CN103846577B - A kind of X100 pipe line steel solder flux used for submerged arc welding and preparation method thereof - Google Patents

A kind of X100 pipe line steel solder flux used for submerged arc welding and preparation method thereof Download PDF

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CN103846577B
CN103846577B CN201410117833.6A CN201410117833A CN103846577B CN 103846577 B CN103846577 B CN 103846577B CN 201410117833 A CN201410117833 A CN 201410117833A CN 103846577 B CN103846577 B CN 103846577B
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solder flux
pipe line
welding
line steel
flux
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CN103846577A (en
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常敬
刘越
张庆红
刘慧�
才艳秋
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JINZHOU SWAN WELDING CONSUMABLES Co Ltd
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JINZHOU SWAN WELDING CONSUMABLES Co Ltd
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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
    • 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
    • B23K2101/00—Articles made by soldering, welding or cutting
    • B23K2101/04—Tubular or hollow articles
    • B23K2101/06—Tubes
    • 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
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/02—Iron or ferrous alloys
    • B23K2103/04—Steel or steel alloys
    • 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
    • B23K9/00—Arc welding or cutting
    • B23K9/18—Submerged-arc welding

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Nonmetallic Welding Materials (AREA)

Abstract

The invention belongs to the solder flux field of material molding, be specifically related to a kind of X100 pipe line steel solder flux used for submerged arc welding and preparation method thereof.The chemical component weight percentage ratio of solder flux is: CaF219～25wt.%, MgO15～30wt.%, Al2O315～20wt.%, CaO2～10wt.%, SiO210～20wt.%, MnO4～6wt.%, TiO25～10wt.%；Its technological process is: dispensing → be dry mixed → wet mixing → pelletize → dry → sinter → sieve → check.The present invention is by changing manganous silicate, wollastonite composition in SJ101 G solder flux, and adds alloying constituent Si Fe, Ti Fe, Mn Fe, Borax, TiO2Deng, mating identical H08C welding wire carries out soldering test, by analyzing the different welding usability of solder flux, the microstructure and mechanical property of welding point, provides foundation for developing a kind of novel X100 pipe line steel sintered flux.The present invention can solve X100 Pipeline Weld Metal intensity and can not reach the grade of mother metal and mate by force, and welding usability all can not meet the problems such as high-strength X100 pipe line steel demand.

Description

A kind of X100 pipe line steel solder flux used for submerged arc welding and preparation method thereof
Technical field
The invention belongs to the solder flux field of material molding, be specifically related to a kind of X100 pipe line steel solder flux used for submerged arc welding And preparation method thereof.
Background technology
Constantly building and expanding along with transport pipelines such as petroleum gases, especially in ruthless area, right The requirement of pipe line steel is more strict, in order to meet the requirement of its adverse circumstances and reduce production cost, in recent years Have developed new high-grade pipe line steel and X100 pipe line steel, but matched sintered flux but phase To delayed.
At present, the sintering of the brands such as SJ101, SJ101-G, BG-SJ101-G that domestic steel tube factory commonly uses Solder flux, mainly for X70, X80 pipe line steel, still can not meet X100 high tensile pipeline steel and greater degree Pipe line steel welding, mate by force owing to X100 Pipeline Weld Metal intensity can not reach the grade of mother metal, and Welding usability all can not meet the demand of high-strength X100 pipe line steel, welds heavy caliber, the life of large wall thickness steel tube Produce requirement, on the premise of mainly ensureing toughness, improve the intensity of Pipeline Weld Metal, SJ101-G solder flux The deposited metal mechanical property of coupling H08C, H03M welding wire is shown in Table 1.
Table 1H08C, H03M welding wire deposited metal mechanical property
σs/MPa σb/MPa δ5/% Akv(-20℃)/J
H08C+SJ101-G 454～500 537～542 23～30 134
H03M+SJ101-G 562～640 637～692 21～23 159
As can be seen from Table 1, H08C, H03M welding wire coupling SJ101-G, its deposited metal can not meet The use requirement of X100 pipe line steel, produces needs to meet the actual submerged arc welding of X100 pipe line steel, improves Weld strength and toughness, it is necessary to take into account the submerged arc welding flux developing other alloy system mates suitable welding wire for submerged-arc welding, Adjust microalloy element and control impurity element (as controlled O, N, S, P content) in weld metal, to carry The degree of purity of high deposited metal.
The subject matter that the welding of X100 pipe line steel exists is how to reach optimal of intensity, toughness and weldability Join, to improve strength of welded joint and toughness as target, to Ti, B, Mn of weld(ing) deposit transition trace Deng alloying element, increasing flux basicity and improve the low-temperature impact toughness of deposited metal, suppression is without eutectoid effectively Ferritic precipitation, makes weld seam metallographic structure obtain acicular ferrite structure tiny, uniform, thus improves weldering Seam metal strength and low-temperature impact toughness.Alloying must be on the premise of protection component be safe and reliable, to the greatest extent Yield strength and tensile strength may be improved, thus reach to alleviate the purpose of construction weight, saving steel.
Summary of the invention
It is an object of the invention to provide a kind of X100 pipe line steel solder flux used for submerged arc welding and preparation method thereof, solve X100 Pipeline Weld Metal intensity can not reach the grade of mother metal and mate by force, and welding usability all can not meet The problems such as high-strength X100 pipe line steel demand.
