%, CaCO3 5-10 wt%, BaCO3 5-10 wt%, Na2O 2-4 wt%, Li2CO31-4 wt% and ReF 2-6 wt%. It has high grain strength, moisture absorbing resistance and S and P content meeting the requirement of relevant national standard, diffusion hydrogen content lower than 5 ml/100 g. It is fitted with 10NiCrMoTi welding wire and 05Ni3Mn2MoTi welding wire for low temperature no-preheating welding in ship yard and can result in excellent joint mechanical performance. It has excellent technological performance, smooth weld seam, good spreading, smooth transition to the base material and good slag eliminating performance.

Description

High basicity, low activity, ultralow hydrogen sintered flux
Affiliated technical field
The invention belongs to the solder flux of solder technology, relate to a kind of high basicity, low activity, ultralow hydrogen sintered flux, be mainly used in the submerged-arc welding of Hi-Stren steel.
Background technology
Authorization CN87102741B " high-basicity sintered flux " introduced a kind of be used for low-alloy high-strength steel especially heavy wall adopted BaO-MgO-CaF with the sintered flux of steel welding 2-Al 2O 3Type slag system and Na 2AlF 6And Li 2Agglutinants such as O mainly are to improve the anti-moisture absorption ability of solder flux by adding above-mentioned agglutinant;
Publication number CN86102751A " sintering flux with ultra-low hydrogen and high alkaline sintered by high temp " introduced be mainly used in low-alloy high-strength steel especially heavy wall adopted MgO-CaO-Al with the sintered flux of steel welding 2O 3-CaF 2Slag system, flux basicity 2.3~2.6, principal character is that weld metal does not increase Si, do not return P, is suitable for the welding of heavy wall narrow-clearance submerged arc welding;
It is 3.0~3.7 sintered flux that authorization CN1013086B " a kind of high-basicity sintered flux " has introduced basicity, by adding rare earth element, improves the form of field trash in the weld seam, improves the low-temperature flexibility of weld seam;
Publication number CN1415454A " a kind of sintered flux that is used for multifibres, high speed Lincoln weld " has introduced multifibres, the high speed submerged arc welding flux of low-carbon micro steel-alloys such as being used for pipeline, boats and ships, boiler, pressure vessel, bridge structure;
Publication number CN1326838A " fluoric alkali high toughness sintered flux " has introduced and has cooperated the sintered flux that is suitable for the welding of X series pipe line steel steel pipe with the H08C welding wire;
Publication number CN1107770A " sintering flux with ultra-low hydrogen and high alkaline sintered by high temp " has introduced the solder flux that is mainly used in nuclear reactor pressure container and other important pressure vessel welding, cooperates with corresponding welding wire to have good anti-irradiation fragility and welding technological properties.
Whether the sintered fluxs such as SJ101, SJ102 that adopt in a large number on several sintered fluxs that above-mentioned patent is introduced and the present domestic market all do not propose this solder flux and are applicable under the shipyard harsh environmental conditions, build the welding of important Ship Structure, the especially ability of the anti-cold crack of welding material under cryogenic conditions at the higher Hi-Stren steel of alloy content.Technical elements, above-mentioned solder flux all do not carry out the activity control of solder flux, although the solder flux that has has adopted higher basicity, the activity of solder flux is not low.The sintered flux that authorization CN87102741B introduces adopts agglutinant to improve the anti-moisture absorption ability of solder flux, needs to increase the operation of making agglutinant together.Although the solder flux that has in the above-mentioned solder flux has added carbonate, too high sintering temperature does not almost have carbonate in the finished product solder flux residual.
Summary of the invention
The object of the present invention is to provide a kind of high basicity, low activity, ultralow hydrogen sintered flux, be used under the shipyard environmental condition, adopting the higher Hi-Stren steel of alloy content to carry out the submerged-arc welding welding that important Ship Structure is built.
Compared with prior art, the present invention has adopted following technological approaches: 1. control oxygen content in the weld metal by the activity of control solder flux, improve the weld metal low-temperature flexibility; 2. the interpolation by compound carbonate, and the sintering temperature of control solder flux make residual an amount of carbonate in the finished product solder flux, reach the purpose that reduces the weld metal diffusible hydrogen; 3. by single Li 2CO 3Adding, improve the anti-moisture absorption ability of solder flux.
