CN112496596A - Sintered flux for hydrogen-resistant steel, method for producing same, and deposited metal - Google Patents
Sintered flux for hydrogen-resistant steel, method for producing same, and deposited metal Download PDFInfo
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- 230000004907 flux Effects 0.000 title claims abstract description 104
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 84
- 239000001257 hydrogen Substances 0.000 title claims abstract description 83
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 68
- 239000010959 steel Substances 0.000 title claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000003466 welding Methods 0.000 claims abstract description 94
- 239000002893 slag Substances 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 26
- 239000010431 corundum Substances 0.000 claims abstract description 26
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 24
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 24
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 24
- 235000014380 magnesium carbonate Nutrition 0.000 claims abstract description 24
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 23
- 239000010456 wollastonite Substances 0.000 claims abstract description 23
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 29
- 238000012216 screening Methods 0.000 claims description 29
- 238000002156 mixing Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 17
- 238000003723 Smelting Methods 0.000 claims description 15
- 238000005245 sintering Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 11
- 229910052748 manganese Inorganic materials 0.000 abstract description 6
- 239000010953 base metal Substances 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- 238000011160 research Methods 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 32
- 230000007797 corrosion Effects 0.000 description 17
- 238000005260 corrosion Methods 0.000 description 17
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 15
- 235000019353 potassium silicate Nutrition 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 11
- 238000005336 cracking Methods 0.000 description 10
- 239000011572 manganese Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 238000007373 indentation Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Images
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3053—Fe as the principal constituent
- B23K35/3073—Fe as the principal constituent with Mn as next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Nonmetallic Welding Materials (AREA)
Abstract
The invention relates to the technical field of welding materials, and discloses a sintered flux for hydrogen-resistant steel, a preparation method thereof and deposited metal, wherein the sintered flux for hydrogen-resistant steel comprises 25-38% by weight of magnesite, 21-30% by weight of white corundum, 1.5-3.0% by weight of wollastonite, 6.0-9.8% by weight of molten flux slag, 33.4-40% by weight of alkali fluoride and 0.05-0.2% by weight of rare earth; a method of making the flux and a deposited metal are also disclosed. The flux of the invention researches out a flux with lower oxidizability, is easy to weld a hydrogen-resistant steel base metal, has good arc protection during welding, effectively isolates O, N and H in the air, and effectively desulfurizes, dehydrogenates and deoxidizes through special slag design to obtain a high-quality welding seam matched with the hydrogen-resistant steel by controlling the source of S, P harmful elements in raw materials and the Mn and Ni content in deposited metal and designing reasonable slag system and deposited metal chemical components.
Description
Technical Field
The invention belongs to the technical field of welding materials, and particularly relates to a sintered flux for hydrogen-resistant steel, a preparation method of the sintered flux and deposited metal.
Background
Pressure vessels are used in a large number in the petrochemical industry, and the problem of hydrogen sulfide corrosion is common in the pressure vessels. In production, Hydrogen Induced Cracking (HIC) and hydrogen sulfide stress corrosion cracking (SSC) are the causes of pressure vessel failure due to wet hydrogen sulfide corrosion. Q235/345R (HIC) hydrogen-resistant steel is a steel material commonly used in the petrochemical pressure vessel at present. The Q235/345R (HIC) hydrogen-resistant steel and the matched welding material thereof need to strictly control the S, P content (P is less than or equal to 0.015 and S is less than or equal to 0.004) of the steel while controlling the Mn content, the control quantity of S, P of a welding seam is that S is less than or equal to 0.010 percent and P is less than or equal to 0.020 percent, and the steel must have ultralow diffusible hydrogen content, good Hydrogen Induced Cracking (HIC) resistance and hydrogen sulfide stress corrosion cracking (SSC) resistance. This new steel grade (hydrogen-resistant steel) is now widely used in the manufacture of pressure vessels. The hydrogen-resistant steel welding material matched with the hydrogen-resistant steel is used as a large-demand welding material in the petrochemical pressure vessel and pipeline industry, the demand of the products is large, the annual demand of the hydrogen-resistant steel welding material is more than 500 tons, the domestic brands are few, and the levels of similar welding material products are different.