The technical scheme is that
A kind of X100 pipe line steel solder flux used for submerged arc welding, the chemical component weight percentage ratio of solder flux is: CaF219～ 25wt.%, MgO15～30wt.%, Al2O315～20wt.%, CaO2～10wt.%, SiO210～20 Wt.%, MnO4～6wt.%, TiO25～10wt.%.
Described X100 pipe line steel solder flux used for submerged arc welding, also includes: account for the bonding of described solder flux 15～20wt.% Agent.
Described X100 pipe line steel solder flux used for submerged arc welding, the chemical component weight percentage ratio of preferred solder flux is: CaF219～25wt.%, MgO20～30wt.%, Al2O317～20wt.%, CaO3～10wt.%, SiO212～16wt.%, MnO4～6wt.%, TiO26～9wt.%.
Described X100 pipe line steel solder flux used for submerged arc welding, also includes: B2O31.5～3.0wt.%, NaO21.0～ 2.5wt.%。
Described X100 pipe line steel solder flux used for submerged arc welding, also includes: Ti0.01～0.02wt.%, B0.002～ 0.006wt.%。
Described X100 pipe line steel solder flux used for submerged arc welding, adds alloying constituent as required: Si-Fe, Ti-Fe, Mn-Fe One of or two or more, add the Si-Fe alloying constituent weight 3～6wt.% of siliceous 75wt%, titaniferous 30wt%'s Ti-Fe alloy grain weight amount 3～6wt.%, below carbon containing 0.7wt%, low-carbon Mn-Fe containing manganese 75～80wt% Weight 4～8wt.%.
Described X100 pipe line steel solder flux used for submerged arc welding, basicity B of X100 pipe line steel solder flux used for submerged arc weldingⅡwFor 1.5～2.1.
The preparation method of described X100 pipe line steel solder flux used for submerged arc welding, specifically comprises the following steps that
(1) dispensing
Weighing up needed raw material by formula components to be placed in same container, slag former mineral dust accounts for raw material gross weight 90～95wt.%, alloying constituent accounts for the 5～10wt.% of raw material gross weight；Wherein, the granularity of slag former mineral dust It is 200 mesh～300 mesh；Alloying constituent is one of Si-Fe, Ti-Fe, Mn-Fe or two or more；
(2) it is dry mixed
The dispensing prepared in container is stirred 20～25 minutes, makes each powder mix homogeneously；
(3) wet mixing
Sodium KP1 is added in above-mentioned powder the most by evenly mixing with 180～220ml/ kilogram of raw material, enters Wet the stirring of row becomes semisolid；
(4) pelletize
By the wet feed that stirs rubbing granulating back and forth in container basin, and by 10～30 mesh sieves；
(5) dry
Evaporating the attached water of wet grain particle surface, drying temperature is 120～160 DEG C, programming rate be 120～ 160 DEG C/h；
(6) sintering
Eliminate further the water of crystallization in solder flux, the flux particle of drying is put into heating furnace is heated to 740～ 760 DEG C, it is incubated 80～100 minutes；
(7) sieve
The solder flux sintered passes through 10～60 mesh sieves, through checking qualified formation X100 pipe line steel solder flux used for submerged arc welding.
The preparation method of described X100 pipe line steel solder flux used for submerged arc welding, it is preferable that step (4) crosses 14 mesh Sieve.
The preparation method of described X100 pipe line steel solder flux used for submerged arc welding, it is preferable that agglomerant in step (6) Skill is as follows:
(1) room temperature is 3.0～4.0 DEG C/min with programming rate, is warming up to 340～360 DEG C, is incubated 80～100 Minute；
(2) continuing with programming rate is 4.5～5.0 DEG C/min, is warming up to 740～760 DEG C, is incubated 80～100 Minute；
(3) room temperature is cooled to the furnace.
The mentality of designing of the present invention is:
The present invention is by adding trace alloying element and improving flux basicity in sintered flux, high alkalinity fluorine alkaline type welds Agent is conducive to the desulfurization of weld metal, dephosphorisation reaction, it is also possible to the oxygen content in reduction weld metal, and favorably In the transition of alloying element, improve impact toughness of welded joint.Intensity and the low-temperature impact of heightening deposited metal are tough Property, primary concern is that the alloying element in solder flux promotes that weld metal latus inframedium bar ferrite is to acicular ferrite Change.In the selection of solder alloy agent, weld seam adds Ti, B can be introduced by welding wire and solder flux, passes through Welding wire add Ti without difficulty, but add B time, owing to B is active element, scaling loss in welding wire steel smelting process Seriously, and in weld metal, add B the most rationally by solder flux, add B to solder flux2O3(Borax) can produce Raw reduction reaction, and B2O3It is prone to reduction.