High basicity of the present invention, low activity, ultralow hydrogen sintered flux are that the composition by following weight percentage constitutes: 28~33%MgO, 12~20%CaF 2, 16~22%Al 2O 3, 8~15%SiO 2, 5~10%CaCO 3, 5~10%BaCO 3, 2~4%Na 2O, 1~4%Li 2CO 3, 2~6%R EF.This solder flux adopts common sintered flux preparation method, that is: will do by the powder that mentioned component is formed mix, wet mixing, granulating, low temperature drying, high temperature sintering, sieve, finished product packing etc., consider the resolution characteristic of various carbonate, sintering temperature is controlled between 650~780 ℃.
Be used under the shipyard environmental condition, adopting the higher Hi-Stren steel of alloy content to carry out the submerged-arc welding welding of important shipbuilding, cooperate the low alloy steel welding wire that is complementary with the steel plate composition, also require solder flux good anti-moisture absorption ability to be arranged, reach ultralow hydrogen and require (less than 5ml/100g for avoiding producing weld crack, mercury process or chromatography), low S, P content in the weld metal, cooperate with welding wire to have the good mechanical performance and solder flux has good welding technological properties (appearance of weld, surface quality, the removability of slag) etc.
Obtain good weld metal mechanical property in order to guarantee that solder flux cooperates with welding wire, the alloying of welding wire is absolutely necessary, but also will control the Physical Metallurgy characteristic of solder flux.Basicity is one of Physical Metallurgy approach of control solder flux, but only this point still is not enough.According to welding Physical Metallurgy theory, the activity of solder flux slag is the major influence factors of oxygen content in the weld metal.The basicity formula of solder flux is as follows:
Each oxide can add BaO, SrO in this formula molecule as alkaline components all by weight percentage in the formula.Calculate by this, the basicity of solder flux is controlled in 2.4~2.8 the scope, with the processing performance of coordinating solder flux and the relation between the weld metal mechanical property.
The activity formula of solder flux is as follows:
In the formula
Figure A20041006033900052
Same BaO, SrO also can count in the formula by being equal to CaO.
Activity according to solder flux is classified, and solder flux can be divided into: high activity solder flux (A f〉=0.6), activated rosin flux (A f=0.6~0.3), low activity solder flux (A f=0.3~0.1) and inertia solder flux (A f≤ 0.1) four big classes, in order to obtain the good low-temperature impact toughness of weld metal, sintered flux of the present invention is by the A of control solder flux f≤ 0.15, promptly control oxygen content in the weld metal with the low activity solder flux, mainly be SiO in the control solder flux 2Content realize.
The anti-moisture absorption performance of solder flux also has influence on the use of solder flux under the shipyard environmental condition.The solder flux of anti-moisture absorption ability can adsorb a large amount of moisture in welding process, also cause the generation of crackle in the welding process.Therefore the anti-moisture absorption ability that improves solder flux is the key that this solder flux uses at shipyard.Improve the anti-moisture absorption ability of solder flux, the influence of several respects factors such as flux preparing process, flux composition, sintering schedule is arranged.Solder flux manufacturing process of the present invention stirs by powerful after the solder flux wet mixing, makes the particle densification of solder flux, and after granulating by the stranding of rolling of certain hour, make the surface ratio of solder flux slick and sly, improve the anti-moisture absorption ability of solder flux.According to sintering theory, a spot of liquid phase participates in improving the compactness extent of sintered body in the solid-phase sintering process.Added Li in the solder flux of the present invention 2CO 3Low melting point, and the sintering temperature of determining like this makes that like this sintering degree of solder flux is finer and close between 650~780 ℃, anti-moisture absorption ability is better, adds Li in the solder flux 2CO 3Main effect promptly be this, Li simultaneously 2CO 3Also can play the effect of stable arc.
One of three big factors that influence welding point generation weld crack under the low temperature and high humidity environmental condition are the effects of hydrogen, so welding cold cracking is also referred to as hydrogen induced cracking.And the source of hydrogen is made up of two parts in the welding process, extraneous moisture is invaded in the first welding process, if the anti-moisture absorption ability of solder flux will cause the large quantity of moisture that solder flux sucks in the welding process to decompose, thereby cause the rapid increase of hydrogen content in the weld metal.The various moisture (adsorbed water, the crystallization water and water of constitution) that another approach of the source of hydrogen is in the raw material to be comprised, when selecting raw material for use, selected solder flux of the present invention the raw material that do not contain or contain less various moisture for use, and adopted higher sintering temperature (650~780 ℃), the source that has further reduced hydrogen.But under shipyard low temperature and high humidity environmental condition, also be not enough so only.According to Welding Metallurgy and physical chemistry theory, the hydrogen dividing potential drop can promote the rapid diffusion of hydrogen in the welding pool to overflow in the reduction arc atmosphere, and residual carbonate decomposites CO in the solder flux in welding process 2Can reduce the dividing potential drop of hydrogen in the welding arc atmosphere, thereby reduce the influence of hydrogen.The present invention has studied the carbonate that adopts usually in several solder flux in research process, as CaCO 3, BaCO 3, Li 2CO 3, SrCO 3Resolution characteristic, determine compound interpolation by several carbonate of material, and sintering temperature and time by the control solder flux are controlled carbonate content residual in the solder flux, guarantee to meet in the welding process ultralow hydrogen requirement, and solder flux has good welding technological properties simultaneously.