Researches show that long and narrow grains in the metallographic structure of the hydrogen-resistant steel are easy to generate transgranular fracture, and the small-size grains can reduce the transmission of hydrogen atoms, so that the occurrence of hydrogen sulfide corrosion is inhibited. Structural defects in some grains tend to increase the susceptibility to hydrogen induced cracking. Therefore, the influence of the grain structure on hydrogen induced cracking radically solves the problem of corrosion of the steel by hydrogen sulfide. The types and contents of alloy elements in the hydrogen-resistant steel material are different, so that the material has larger sensitivity difference to hydrogen sulfide corrosion. Related studies have found that S, P, as well as more Mn, Ni, etc., will be detrimental to the weld structure of hydrogen resistant steel, with higher strength and greater susceptibility to hydrogen embrittlement of the steel, since hardness and strength depend on chemical composition and crystal structure. S is mainly present in the steel in the form of FeS and MnS, of which FeS is the most harmful. When the weld is solidified, sulfur segregation is distributed in the grain boundary in the form of low-melting-point eutectic, and becomes the weakest part in the weld metal. And is easy to crack along the direction under the action of welding stress, namely, thermal crack. Secondly, as the S content increases, the tensile, yield, impact absorption energy and crack resistance of the weld metal all tend to decrease. The harm of H in the welding process is mainly manifested as hydrogen-induced pores, hydrogen white spots, hydrogen embrittlement and cold cracks, which all lead to the possibility of hydrogen-induced cracking after welding. And the existence of O in the welding seam has great influence on the corrosion of hydrogen sulfide. Research shows that oxygen can accelerate the corrosion rate of hydrogen sulfide to metal, and if oxygen exists in the medium, the corrosion rate of hydrogen sulfide to metal is increased rapidly, and pitting corrosion is generated rapidly.
As a hydrogen-resistant steel material widely used in the petrochemical industry, most of the steel materials work in a medium environment with high corrosivity, and therefore a welding material matched with the hydrogen-resistant steel also has the characteristic of being matched with a parent metal.
Disclosure of Invention
Therefore, a first object of the present invention is to provide a sintered flux for hydrogen-resistant steel, which is designed to have a reasonable slag system by controlling the source of S, P and the contents of Mn and Ni in the raw materials, to develop a flux with low oxidizability, which is easy to weld the base metal of hydrogen-resistant steel, has good arc protection during welding, effectively isolates [ O ], [ N ] and [ H ] from the air, and is designed to effectively desulfurize, dehydrogenate and deoxidize through special slag to obtain a good quality weld bead matching with hydrogen-resistant steel. The flux is matched with a special welding wire to weld a base metal for alloy transition, so that the difficulty in the research and development technology of hydrogen-resistant steel can be solved, the welded weld metal has the strength similar to that of a used Q235/345R (HIC) body, and the deposited metal has excellent properties of low S, low P, ultralow hydrogen, high toughness, good corrosion resistance, low crack sensitivity and the like.
The second object of the present invention is to provide a method for producing a sintered flux for hydrogen-resistant steel.
A third object of the present invention is to provide a deposited metal.
The specific contents are as follows:
the invention provides a sintered flux for hydrogen-resistant steel, which comprises, by weight, 25-38% of magnesite, 21-30% of white corundum, 1.5-3% of wollastonite, 6-9.8% of smelting flux slag, 33.4-40% of alkali fluoride and 0.05-0.2% of rare earth.
In the flux of the present invention,
(magnesite 25-38%)
The magnesite used in the invention has an ultra-low S, P level after being purified by a specific method. Magnesite is used as a slag forming agent and is very important for slag and weld forming. However, since the melting point is high, the viscosity of slag is rapidly increased during welding, slag is shortened from long slag, the melting temperature and the solidification temperature of slag are increased, the fluidity of slag is suppressed, the weld bead is poor in formation, the spreading performance is poor, the center of a weld bead is raised, slag is hardened, and slag removal is difficult, magnesite must be added together with an acidic oxide (white corundum), and the fluidity of slag can be effectively controlled. The adding amount of the magnesite is controlled to be 25-38%.
