CN104169451B - Ferrite-group stainless steel - Google Patents
Ferrite-group stainless steel Download PDFInfo
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- CN104169451B CN104169451B CN201380014308.5A CN201380014308A CN104169451B CN 104169451 B CN104169451 B CN 104169451B CN 201380014308 A CN201380014308 A CN 201380014308A CN 104169451 B CN104169451 B CN 104169451B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0447—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the heat treatment
- C21D8/0473—Final recrystallisation annealing
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
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- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/005—Ferrite
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Abstract
The present invention provides surface texture and the ferrite-group stainless steel with the excellent corrosion resistance of the weld part of austenite stainless steel.A kind of ferrite-group stainless steel, it is characterised in that contain C in terms of quality %：0.003~0.015%, Si：0.05~0.30%, Mn：0.10~0.35%, P：Less than 0.06%, S：Less than 0.02%, Cr：17.0~19.0%, Ni：More than 0.10% and less than 0.30%, Ti：0.10~0.40%, Nb：0.005% less than 0.050%, Mo：Less than 0.20%, N：0.005~0.015%, Cu：0.30~0.50%, Mg：Less than 0.0005%, surplus is made up of Fe and inevitable impurity.
Description
Technical field
The present invention relates to surface texture and with austenite stainless steel (austenitic stainless steel)
The ferrite-group stainless steel (ferritic stainless steel) of the excellent corrosion resistance of weld part.
Background technology
In stainless steel, austenite stainless steel SUS304 (18%Cr-8%Ni) (Japanese Industrial Standards, JIS G4305) by
Utilized extensively in its excellent corrosion resistance, still, the steel grade is due to largely containing Ni, therefore price is high.Therefore,
As the steel grade with the excellent corrosion resistance suitable with SUS304, the stainless steel described in patent document 1 is developed.
Patent Document 1 discloses a kind of ferrite series stainless steel plate, is formed as composition, contains C in terms of quality %：
Less than 0.03%, Si：Less than 1.0%, Mn：Less than 0.5%, P：Less than 0.04%, S：Less than 0.02%, Al：Less than 0.1%,
Cr：More than 20.5% and less than 22.5%, Cu：More than 0.3% and less than 0.8%, Ni：Less than 1.0%, Ti：4 × (C%+
N% more than) and less than 0.35%, Nb：Less than 0.01%, N：Less than 0.03%, C+N：Less than 0.05%, surplus is by Fe and can not
The impurity avoided is formed.
In addition, the ferrite-group stainless steel such as JIS-SUS444, JIS-SUS430J1L is compared with austenite stainless steel,
With stress corrosion opening cracking maleate sensitivity (Stress Corrosion Cracking sensitivity) it is small, do not contain price become
Feature, material or water tank, the construction materials as the exhaust system components of automobile such as dynamic big Ni widely use.
But be typically due to ferrite-group stainless steel processability, particularly elongation it is poorer than austenite stainless steel, because
This uses austenite stainless steel in the unworkability part that can not be shaped by ferrite-group stainless steel.Therefore, most cases
Under, austenite stainless steel is combined with ferrite-group stainless steel and forms a composition product.In this case, each part leads to mostly
Solder bond is crossed, as welding method, mainly using TIG weld (Tungsten Inert Gas welding, Tungsten Inert gas
Body shielded arc welding), good corrosion resistance same with mother metal is also required to weld part (weld zone).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-77496 publications
Patent document 2：Japanese Unexamined Patent Publication 8-10823 publications
The content of the invention
Invent problem to be solved
Ferrite-group stainless steel disclosed in patent document 1 has good corrosion resistance in the weld part of identical steel grade.
But when steel grade different with SUS304 etc. carries out TIG weld, that the corrosion resistance for producing weld part reduces than mother metal be present
The problem of.