A large amount of theory and practice prove that interpolation proper amount of rare-earth element can change the inclusion morphology in the weld metal in the weld metal, makes the inclusion particle nodularization, thereby improves the low-temperature flexibility of weld metal.Usually adopt the mode of rare earth alloy to add rare earth element, these rare earth alloies obtain oxidation when high temperature sintering, make weld metal oxygenation in the welding process, and weld metal toughness is worsened.The present invention passes through R EThe addition manner of F has promptly been eliminated the influence of weld seam oxygenation, and by with the cooperatively interacting of low-alloy welding wire, make weld metal obtain good toughness.
The purpose of residual carbon hydrochlorate is in order to reduce the weld metal diffusible hydrogen content in the solder flux, is exactly the welding procedure variation of solder flux but bring another problem, especially easily forms surface pressing pit in welding process.This need improve the gas effusion characteristic that produces in the welding process by physical characteristic, the especially viscosity coefficient of dross of regulating the solder flux slag.CaF 2As the main raw material(s) of solder flux, have the effect that reduces diffusible hydrogen on the one hand, have positive effect to regulating solder flux slag characteristic on the other hand.By repetition test, determine to add CaF in the solder flux of the present invention 2The OK range of content is 12~20%.Technological other aspects of solder flux also are by debugging repeatedly as the deslag performance of the sprawling of weld metal, solder flux, reach a good effect.
Low S in the weld metal, P content be by adopting S, raw material that P content is low, and the taking off S, take off P effect and employing S of CaO, the approach such as low alloy steel welding wire that P content is lower realize.
High basicity, low activity, ultralow hydrogen sintered flux that the present invention proposes, the granule strength of solder flux is better, the anti-moisture absorption ability of solder flux, S, P content all satisfy GB12470 " low-alloy steel used for submerged arc welding solder flux " requirement, the diffusible hydrogen content of solder flux is low, satisfies the ultralow hydrogen requirement of diffusible hydrogen content less than 5ml/100g.Cooperate with the 10NiCrMoTi welding wire and cooperate with the 05Ni3Mn2MoTi welding wire, weld metal has good joint mechanical property, carries out not pre-thermal weld under the shipyard cryogenic conditions, does not find weld crack.The processing performance of solder flux is good, and the face of weld fairing is sprawled well, and with the mother metal transitions smooth, the removability of slag is good.
The specific embodiment
The proposition embodiment of the invention is as follows:
In the concrete chemical composition such as table 1 of embodiment, adopted two kinds of 10NiCrMoTi welding wires and a kind of 05Ni3Mn2MoTi welding wire to cooperate with it and welded.The steel plate of 10NiCrMoTi welding wire welding is the thick 11NiCrMoV steel plate of 16mm, and the steel plate of 05Ni3Mn2MoTi welding wire welding is the thick 10CrNi3MoV steel plate of 24mm.The chemical composition such as the table 2 of two kinds of welding wires, postwelding have been measured the chemical composition and the mechanical performance of weld metal, and it the results are shown in table 3 and table 4, and have carried out rigidity butt joint welding cracking test under the shipyard environmental condition, and it the results are shown in table 5.