(21-30% of white corundum)
White corundum is an amphoteric oxide whose main component is aluminum oxide (Al)2O3) The content is more than 99 percent, the impurity content is low, and the requirement of ultra-low S, P of the welding flux for the hydrogen-resistant steel is facilitated. The white corundum is acidic in the flux slag system, has the function of increasing the surface tension of slag, is a regulator of the viscosity of the slag, and can effectively solve the problems of poor spreading, protruding center of a welding bead, difficult slag removal and the like caused by adding magnesite. The research shows that the increase of a certain amount of white corundum can reduce the tendency of indentation and indentation generation, but the excessively high content of white corundum can make the radian of a welding seam sharper and unsmooth, easily generate air holes and pockmarks, harden a slag shell, and the excessively low content of white corundum can make the surface of the welding seam uneven, generate the defects of indentation, undercut and the like, and influence the formation of the welding seam. Therefore, the amount of the white corundum added is controlled to be 21-30%.
(wollastonite 1.5 to 3.0%)
Wollastonite is a calcium silicate with microscopic crystallites of a generally needle-like or fibrous white powder with about 48.3% CaO and SiO2The flux is about 51.7 percent, and still contains a certain amount of Fe, Na, Mg, Al and the like, because the wollastonite has a special crystal grain shape, and all components in the flux are tightly combined together by taking the wollastonite as a medium, the particle strength can be effectively improved, the pulverization rate of particles during the transportation and use of the product is reduced, and the problems of air holes, pressure pits and the like caused by the increase of fine powder and the obstruction of gas escape are avoided. The adding amount of wollastonite in the invention is controlled to be 1.5-3.0%.
(6-9.8% of molten flux slag)
The smelting flux slag is the welding slag recovered after the smelting flux is welded. The temperature of a smelting furnace is up to 1250-1350 ℃ during production of the smelting flux, so that raw materials are molten, the raw materials can fully react at the temperature close to a molten pool, and the produced smelting flux is usuallyIs in a glass shape. Because of the special melting mode, the slag formed after welding still keeps the original glass shape. The molten flux slag is added into the sintered flux, so that the reaction of a molten pool can be more sufficient, the surface glossiness of a welding seam is good, the width of the welding seam is increased, and the melting amount of a welding wire is correspondingly increased, thereby improving the welding efficiency. Because the slag still contains a large amount of MnO and SiO after the welding of the melting flux2And a small amount of CaF2Are present. Therefore, the addition amount of the low-manganese high-silicon smelting flux slag is controlled to be 6-9.8%. At the time of welding, the following reaction occurs:
Mn+Fe=FeO+Mn，
SiO2+2Fe=2FeO+Si，
CaF2+H2O=CaO+2HF↑,
can be weld metal transition alloy, and can supplement the alloy in the welding wire and avoid the burning loss of the alloy during welding. Meanwhile, the reduced Mn and Si play roles in deoxidation and desulfurization in a molten pool, and the content of S, O in a welding seam can be effectively reduced.
(basic fluoride 33.4-40%)
The alkaline fluoride is a main material for reducing the diffusible hydrogen in the welding seam, can increase the alkalinity of the welding flux, improve the toughness of the welding seam, effectively reduce the high-temperature viscosity of the slag and improve the fluidity of the slag; the alkaline fluoride is easy to ionize, F-generated by ionization can improve electric arc conductivity, reduce the partial pressure of hydrogen in the electric arc atmosphere and the content of oxygen in deposited metal, and is beneficial to improving the low-temperature impact toughness of weld metal. The invention controls the addition of the alkaline fluoride within 33.4-40%, which can stabilize the arc, and the addition over 40% can cause the arc instability.
(rare earth 0.05-0.2%)
The rare earth is used as an active agent, has a good purification effect on weld metal, can improve weld structure and refine grains, changes the form, size and distribution of inclusions, has the functions of deoxidation, dehydrogenation and desulfurization, can reduce the content of harmful elements in the weld metal, and improves the low-temperature impact toughness of the weld metal. The invention controls the addition amount of the rare earth to be 0.05-0.2%.
Secondly, the invention provides a preparation method of the sintered flux for the hydrogen-resistant steel, which comprises the following steps:
s1, uniformly mixing the components of the sintered flux, adding the adhesive, uniformly stirring and granulating to obtain a material;
s2, baking the materials;
s3, screening the baked materials;
s4, sintering the screened qualified materials at high temperature, and screening for the second time to obtain the sintered flux.