1, the composition design of solder flux
Generally, sintered flux adds, such as: fluorite, crude magnesium sand, aluminum vitriol with the form of various mineral Soil, wollastonite, Borax, silicon dioxide, manganosite, titanium dioxide, sodium oxide etc., mineral mainly contains Oxide and fluoride etc. are (such as: MnO, SiO2、CaO、MgO、Al2O3、CaF2、TiO2、B2O3、 NaO2Deng), it is considered to the weld metal deoxidation problem in the alloying of weld metal and welding process, so adding Appropriate ferroalloy (such as: Ti-Fe, Si-Fe, Mn-Fe etc.).By the addition of alloying constituent, play refinement Crystal grain, the purpose of increase weld seam AF forming core, have certain rush to improving acicular ferrite content in weld metal Enter effect.Wherein:
CaF2Deriving from fluorite, belong to alkaline fluoride, fusing point is relatively low, it is possible to effectively reduce cinder high-temperature viscosity, Improve slag fluidity, and improve electric conductivity, improve appearance of weld, to improving welding procedure, improve deposition gold Belong to mechanical performance and have the biggest effect, rational CaF2Content can play the effect of stable electric arc.CaF2In weldering Decomposing in connecing reaction, [F] of generation catches reduction reaction in slag and produces [O2-], suppress [O2-] to molten Transition in metallisation, thus reduce [the O in deposited metal2-] oxygen content, and reduce [the H in arc atmosphere+] Dividing potential drop.But, too high levels can affect the stability of welding arc, cause simultaneously slag cross dilute affect weld seam become Shape, a certain amount of CaF2With Al2O3The slag formed that matches has weight to the non-metallic inclusion reduced in weld seam Want meaning.In the present invention, CaF2Content control 19～25wt.%.
MgO derives from crude magnesium sand, belongs to strong basicity oxide, and fusing point is 2800 DEG C, as adjusting slag Basicity and add, be also that the control of a kind of excellent slag making materials and butt welded seam shape has good effect, high It is changed into stable cubic crystal after temperature heating.Also have raising deposited metal impact flexibility, reduction diffusible hydrogen contains The effect of amount, but MgO fusing point is higher, increases viscosity coefficient of dross, improves slag solidification temperature, the stream of suppression slag Dynamic property makes appearance of weld be deteriorated, de-slag difficulty；When content of MgO is less than 15wt.%, slag oxidisability is relatively big, Weld seam part is oxidized to blueness；When content of MgO is higher than 30wt%, owing to its fusing point is higher, slag Mobility is poor, increases the effect of slag surface tension force, and the removability of slag is deteriorated, and appearance of weld can be made less able. In the present invention, in order to ensure Weld Performance, the content of MgO controls 15～30wt.%.
Al2O3Deriving from aluminum vanadine, belong to stable amphoteric oxide, its fusing point is 2050 DEG C, flux constituent Conventional vitreous body slag making materials, and there is the effect increasing slag surface tension force, it is the regulator of viscosity coefficient of dross, Welding bead surface oxidation-resistant can be improved, improve the concentrative effect of electric arc, increase a certain amount of Al2O3Can reduce Impression and tendency thereof, but too high Al2O3Content can make weld seam radian come to a point and unsmooth, be easily generated pore and Pit, is unfavorable for improving de-slag；And Al2O3Content is too low makes again face of weld uneven, occur load mould and The defects such as undercut, affect appearance of weld.In the case of content of MgO is more, for controlling the viscosity of slag, Al should be controlled2O3Content.Al is very big to the affinity of oxygen, so Al2O3It is a kind of stable oxide, The least to the Oxidation of Mn and Si, can effectively suppress CO pore.Along with Al2O3Increase, de-slag Becoming better and better, but face of weld is blueness, on slag, pore also gets more and more, and pit easily occurs in face of weld.This In invention, Al2O3Content control 15～20wt.%.
CaO derives from wollastonite Ca3(Si3O9), add and sintered flux can improve flux basicity, adjust slag Viscosity and mobility, improve welding processing performance.But the easy moisture absorption of CaO increases [H], and CaO ionization potential is relatively Low, add the addition of C aCO3Stabilising arc effect can be played, moreover it is possible to improve desulfurization phosphorus ability, thus reduce weld metal Hot cracking tendency.But as the CaCO in solder flux3When content exceedes a certain limit, CaCO3Pyrolytic is released A large amount of CO2Gas, makes solder flux gas forming amount dramatically increase, and produces serious bulging slag phenomenon；On the contrary, CaCO3Contain Measure too low, then electric arc is unstable, and appearance of weld is deteriorated.In the present invention, the content of CaO control 2～ 10wt.%。
SiO2It is a kind of acidic materials, it is possible to decrease flux basicity, there is again the important function of stable electric arc simultaneously, With CaF in solder flux2Collocation, can effectively suppress the generation of pore, the porosity resistance ability of raising solder flux during weldering knot； SiO simultaneously2Participating in slag making, the freezing point of adjustable slag, surface tension and cinder high-temperature viscosity, butt welded seam shapes Control extremely important；SiO in solder flux2Content too much can make viscosity increase, and reduces the stability of electric arc, but welds SiO when connecing2The content that is mingled with in deposited metal can be made to increase, reduce impact flexibility, in conjunction with X100 pipe line steel Feature, too high SiO2Content can cause welding wire scaling loss excessive, too greatly reduces flux basicity, makes weld seam return Si increases, and low-temperature impact toughness declines.Work as SiO2When content is less than 10%, electric arc is unstable, produces current interruption Phenomenon；Work as SiO2When content is more than 20%, increasing Si in deposited metal, the viscosity of slag is excessive simultaneously, mobility It is deteriorated.In the present invention, SiO2Content control 10～20wt.%.