The solder flux chemical composition (wt%) of table 1 embodiment
Classification MgO CaF 2 Al 2O 3 SiO 2 CaCO 3 BaCO 3 Na 2O Li 2CO 3 R EF
Embodiment A 30 18 21 10 7 8 3 2 1
Embodiment B 33 14 17 13 9 6.5 2.5 3 2
Embodiment C 28 20 22 10 5 10 2.5 1.5 1
Embodiment D 31 12 17.5 15 10 5 4 2.5 3
The welding wire chemical composition (wt%) that table 2 embodiment is adopted
Welding wire Gage of wire C S P Si Mn Cr Ni Mo Ti
10NiCrMoTi-1# 4.0mm 0.078 0.0063 0.0076 0.121 1.04 0.326 1.53 0.106 0.092
10NiCrMoTi-2 0.102 0.0054 0.0073 0.123 1.10 0.330 1.29 0.092 0.107
05Ni3Mn2MoTi 0.01 0.005 0.007 0.08 1.55 / 2.50 0.03 0.11
The corresponding metal chemical composition of table 3 embodiment (wt%)
Welding material C Si Mn S P Ni Cr Mo Ti
10NiCrMoTi-1# silk+embodiment A 0.078 0.192 0.936 0.0056 0.013 1.38 0.472 0.115 0.0086
10NiCrMoTi-2# silk+Embodiment B 0.080 0.200 0.975 0.0048 0.012 1.28 0.478 0.111 0.011
10NiCrMoTi-1# silk+Embodiment C 0.075 0.190 0.912 0.0062 0.012 1.35 0.481 0.121 0.0081
10NiCrMoTi-2# silk+embodiment D 0.083 0.211 0.926 0.0045 0.014 1.24 0.461 0.112 0.010
The 05Ni3Mn2MoTi+ embodiment A 0.046 0.093 1.25 0.010 0.012 2.32 0.179 0.242 /
Table 4 embodiment weld metal mechanical performance
Welding material Rp0.2 MPa Rm MPa A % Z % AKv,J
10NiCrMoTi-1# silk+embodiment A 527.5 602.5 27 73 -40℃:156 -60℃:143
10NiCrMoTi-2# silk+Embodiment B 535 612.5 25.5 74.5 -40℃:190 -60℃:168
The 05Ni3Mn2MoTi+ embodiment A 595 672.5 24 67.5 -20℃:160 -50℃:138
10NiCrMoTi-1# silk+Embodiment C 510 590 23 71 -40℃:123 -60℃:100
10NiCrMoTi-2# silk+embodiment D 525 595 22 72 -40℃:134 -60℃:105
Table 5 embodiment cooperates rigidity butt joint cracking test result under the shipyard environmental condition of welding wire
Welding material Environmental condition Pre-thermal system The face crack rate The section crack rate The root crack rate
10NiCrMoTi-2# silk+Embodiment B 6.9℃37%RH Not preheating 0 0 0
The weld metal diffusible hydrogen content of embodiment A, B, C, D solder flux is respectively 2.25,3.28,4.03,3.55ml/100g (IIW-ISO3690 of International Institute of Welding chromatography determination), and the weld metal diffusible hydrogen content that the glycerine method is measured under the shipyard environmental condition is 0.96ml/100g.The anti-moisture absorption of solder flux A is 0.125%, satisfy GB12470 " low-alloy steel used for submerged arc welding solder flux " regulation less than 0.15% requirement.The S of solder flux A, P content are respectively 0.034% and 0.020%, also satisfy GB12470 " low-alloy steel used for submerged arc welding solder flux " regulation S, P content respectively less than 0.060%, 0.080% requirement.
Find out by all kinds of indexs and the performance of being tested in the foregoing description, adopt solder flux of the present invention to cooperate the low alloy steel welding wire welding low-alloy high-strength steel, the weld metal S, the P content that are obtained are low, and weld metal toughness is good, and anti-cold crack ability is good under the shipyard environmental condition.The foregoing description solder flux processing performance in welding process is good, and the face of weld fairing is sprawled well, and with the mother metal transitions smooth, the removability of slag is good, and welding bead has welded the perk automatically of its skull of back, and face of weld does not adhere to slag.

Claims (1)

1, a kind of high basicity, low activity, ultralow hydrogen sintered flux, it is characterized in that: the composition by following weight percentage constitutes: 28~33%MgO, 12~20%CaF 2, 16~22%Al 2O 3, 8~15%SiO 2, 5~10%CaCO 3, 5~10%BaCO 3, 2~4%Na 2O, 1~4%Li 2CO 3, 2~6%R EF.