Thirdly, the invention provides a deposited metal which is obtained by welding the sintered flux for the hydrogen-resistant steel and a hydrogen-resistant steel submerged arc welding wire; the deposited metal comprises the following chemical components in percentage by weight:
c is more than 0 and less than or equal to 0.19 percent, Mn is more than or equal to 1.0 percent and less than or equal to 1.6 percent, Si is more than or equal to 0.2 percent and less than or equal to 0.60 percent, S is less than or equal to 0.010 percent, P is less than or equal to 0.010 percent, Ni is more than 0 and less than or equal to 0.30 percent, Cu is more than 0 and less than or equal to 0.20 percent, and the balance; the diffusible hydrogen content of the deposited metal is 1.2-2.5 mL/100 g.
The beneficial effects of the invention are as follows:
(1) the flux of the invention strictly controls the source of S, P harmful elements in raw materials and the content of Mn and Ni in deposited metal, designs a reasonable slag system and obtains the flux with low oxidability.
(2) The welding flux disclosed by the invention is easy to weld a hydrogen-resistant steel base metal, has good arc protection during welding, effectively isolates [ O ], [ N ] and [ H ] from air, and effectively desulfurizes, dehydrogenates and deoxidizes through special slag design to obtain a high-quality welding seam matched with the hydrogen-resistant steel.
(3) The welding flux disclosed by the invention is matched with a special welding wire welding base metal for alloy transition, so that the welded welding seam metal has the strength similar to that of a used Q235/345R (HIC) body, and the deposited metal has excellent performances of low S, low P, ultralow hydrogen, high toughness, good corrosion resistance, low crack sensitivity and the like.
Drawings
Fig. 1 is a graph showing the results of the welding test of each sample.
Reference numerals: e represents examples and C represents comparative examples.
Note: the figure is a result graph of the original image obtained by the gray processing.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention provides a sintered flux for hydrogen-resistant steel, which comprises, by weight, 25-38% of magnesite, 21-30% of white corundum, 1.5-3.0% of wollastonite, 6-9.8% of smelting flux slag, 33.4-40% of alkali fluoride and 0.05-0.2% of rare earth.
Preferably, the components comprise, by weight, 25.7% of magnesite, 30% of white corundum, 3% of wollastonite, 7.8% of smelting flux slag, 33.4% of alkaline fluoride and 0.1% of rare earth.
Preferably, the components comprise 34 percent by weight of magnesite, 22 percent by weight of white corundum, 2.6 percent by weight of wollastonite, 7.3 percent by weight of smelting flux slag, 34 percent by weight of alkaline fluoride and 0.1 percent by weight of rare earth.
Preferably, the components comprise, by weight, 27% of magnesite, 25% of white corundum, 2% of wollastonite, 9.80% of smelting flux slag, 36% of alkaline fluoride and 0.2% of rare earth.
Preferably, the components comprise, by weight, 28.5% of magnesite, 23% of white corundum, 1.8% of wollastonite, 8.65% of smelting flux slag, 38% of alkaline fluoride and 0.05% of rare earth.
Preferably, the components comprise, by weight, 25% of magnesite, 27% of white corundum, 1.5% of wollastonite, 6.3% of smelting flux slag, 40% of alkaline fluoride and 0.2% of rare earth.
Preferably, the components comprise, by weight, 38% of magnesite, 21% of white corundum, 1.5% of wollastonite, 6.0% of smelting flux slag, 33.4% of alkaline fluoride and 0.1% of rare earth.
Secondly, the invention provides a preparation method of the sintered flux for the hydrogen-resistant steel, which comprises the following steps:
s1, uniformly mixing the components of the sintered flux, adding the adhesive, uniformly stirring and granulating to obtain a material;
s2, baking the materials;
s3, screening the baked materials;
s4, sintering the screened qualified materials at high temperature, screening for the second time, and screening out finer particles to obtain the sintered flux.
In the present invention, in S1, the binder is 3.1 mode potassium sodium silicate.
In the present invention, the amount of the binder added in S1 is 18 to 21% by weight based on the total weight of the flux.
In the S2 process, the material is baked at a low temperature of 200-230 ℃ for 40 min.
In the invention, in S3, the screening process is to screen out particles except (8-40) meshes by 8-mesh and 40-mesh screens.
In the invention, the high-temperature sintering process is to sinter the mixture at 780-810 ℃ for 40 min.