MnO derives from manganosite, can adjust in deposited metal and measure containing Mn, and it reduces slag fusing point, improves The mobility of slag, beneficially appearance of weld, reduce surface tension, for the removability of slag and the toughness of deposited metal There is important impact.The addition of MnO, can improve the basicity of sintered flux, increases the reproducibility of sintered flux, Purify weld metal.And in fluorine alkaline type sintered flux, MnO is possible not only to as SiO2Reduce slag like that Fusing point, improves slag fluidity, and can reduce surface tension, beneficially appearance of weld.In welding process In with SiO2It is combined into compound silicate, forms good welding slag, protect deposited metal, make deposited metal not Affected by N and O in air, and the manganese element being reduced is primary alloy constituent in weld seam, weldering can be improved Seam intensity and impact flexibility, the Mn being simultaneously reduced and the S chemical combination in weld seam, form MnS and can play again de- The effect of S, reduces weld seam and produces hot cracking tendency, but MnO is often with manganese ore, Mn-rich slag and the shape of manganous silicate Formula adds, and these raw materials typically contain higher S, P content.In the present invention, the content of MnO control 4～ 6wt.%。
TiO2The fusion temperature of slag can be reduced, improve the mobility of slag, promote the poly-of weld metal reduzate Collect and be rejected in slag, and TiO2Can substitute for SiO2Do acidic oxide slag former and add in solder flux, high Wen Shineng and CaF2Reaction generates TiF2, have the effect of resistant to hydrogen pore.And very big with the affinity of O, with The form Dispersed precipitate of molecule oxide, in weld seam, can promote refinement of welded metal, Ti and C The TiC particle butt welded seam formed plays dispersion-strengthened action.B2O3In B be active element, welding wire steel was smelted In journey, scaling loss is serious, and adds B in weld metal the most rationally by solder flux, adds B in solder flux2O3 (Borax) can produce reduction reaction, and B2O3Being prone to be reduced to B, this is conducive to needle-like in weld(ing) deposit Ferritic acquisition.In the present invention, the impact that Ti with B is simultaneously introduced properties of weld is optimal；TiO2Content Control 5～10wt.%, B2O3Content control 1.5～3.0wt.%；Correspondingly, the content control of Ti, B System is at Ti0.01～0.02wt.%, B0.002～0.006wt.%.
NaO2Ionization energy the lowest, can improve arc voltage, reduce cathode protection activation energy, make electronics be prone to Excite, so that electric arc easily ignites and stablizes burning.But, Na+With O2-Affinity very strong, often Make OH-Anion is destroyed and O2-In conjunction with, increase H+Concentration, make in weld seam formed pore.In the present invention, NaO2Content control 1.0～2.5wt.%.
In weld seam, Ti with N affinity is extremely strong, can form TiN, reduces free N in steel, and suppression N's is unfavorable Impact；Ti and Al can make the abundant deoxidation of molten steel, denitrogenation simultaneously, to the weld seam molten bath containing B, can protect B not Easily it is burnt；Add the elements such as B and Mn and can postpone austenite to ferritic transformation, promotion intracrystalline and crystal boundary The formation of acicular ferrite；B and Ti in solder flux is together with microalloies such as Nb and V in X100 pipeline steel Element can form more carbonitride, oxide and complex chemical compound thereof, and these tiny compound particles are in weldering Can be as the core of cenotype forming core when austenite decomposition in seam cooling procedure, beneficially secondary structure refinement.Have Alloying constituent and oxygen have the highest affinity, such as: ferrosilicon, ferromanganese, ferrotianium etc., be alloying constituent the most also It it is the deoxidizer of weld metal.In most cases, sintered flux adds more active deoxidizing agent, these Ferroalloy also plays the effect of alterant simultaneously.
2, slag system selects and basicity controls
Fluorine alkaline type solder flux mates with suitable welding wire and is readily obtained the weld seam that low-temperature impact toughness is higher, because fluorine alkali Type slag system solder flux contains more basic anhydride, easy and SiO2In conjunction with, advantageously reduce SiO2Activity, (Si) and (O) in steel is made to be more likely formed SiO2, promote weld metal deoxidation, reduce the burning of alloying element Damage, thus coordinate with suitable welding wire, be conducive to improving the impact flexibility of weld seam.In the present invention, select fluorine alkali Type slag system MgO-CaF2-Al2O3-CaO-SiO2As the slag system of solder flux, the solder flux code name FB of fluorine alkaline type slag system, Main component: CaF2>=15%, CaO+MgO+Al2O3>=50%, SiO2≤20%。
Basicity is one of leading indicator describing solder flux performance, and it not only affects solder flux processing performance, and affects The mechanical performance of weld seam.When Resistance of Weld Metal impact flexibility requires higher, it is typically chosen the fluorine alkali that basicity is higher Type slag system, is conducive to improving the impact flexibility of weld metal, and when submerged arc welding is tested, main difficulty is Welder Skill performance is difficult to ensure, arc burning is unstable, especially with more difficult during AC welding process. Both required during pipe line steel submerged arc welding that solder flux had good welding technological properties, required again that weld metal had relatively High low-temperature impact toughness, it is therefore necessary to coordinate to solve the contradiction between both.