CNB2004100603397A 2004-12-17 2004-12-17 High alkalinity, low activity, superlow hydrogen sintering type solder Expired - Fee Related CN100374238C (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
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CN101585123A (en) * 2009-06-01 2009-11-25 林肯电气合力(郑州)焊材有限公司 Sintered flux for stainless steel
CN101564804B (en) * 2009-06-05 2011-04-20 中国船舶重工集团公司第七二五研究所 Hard surfacing sintered flux and manufacturing method thereof
CN102601544A (en) * 2012-03-21 2012-07-25 宝鸡市宇生焊接材料有限公司 High-alkalinity high-tenacity low-hydrogen agglomerated flux and preparation method thereof
CN101537550B (en) * 2008-03-19 2012-09-05 上海纪好旺造船科技发展有限公司 Submerged arc sintered flux and production method thereof
CN102085603B (en) * 2009-12-02 2012-11-28 中冶焊接科技有限公司 Fluorine-base type sintered flux used for reducing sulfur and phosphorus contents of welding joint and used in submerged arc hardfacing
CN103273222A (en) * 2013-01-07 2013-09-04 中国船舶重工集团公司第七二五研究所 High-strength high-tenacity sintered flux for afterheat-free welding
CN104400256A (en) * 2014-10-31 2015-03-11 天津市宏远钛铁有限公司 Low-hygroscopicity submerged-arc welding sintered flux and preparation method thereof
CN104708229A (en) * 2013-06-05 2015-06-17 天津大学 Application of low-melting-point flux to large-power TIG welding joint protection
CN105234578A (en) * 2015-08-18 2016-01-13 上海纪好旺造船科技发展有限公司 Marine submerged-arc welding composite sintered flux and preparing method thereof
CN106271223A (en) * 2015-05-12 2017-01-04 海宁瑞奥金属科技有限公司 Phase stainless steel use submerged arc flux-cored wire solder flux
CN106624460A (en) * 2017-01-06 2017-05-10 招商局重工(江苏)有限公司 Low-temperature steel saw sintered flux used for ships
CN109396613A (en) * 2018-11-16 2019-03-01 昆山中冶宝钢焊接材料有限公司 A kind of submerged arc welding flux and its welding procedure for double wire welding
CN112059473A (en) * 2020-09-12 2020-12-11 北京金威焊材有限公司 Ultralow-hydrogen type high-alkalinity high-toughness sintered flux

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JPS6045995B2 (en) * 1982-07-28 1985-10-14 新日本製鐵株式会社 Composite wire for electrogas arc welding
JPS6213295A (en) * 1985-07-02 1987-01-22 Kobe Steel Ltd Strapping material for welding
JPS62151292A (en) * 1985-12-26 1987-07-06 Kawasaki Steel Corp Flux for submerged arc welding
CN1034265C (en) * 1994-06-14 1997-03-19 冶金工业部钢铁研究总院 ultra-low-hydrogen and high-basicity sintered flux

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101537550B (en) * 2008-03-19 2012-09-05 上海纪好旺造船科技发展有限公司 Submerged arc sintered flux and production method thereof
CN101585123A (en) * 2009-06-01 2009-11-25 林肯电气合力(郑州)焊材有限公司 Sintered flux for stainless steel
CN101564804B (en) * 2009-06-05 2011-04-20 中国船舶重工集团公司第七二五研究所 Hard surfacing sintered flux and manufacturing method thereof
CN102085603B (en) * 2009-12-02 2012-11-28 中冶焊接科技有限公司 Fluorine-base type sintered flux used for reducing sulfur and phosphorus contents of welding joint and used in submerged arc hardfacing
CN102601544A (en) * 2012-03-21 2012-07-25 宝鸡市宇生焊接材料有限公司 High-alkalinity high-tenacity low-hydrogen agglomerated flux and preparation method thereof
CN103273222A (en) * 2013-01-07 2013-09-04 中国船舶重工集团公司第七二五研究所 High-strength high-tenacity sintered flux for afterheat-free welding
CN104708229A (en) * 2013-06-05 2015-06-17 天津大学 Application of low-melting-point flux to large-power TIG welding joint protection
CN104400256A (en) * 2014-10-31 2015-03-11 天津市宏远钛铁有限公司 Low-hygroscopicity submerged-arc welding sintered flux and preparation method thereof
CN106271223A (en) * 2015-05-12 2017-01-04 海宁瑞奥金属科技有限公司 Phase stainless steel use submerged arc flux-cored wire solder flux
CN106271223B (en) * 2015-05-12 2019-01-22 海宁瑞奥金属科技有限公司 Phase stainless steel use submerged arc welding material
CN105234578A (en) * 2015-08-18 2016-01-13 上海纪好旺造船科技发展有限公司 Marine submerged-arc welding composite sintered flux and preparing method thereof
CN106624460A (en) * 2017-01-06 2017-05-10 招商局重工(江苏)有限公司 Low-temperature steel saw sintered flux used for ships
CN106624460B (en) * 2017-01-06 2021-06-04 招商局重工(江苏)有限公司 Marine low-temperature steel submerged-arc welding sintered flux
CN109396613A (en) * 2018-11-16 2019-03-01 昆山中冶宝钢焊接材料有限公司 A kind of submerged arc welding flux and its welding procedure for double wire welding
CN112059473A (en) * 2020-09-12 2020-12-11 北京金威焊材有限公司 Ultralow-hydrogen type high-alkalinity high-toughness sintered flux

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