In the invention, the granularity of the welding flux is 8-40 meshes.
When the granularity of the welding flux is too large, the clearance of the welding flux particles after covering is too large, the protection of the arc atmosphere is not enough and is easily influenced by air, so an 8-mesh screen is selected to screen out the large-particle welding flux; the particle size is too small, or the fine powder is too much, the air permeability is not good during welding, the gas generated during welding is not easy to discharge, and the defects such as indentation and the like are easy to generate, so a 40-mesh screen is selected to screen out the fine powder.
Thirdly, the invention provides a deposited metal which is obtained by welding the sintered flux for the hydrogen-resistant steel and a hydrogen-resistant steel submerged arc welding wire; the deposited metal comprises the following chemical components in percentage by weight:
less than or equal to 0.19 percent of C and not containing 0 percent, Mn1.0-1.6 percent, Si0.2-0.60 percent, less than or equal to 0.010 percent of S and not containing 0 percent, less than or equal to 0.010 percent of P and not containing 0 percent, less than or equal to 0.30 percent of Ni and not containing 0 percent, less than or equal to 0.20 percent of Cu and not containing 0 percent, and the balance of Fe and inevitable impurities.
Fourthly, the invention provides deposited metal which is obtained by welding the sintered flux for the hydrogen-resistant steel and a hydrogen-resistant steel submerged arc welding wire; the diffusible hydrogen content of the deposited metal is 1.2-2.5 mL/100 g.
< example >
Example 1
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 38 Be, stirring and mixing, wherein the adding amount of the potassium-sodium water glass accounts for about 18% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the welding flux No. 1 with the alkalinity of 2.7.
Example 2
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 41 Be, stirring and mixing, wherein the adding amount of the potassium-sodium water glass accounts for about 20% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the welding flux No. 2 with the alkalinity of 3.0.
Example 3
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 39 Be, stirring and mixing, wherein the adding amount of the potassium-sodium water glass accounts for about 21% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the welding flux No. 3 with the alkalinity of 3.0.
Example 4
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 42 DEG Be 42%, stirring and mixing, wherein the adding amount of the potassium-sodium water glass is about 19% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the welding flux No. 4 with the alkalinity of 2.8.
Example 5
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 40 Be, stirring and mixing, wherein the adding amount of the potassium-sodium water glass accounts for about 21% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with the (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the flux No. 5 with the alkalinity of 2.9.
Example 6
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 38 Be, stirring and mixing, wherein the adding amount of the potassium-sodium water glass accounts for about 18% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the welding flux No. 6 with the alkalinity of 3.0.
< comparative example >
Comparative example 1
The weight ratio of each component of the sintered flux for the hydrogen-resistant steel is shown in table 1.
The preparation method comprises the steps of weighing the components of the welding flux according to the proportion, placing the raw materials of the components in a mixer, stirring and mixing uniformly to obtain powder, adding 3.1 model potassium-sodium water glass with Baume concentration of 39 Be, stirring and mixing, wherein the adding amount of the potassium-sodium water glass accounts for about 20% of the total weight of the powder. And meanwhile, mixing the powder materials to form particles, granulating, baking at the low temperature of 200-230 ℃ for 40min, screening the particles except the particles with the (8-40) meshes by using a screen after baking at the low temperature, sintering at the high temperature of 780-810 ℃ for 40min, screening again, and screening by using a 40-mesh screen to remove fine powder to obtain the comparative flux with the alkalinity of 2.9.
Table 1 flux ingredients ratio table (in mass%)
(examples are represented by E, comparative examples are represented by C)
| Sample (I) | Magnesite | White corundum | Wollastonite | Melting of flux slag | Basic fluorineArticle of manufacture | Rare earth element |
| E1 | 25.7 | 30 | 3 | 7.8 | 33.4 | 0.1 |
| E2 | 34 | 22 | 2.6 | 7.3 | 34 | 0.1 |
| E3 | 27 | 25 | 2 | 9.8 | 36 | 0.2 |
| E4 | 28.5 | 23 | 1.8 | 8.65 | 38 | 0.05 |
| E5 | 25 | 27 | 1.5 | 6.3 | 40 | 0.2 |
| E6 | 38 | 21 | 1.5 | 6 | 33.4 | 0.1 |
| C1 | 40 | 13 | 1 | 4 | 42 | 0 |
< test example >
A Q345 common steel plate with the thickness of 25mm is taken as a test steel plate, and an edge is piled by adopting a special welding rod for hydrogen-resistant steel. The welding tests were carried out by using flux Nos. 1 to 6 in examples and comparative flux in comparative examples as test samples and using a submerged arc welding wire XY-S50SHA for hydrogen-resistant steel. The special welding wire comprises, by weight, 0.098% of C, 1.38% of Mn, 0.20% of Si, 0.003% of S, 0.005% of P, 0.06% of Cr, 0.02% of Ni, 0.053% of Mo, 0.06% of Cu, and the balance of Fe and inevitable impurities.