Basicity B used according to International Institute of WeldingⅡwComputing formula:
B IIw = CaO + MgO + BaO + Na 2 O + CaF 2 + 0.5 ( MnO + FeO ) SiO 2 + 0.5 ( Al 2 O 3 + TiO 2 + ZrO 2 )
In formula, each compound all represents the mass fraction in solder flux, and high alkalinity fluorine alkaline type solder flux is conducive to weldering The seam desulfurization of metal, dephosphorisation reaction, it is also possible to reduce the oxygen content in weld metal, and beneficially alloying element Transition, improve impact toughness of welded joint.The change of flux basicity can directly affect the performance of solder flux, this Basicity B of bright middle sintered fluxⅡwIt is 1.5～2.1.
Advantages of the present invention and providing the benefit that:
1, the composition such as manganous silicate, wollastonite during the present invention changes sintered flux SJ101-G, by improving solder flux alkali Degree, adds alloying constituent Si-Fe, Ti-Fe, Mn-Fe, TiO2With Borax etc., in weld metal, transition trace closes Gold dollar usually improves intensity, improves flux basicity and improves the low-temperature impact toughness of weld metal.
2, the present invention can improve deoxy performance in weld metal, and improves solder flux welding technological properties, optimizes Two groups of flux constituents carry out soldering test, make full use of the pass between weld metal composition, tissue and performance three System, improves the toughness and tenacity of deposited metal.
H10Mn2(EH14), H08Mn2MoA 3, sintered flux of the present invention can be with welding wire for hidden arc welding: (EA3), H08MnMo(EA2) etc. the use that matches.
4, the present invention strengthens weld metal matrix by additional element, controls weld seam hardenability, phase alternating temperature Degree, grain size, grain form etc. and then control microstructures of weld metals, and reduce its loss in toughness as far as possible.
The elements such as C, Si, P, S, the N that can significantly raise brittle transition temperature during 5, the present invention reduces weld seam Content is to ensure toughness, and C has been down to low carbon levels, to reduce the carbon equivalent of weld metal, tendency of hardenability And crack-sensitivity coefficient, and adapt to high efficiency big electric current, high heat-input welding.
6, the present invention reduces the content having infringement alloying element in wlding to toughness as far as possible, selects to damage toughness Less alloying element strengthens weld metal matrix.
7, the alloying element that the present invention adds should make the rate of cooling scope of formation acicular ferrite and bainite become Width, adds trace alloying element, forms effective field trash and suppress Ovshinsky at cyrystal boundary segregation in austenite crystal Body crystal boundary migration, thus promote acicular ferrite nucleating, control acicular ferrite and granular bainite content ratio.
8, the present invention selects suitable deposited metal alloying element, and controls restricted element, connects improving welding Head weather-resistance.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of sintered flux of the present invention.
Fig. 2 is embodiment 1-2 impact fracture morphology analysis.Wherein, (a) is embodiment 1 macrofracture photo； B () is embodiment 2 macrofracture photo；C () is that embodiment 1 scans fracture photo；D () is embodiment 2 Scanning fracture photo.
Fig. 3 is the metallographic structure figure of embodiment 1 deposited metal.
Fig. 4 is the metallographic structure figure of embodiment 2 deposited metal.
Fig. 5 is the metallographic structure figure of embodiment 3 deposited metal.
Fig. 6 is the metallographic structure figure of embodiment 4 deposited metal.
Detailed description of the invention
In the present invention, the main chemical component weight percentage ratio of X100 pipe line steel solder flux used for submerged arc welding is: CaF219～ 25wt.%, MgO15～30wt..%, Al2O315～20wt.%, CaO2～10wt.%, SiO210～20wt.%, MnO4～6wt.%, TiO25～10wt.%.It addition, also include: account for described solder flux main chemical composition 15～ The binding agent (sodium KP1) of 20wt.%.
In the present invention, X100 pipe line steel solder flux used for submerged arc welding can also include: B2O31.5～3.0wt.%；NaO2 1.0～2.5wt.%.
In the present invention, X100 pipe line steel solder flux used for submerged arc welding can also include: Ti0.01～0.02wt.%, B 0.002～0.006wt.%.
In the present invention, basicity B of X100 pipe line steel solder flux used for submerged arc weldingⅡwIt is 1.5～2.1.
As it is shown in figure 1, the preparation method of X100 pipe line steel solder flux used for submerged arc welding of the present invention is as follows:
(1) dispensing
Weighing up needed raw material by formula components to be placed in same container, slag former mineral dust accounts for raw material gross weight 90～95%, alloying constituent accounts for the 5～10% of raw material gross weight；Wherein, the granularity of slag former mineral dust is 200 Mesh～300 mesh.Alloying constituent is one of Si-Fe, Ti-Fe, Mn-Fe or two or more；
In sintered flux, the chemical composition of slag former and physical property determine the processing performance of solder flux, select slag making group Thing is become to should ensure that slag has certain viscosity, relatively low fusion temperature and sufficiently wide liquid solidification temperature.Cause This, determine that the slag former of sintered flux and alloying constituent composition are: slag former accounts for mineral dust raw material gross weight 90～95%, alloying constituent accounts for the 5～10% of raw material gross weight.