The results of the welding test are shown in fig. 1.
Welding tests show that when welding is carried out by using the welding flux No. 1-6, the welding process is excellent, slag is easy to remove, the weld joint is attractive in appearance, the straightness is good, and the defects of indentation, slag inclusion, pores, cracks and the like are avoided.
When the comparative flux is adopted for welding, the process is not good. The reason is that the magnesite content is high, the hardness of a slag shell is high, the surface corrugation of a welding bead is thick, the slag removal is poor, and slag is adhered to one side of a base material; welding in the groove, welding slag is not easy to break and is easy to clamp in the groove, operation is difficult, and welding efficiency is low; the white corundum content is low, so that the metal wettability of a welding seam is poor, the transition of a welding bead is not smooth, and impurities and incomplete fusion are easy to appear; the content of wollastonite is low, a slag shell of slag is too thin, and the protection to welding seam metal is poor; the manganese alloy content is low, the weld strength can not meet the design requirement, the S removal is insufficient, and the S content of the deposited metal is increased; the basic oxide is too high, the partial pressure of HF is too high, so that the electric arc is unstable, the surface of a welding seam is large and pits are formed, air in an electric arc environment is easy to intrude, the H O N is increased, the cracks in a hydrogen induced crack (R-HIC) resistant test are obvious, the Sulfide Stress Corrosion (SSC) resistant test is unqualified, and the pits are formed in a welding bead so as to influence the use.
The weld joint was also measured, and the chemical composition and mechanical properties of the deposited metal were measured, and the test results are shown in tables 2 and 3.
Table 2 deposited metal chemical composition measurement results (mass fraction%)
| Test sample | C | Mn | Si | S | P | Ni | Cu |
| E1 | 0.058 | 1.34 | 0.21 | 0.0014 | 0.0068 | 0.041 | 0.061 |
| E2 | 0.051 | 1.41 | 0.24 | 0.0018 | 0.0061 | 0.035 | 0.065 |
| E3 | 0.054 | 1.52 | 0.31 | 0.0016 | 0.0081 | 0.042 | 0.075 |
| E4 | 0.053 | 1.45 | 0.25 | 0.0014 | 0.0067 | 0.038 | 0.064 |
| E5 | 0.051 | 1.19 | 0.22 | 0.0016 | 0.0059 | 0.031 | 0.067 |
| E6 | 0.052 | 1.60 | 0.25 | 0.0015 | 0.0064 | 0.040 | 0.070 |
| C1 | 0.054 | 0.7 | 0.27 | 0.0034 | 0.014 | 0.043 | 0.072 |
TABLE 3 measurement results of mechanical properties of deposited metal
| Test sample | Tensile strength Rm (mpa) | Yield strength Rp0.2 (Mpa) | Elongation A (%) | 40 ℃ impact energy KV2 (J) | Diffusing hydrogen | R-HIC | SSC |
| E1 | 550 | 499 | 31 | 193 | 1.4 | Qualified | Qualified |
| E2 | 535 | 415 | 34 | 204 | 1.2 | Qualified | Qualified |
| E3 | 586 | 409 | 32 | 216 | 2.5 | Qualified | Qualified |
| E4 | 568 | 432 | 30 | 210 | 2.0 | Qualified | Qualified |
| E5 | 521 | 429 | 35 | 190 | 1.8 | Qualified | Qualified |
| E6 | 610 | 501 | 32 | 181 | 1.3 | Qualified | Qualified |
| C1 | 483 | 345 | 15 (fracture hydrogen white point, cause elongation failure) | 186 | 3.8 | Fail to be qualified | Fail to be qualified |
Note: in Table 3, tensile strength refers to tensile strength of the welded joint, and R-HIC and SSC refer to hydrogen induced cracking resistance and sulfide stress corrosion resistance tests of the welded joint.
As can be seen from tables 2 and 3, in 6 welding experiments in the examples, the arc stability, the slag detachability and the weld performance are good, and S, P, the impurity content and the diffusible hydrogen content are low, and meanwhile, the hydrogen induced cracking resistance and the sulfide stress corrosion resistance are good.
In conclusion, the welding seam welded by the welding flux has the characteristics of low content of S, P and low content of diffused hydrogen, which are similar to those of a Q235/345R (HIC) hydrogen-resistant steel body, good hydrogen-induced cracking resistance, hydrogen sulfide stress corrosion resistance and the like; the method is suitable for welding in a hydrogen-resistant steel production environment, and the weld metal with the defects of attractive weld formation, slag inclusion, indentation, air holes and the like is obtained.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The sintered flux for the hydrogen-resistant steel is characterized by comprising, by weight, 25-38% of magnesite, 21-30% of white corundum, 1.5-3% of wollastonite, 6-9.8% of smelting flux slag, 33.4-40% of alkaline fluoride and 0.05-0.2% of rare earth.
2. The sintered flux for hydrogen-resistant steel as claimed in claim 1, wherein the components comprise, by weight, 25.7% of magnesite, 30% of white corundum, 3% of wollastonite, 7.8% of molten flux slag, 33.4% of alkali fluoride and 0.1% of rare earth.
3. The sintered flux for hydrogen-resistant steel as claimed in claim 1, wherein the components comprise, by weight, 34% of magnesite, 22% of white corundum, 2.6% of wollastonite, 7.3% of molten flux slag, 34% of alkali fluoride and 0.1% of rare earth.
4. The sintered flux for hydrogen-resistant steel as claimed in claim 1, wherein the components comprise, by weight, 27% of magnesite, 25% of white corundum, 2% of wollastonite, 9.80% of molten flux slag, 36% of alkali fluoride and 0.2% of rare earth.
5. The sintered flux for hydrogen-resistant steel as claimed in claim 1, wherein the components comprise, by weight, 28.5% of magnesite, 23% of white corundum, 1.8% of wollastonite, 8.65% of molten flux slag, 38% of alkali fluoride and 0.05% of rare earth.
6. The sintered flux for hydrogen-resistant steel as claimed in claim 1, wherein the components comprise, by weight, 25% of magnesite, 27% of white corundum, 1.5% of wollastonite, 6.3% of molten flux slag, 40% of alkali fluoride and 0.2% of rare earth.
7. The sintered flux for hydrogen-resistant steel as claimed in claim 1, wherein the components comprise, by weight, 38% of magnesite, 21% of white corundum, 1.5% of wollastonite, 6.0% of molten flux slag, 33.4% of alkali fluoride and 0.1% of rare earth.
8. A method for preparing a sintered flux for hydrogen resistant steel as set forth in any one of claims 1 to 7, characterized by comprising the steps of:
s1, uniformly mixing the components of the sintered flux, adding the adhesive, uniformly stirring and granulating to obtain a material;
s2, baking the materials;
s3, screening the baked materials;
s4, sintering the screened qualified materials, and carrying out secondary screening to obtain the sintered flux.
9. The method for producing a sintered flux for hydrogen resistant steel as claimed in claim 8, wherein the particle size of the sintered flux is 8 to 40 mesh.
10. A deposited metal obtained by welding the sintered flux for hydrogen-resistant steel according to any one of claims 1 to 7 with a submerged arc welding wire for hydrogen-resistant steel;
the deposited metal comprises the following chemical components in percentage by weight: c is more than 0 and less than or equal to 0.19 percent, Mn is more than or equal to 1.0 percent and less than or equal to 1.6 percent, Si is more than or equal to 0.2 percent and less than or equal to 0.60 percent, S is less than or equal to 0.010 percent, P is less than or equal to 0.010 percent, Ni is more than 0 and less than or equal to 0.30 percent, Cu is more than 0 and less than or equal to 0.20 percent, and the balance;
the diffusible hydrogen content of the deposited metal is 1.2-2.5 mL/100 g.
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