(2) it is dry mixed
The dispensing prepared in container is stirred 20～25 minutes, makes each powder mix homogeneously；
(3) wet mixing
Sodium KP1 (industry sodium potassium silicate) is added above-mentioned having mixed with every 180～220ml/ kilogram of raw material Close in uniform powder, carry out wet stirring and become semisolid；
In industry sodium potassium silicate, sodium potassium weight ratio is 1:1 or 2:1 or 3:1, ripple magnesium degree Be (20 DEG C) 41.0～49.5.
(4) pelletize
By the wet feed that stirs rubbing granulating back and forth in container basin, and by 10～30 mesh sieves (preferably 14 mesh sieves)；
(5) dry
Evaporating the attached water of wet grain particle surface, drying temperature is 120～160 DEG C, programming rate be 120～ 160 DEG C/h；
(6) sintering
Eliminate further the water of crystallization in solder flux, the flux particle of drying is put into heating furnace is heated to 740～ 760 DEG C, it is incubated 80～100 minutes；
(7) sieve
The solder flux sintered passes through 10～60 mesh sieves, through checking qualified formation X100 pipe line steel solder flux used for submerged arc welding.
In the present invention, flux particle can not completely cut off the most greatly air conservation weld seam very well, causes alloy transfer Bad；The least then breathability Wang Liang of flux particle, dust is excessive, and causes weld seam slag inclusion.Be dried at solder flux, Dry, in sintering process will necessarily some solder flux due to aspects such as pelletizes, granule strength is the highest, And then become tiny granule or fine powder, so the solder flux after sintering is carried out sieving being very important.
In step (6), preferred sintering process is as follows:
(1) room temperature is 3.0～4.0 DEG C/min with programming rate, is warming up to 340～360 DEG C, is incubated 80～100 Minute；
(2) continuing with programming rate is 4.5～5.0 DEG C/min, is warming up to 740～760 DEG C, is incubated 80～100 Minute；
(3) room temperature is cooled to the furnace.
In the present invention, add raw material Si-Fe, Ti-Fe, Mn-Fe one or more time, in solder flux Corresponding chemical component weight percentage ratio is: the Si-Fe weight 3～6wt.% of siliceous 75wt%, titaniferous 30wt% Ti-Fe alloy grain weight amount 3～6wt.%, below carbon containing 0.7wt%, low-carbon Mn-Fe containing manganese 75～80wt% Weight 4～8wt.%.
It addition, B can be added as required when dispensing2O3And NaO2。
Below by embodiment and accompanying drawing, the present invention is further elaborated on.
Embodiment 1-2
As shown in table 2, in embodiment 1-2, the chemical composition of X100 pipe line steel is as follows:
The chemical composition (wt.%, surplus Fe) of X100 pipe line steel in table 2 embodiment
C Mn Si Al Ti V Cr Ni Cu Mo P S
0.083 1.66 0.27 0.33 0.34 0.33 0.29 1.1 1.04 0.53 0.009 0.002
As shown in table 3, in embodiment 1-2, the mechanical property of X100 pipe line steel is as follows:
The mechanical property of X100 pipe line steel in table 3 embodiment
σ s(MPa) σ b(MPa) δ (%) Contraction percentage of area Ψ % Hardness (HV) Akv(-20 DEG C)/J
≥615 ≥760 ≥17 ≥40 220～270 200～240
As shown in table 4, in embodiment 1-2, the chemical composition of H08C welding wire is as follows:
The chemical composition (wt.%, surplus Fe) of H08C welding wire in table 4 embodiment
C Si Mn Mo Ti B S P
0.007 0.25 1.58 0.34 0.11 0.005 0.002 0.011
As shown in table 5, in embodiment 1-2, sintered flux chemical composition is as follows:
The main chemical composition of sintered flux (wt.%) in table 5 embodiment
Numbering SiO2 MgO Al2O3 CaF2 CaO MnO TiO2
Embodiment 1 12.7 29.9 19.3 22.6 3.7 5.4 6.4
Embodiment 2 12.9 20.9 19.5 25.0 9.5 5.6 6.6
As shown in table 6, in embodiment 1-2, the welding procedure scoring of solder flux is as follows:
The welding procedure scoring of solder flux in table 6 embodiment
Flux composition Arc stability The removability of slag Appearance of weld Comprehensive grading
Embodiment 1 90 93 94 93
Embodiment 2 90 90 92 91
The test solder flux coupling H08C welding wire of embodiment 1 and embodiment 2, welding condition is: welding electricity Pressure 30V, welding current 550A, weldering speed 44cm/min.Arc stability, de-slag, weld seam in welding process The welding usability such as shaping are good, and gained metal chemical composition is following (table 7):
The deposited metal composition (wt.%, surplus Fe) of solder flux in table 7 embodiment
Sample C Mn Si Ti P S
Embodiment 1+H08C 0.055 1.76 0.89 0.035 0.024 0.013
Embodiment 2+H08C 0.051 1.50 0.43 0.026 0.019 0.014
The relatively chemical composition of postwelding weld(ing) deposit, significant difference is embodiment 1 solder flux weld metal Mn, Si constituent content is apparently higher than the content in embodiment 2 solder flux weld metal.According to soldering theory, 1600 DEG C time, the order that oxygen affinity is ascending is by each element: Cu, Ni, Co, Fe, W, Mo, Cr, Mn、V、Si、Ti、Zr、Al.Owing to the Fe concentration in weld zone is maximum, the most necessarily there is the Fe of part Oxidized；Ni is in the element on the Fe left side, owing to concentration is relatively low, and also the least with the affinity of oxygen, therefore Oxidational losses is the least.Although Mo, Cr are positioned at the right side of Fe, but due to they affinitys with oxygen and Fe Close, and in molten drop with molten pool metal, concentration is on the low side, and so oxidization burning loss is less, transfer coefficient is bigger； Although the concentration of Mn, Si, Ti is the highest, but owing to the affinity with oxygen is very big, so oxidization burning loss is more serious. Additionally, Ti is due to very active, also will react with the nitrogen in arc atmosphere, generate TiN etc., this will Cause the further reduction of its recovery.
As in figure 2 it is shown, select embodiment 1, embodiment 2 solder flux coupling H08C welding wire, welded deposited metal Low temperature (-20 DEG C) impact fracture macro morphology and sem analysis, being observed by impact fracture macro morphology can To find out: the fracture corresponding to embodiment 1 solder flux there occurs obvious plastic deformation before fracturing, shear labial surface Long-pending very big, in irregular shape, see Fig. 2 (a)；Only there is a small amount of change in embodiment 2 solder flux deposited metal fracture Shape, fracture is smooth, sees Fig. 2 (b).By SEM photograph it can be seen that the low-temperature impact of embodiment 1 weld seam is broken Split for ductile rupture, the fracture apperance almost all dimple fracture feature of pars fibrosa and radiation area under scanning electron microscope, Belonging to typical ductile fracture pattern, ballistic work now is higher, sees Fig. 2 (c)；Embodiment 2 fracture apperance In some dimple, some pattern is the cleavage fracture of river pattern, this be mainly at direct stress In the lower crystal grain of effect, interatomic bond key destroys and the transgranular fracture that formed, also has step-like edge in this fracture simultaneously Brilliant fracture apperance, this fracture is to be formed owing to coarse grains reduces the inhibition of crystal boundary On Crack Propagation Grain boundary fracture, there is no obvious plastic deformation, fracture is concordant, belongs to brittle fracture, therefore its welding toughness Can be lower, see Fig. 2 (d).
Containing graininess particle bottom the dimple of weld seam fracture, these particles are typically all and reacted in Welding Metallurgy The field trash formed in journey, the second phase constitution common in deposited metal when field trash is welding, occur mainly with The series of physical chemical reaction of weld zone, i.e. includes that each type oxide that deoxygenation generates is mingled with, also includes The carbon of Precipitation during solid-state phase changes, nitride, this illustrates that the mechanism of production of toughness nest is micropore accumulation type Mechanism, is shown in Fig. 2 (c)；Figure can be seen that little cleavage crystal face, river pattern, little cleavage step and tear The typical pattern of the quasi-cleavage fractures such as rib, is shown in Fig. 2 (d), Quasi cleavage by between be clearly present some ductility ridges, It is mainly made up of tiny dimple, and it there are the improvement helping sample impact flexibility.
As Figure 3-Figure 4, can from embodiment 1 and embodiment 2 solder flux obtained deposited metal microstructure Going out, embodiment 1 solder flux deposited metal is organized as acicular ferrite and substantial amounts of granular bainite line and staff control, its Yield strength is apparently higher than X100 pipe line steel mother metal yield strength, and low-temperature impact toughness is obviously improved. The deposited metal of embodiment 2 solder flux then contains acicular ferrite, block pro-eutectoid ferrite and thick side plate Bar Martensite-Bainite Mixed Microstructure.
This is owing in embodiment 1 formula, the content of MgO is higher than embodiment 2 formula, big when containing in molten bath When measuring the slag of MgO, under the high temperature action of electric arc, MgO can be brought in weld metal into and be mingled with, weld seam Oxygen content increases, and makes weld seam alloying component decline simultaneously；MgO is a kind of excellent slag making materials and right simultaneously The control of weld shape has good effect, is changed into stable cubic crystal after high-temperature heating, is also that slag sticks The regulator of degree, adjusts the mobility of slag, has the effect increasing slag surface tension force, improves the physics of slag Performance, makes weld seam have the good removability of slag.
Mn, as main alloying element, the kinetics that appreciable impact austenite changes, is conducive to refinement ferrum element Body crystal grain, refines bainite ferrite slip, thus improves the intensity of weld seam, reduces ductile-brittle transition temperature.And In solder flux, the content of MnO is the highest, and the Mn element of transition in weld metal is the most.In embodiment 1 and reality Executing in 2 two kinds of formula of example, the content of embodiment 1 solder flux MnO is more than embodiment 2 solder flux, it can be seen that real Execute ferritic crystal grain in example 1 joint the most tiny in the welding point of embodiment 2 flux composition.
The experiment results understands, and metallographic structure is mainly with the line and staff control such as acicular ferrite and granular bainite Composition, after adding trace Ti, brittle temperature district disappears, and is more easy to raw than Nb (N, C) at austenite high-temperature region TiN Becoming, result of the test disclosure satisfy that X100 Pipeline Welded Joints mechanical property requirements, shows that the present invention is for meeting The high intensity of X100 Pipeline Welded Joints, high tenacity, the sintered flux of the performance such as corrosion-resistant.
As shown in table 8, the mechanical property using the welding point of embodiment 1-2 is as follows:
Table 8 uses the mechanical property of the welding point of embodiment
Relatively both deposited metal compositions, the Mn content in embodiment 1 is somewhat higher, and Si content is also The highest.And the increase of Mn content, improved the intensity of steel by solution strengthening, be that pipe line steel compensates because of C Content reduces and causes the main and most economical intensified element of loss of strength.The formation of Mn suppression pearlite, Simultaneously facilitating bainite to be formed, Mn still expands the element of γ phase region, it is possible to decrease γ → α phase transition temperature of steel, Contribute to obtaining tiny phase-change product, the toughness of steel can be improved, reduce ductile-brittle transition temperature.Then make in weld seam Ferrite side plate fades away, and acicular ferrite size reduces further.Ti element is strong solid N element, Can form the TiN precipitated phase of tiny high-temperature stable, this tiny TiN particle can hinder deposition gold effectively Belong to Austenite Grain Growth when reheating, be favorably improved Nb solid solubility in austenite, simultaneously to changing The impact flexibility of kind welding heat affected zone has obvious effect.
Embodiment 3-4
It is with embodiment 1-2 difference: as it is shown in figure 5, embodiment 3 sintered flux adds alloying constituent TiO2And borax anhydrous, other flux constituent is constant, there is strong reciprocal action, in weld seam between B and Ti Not having enough Ti, the Beneficial Effect of B is little；On the contrary, there is no B, Ti to promoting needle-like in weld seam The effect that ferrite is formed is the best.When B and Ti too high levels, by promoting the formation of upper bainite, make Welding seam toughness decline, its reason is probably: the joint effect of Ti and B butt welded seam tissue and performance mainly due to Ti protects the B of remnants not oxidized by forming TiN, thus has certain free B to austenite grain boundary Segregation, separates out the carbide Fe of substantial amounts of B on crystal boundary23(BC)6, it generates prior to ferrite, thus may be used See that Ti in weld metal, B element content all can not be the highest.
As shown in Figure 6, embodiment 4 sintered flux adds alloying constituent TiO2And borax anhydrous, weld(ing) deposit Great changes will take place for tissue, is mainly carbide by white ferrite, little black patch for bending formula body and gray area Intensive settling zone forms, and is organizing the formation of and the weld seam metallographic structure of distributions and embodiment 3 sintered flux Similar, the low-temperature impact toughness causing weld metal is lower.
As shown in table 9, the sintered flux chemical composition using embodiment 3-4 is as follows:
The main chemical composition of table 9 embodiment sintered flux (wt.%)
Numbering SiO2 MgO Al2O3 CaF2 CaO MnO TiO2 B2O3 NaO2
Embodiment 3 15.1 25.5 18.8 20.5 5.6 4.3 7.2 1.7 1.3
Embodiment 4 15.6 21.6 17.7 19.0 7.5 5.8 8.3 2.3 2.2
As shown in table 10, the mechanical property using the welding point of embodiment 3-4 is as follows:
Table 10 uses the mechanical property of the welding point of embodiment
Embodiment result shows, the present invention is by the selection of sintered flux slag system, the selection of basicity, alloying constituent The changes of interpolation and flux constituent etc. are many-sided to be considered, optimization flux constituent is developed one and met X100 pipeline The high intensity of steel welded joint, high tenacity, the submerged arc sintered flux of the performance such as corrosion-resistant.The present invention is by changing Manganous silicate, wollastonite composition in SJ101-G solder flux, and add alloying constituent Si-Fe, Ti-Fe, Mn-Fe, Borax, TiO2Deng, mating identical H08C welding wire carries out soldering test, by analyze different solder flux welding usability, The microstructure and mechanical property of welding point, provides foundation for developing a kind of novel X100 pipe line steel sintered flux. The present invention passes through the means such as metallurgical microscope, scanning electron microscope, the microstructure of Welded Joints, impact fracture shape The chemical composition of looks and deposited metal is observed and is analyzed, by the experiment results of high performance sintered solder flux Understanding, the yield strength of postwelding weld metal and low-temperature impact toughness disclosure satisfy that X100 Pipeline Welded Joints Mechanical property requirements.

Claims (3)

1. an X100 pipe line steel solder flux used for submerged arc welding, it is characterised in that the chemical component weight percentage ratio of solder flux is: SiO2 12.7；MgO 29.9, Al2O3 19.3, CaF2 22.6, CaO 3.7, MnO 5.4, TiO2 6.4。
2. an X100 pipe line steel solder flux used for submerged arc welding, it is characterised in that the chemical component weight percentage ratio of solder flux is: SiO2 12.9；MgO 20.9, Al2O3 19.5, CaF2 25.0, CaO 9.5, MnO 5.6, TiO2 6.6。
3. according to the X100 pipe line steel solder flux used for submerged arc welding described in claim 1 or 2, it is characterised in that basicity B of X100 pipe line steel solder flux used for submerged arc weldingⅡwIt is 1.5～2.1.
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