This is due to generate so-called sensitization (sensitization) and the corrosion resistance of weld part is deteriorated, and this is quick
Thermal history when change is due to welding make C, N in steel and Cr with reference to and with Cr carbide (chromium carbides, such as
Cr23C6Deng) or Cr nitride (chromium nitrides, CrN2Deng) form crystal boundary separate out, thus produced near crystal boundary
Raw Cr concentration is less than caused by the poor Cr layers (chromium depletion layer) of mother metal.
Generally, in order to prevent the corrosion resistance of the weld part as caused by sensitization from deteriorating, take that C, N's in steel is reduced is same
Ti appropriate Shi Tianjia, C, N are fixed in the form of Ti carbonitrides, so as to prevent the generation of Cr carbide, Cr nitride
Method.With it, the TIG weld portion between ferrite series stainless steel plate disclosed in patent document 1 show it is good
Corrosion resistance.
But the C content of the ferrite series stainless steel plate is about 0.01%, on the other hand, SUS304 etc. C content is up to
0.04~0.05%, therefore, generally, in the engagement with the contour stainless steels containing C of SUS304, in order to by same Ti add and
Prevent from being sensitized, it is necessary to improve Ti additions to about 1.0%.
But when Ti to about 1.0% is added in ferrite-group stainless steel, the Ti in solidification in molten steel and N is sent out sometimes
Raw reaction, forms TiN and separates out.The ductility shortcomings of the TiN at high temperature, form scar, surface texture in hot-rolled process
It is deteriorated.Scar caused by so is deeper, though annealed by hot rolled plate, pickling, cold rolling afterwards, cold-reduced sheet annealing, pickling etc.
Also will not eliminate, therefore, unless the processing for largely cutting hot-roll annealing pickling plate surface by grinder grinding etc. is carried out, it is no
The surface blemish for being referred to as so-called titanium striped (stringer caused by titanium nitrides) can be then formed, is made
The surface texture of cold rolled annealed acid-cleaning plate is significantly deteriorated.
In addition, in the case of TIG weld, at surface, the back side typically each by inert gas shielding so as to as far as possible will not
Formed in weld part and be referred to as being welded under conditions of tempering colour (temper color) thin oxide film thereon (oxide layer)
Connect, but in the process of reality, the gas shield is insufficient, exists due to being mixed into for N in air and encourages the quick of the foregoing description
The problem of change.
In addition, the advantages of largely also high Ni of price steel grade is not used in the presence of infringement in the high Ti of addition price is asked
Topic.
The present invention be in view of such situation complete, its object is to provide having superior surface quality and not only with iron
Plain system stainless steel and when being welded with austenite stainless steel weld part corrosion resistance also excellent ferrite-group stainless steel.
For solving the method for problem
The present inventor in order to realize above-mentioned problem, for steel chemical composition to mother metal portion and the corrosion resistance band of weld part
The influence come and the surface texture (titanium streak artifacts) of steel plate, careful investigation, research are carried out, has obtained following seeing
Solution.
(1) promote the concentration of element by optimizing ferritic phase, make the tissue shape with the weld part of austenite stainless steel
Into martensitic phase (marutensite phase), thus, it is possible to prevent from being sensitized.This is because, C, N of martensitic phase solid solution limit
Greatly.
(2) when adding the Nb of denier, at a high temperature of the temperature separated out higher than Ti nitride, Nb nitride separates out.
Thereafter the Nb nitride turns into the nucleating point of Ti carbonitrides in cooling procedure, and promoting Ti sensitization prevents effect.
(3) generally, when adding Nb, the recrystallization temperature rise of steel plate, but if the Nb of addition denier, then hardly deposit
, can be using the production line of the carbon steel disclosed in such as patent document 2 in the disadvantage of the recrystallization temperature of rise steel plate
Cheap high speed acid washing method.
(4) gas shield is incomplete when welding and the N in air is mixed into weld part, as long as containing suitable in steel
The Al of amount, then AlN is generated in weld part, can prevent from being sensitized.As long as in addition, containing appropriate Sb in steel, then in weld part
Sb and N compound is generated, so as to prevent from being sensitized.
(5) it is due to caused by TiN thick existing for pole skin section in steel plate the main reason for titanium streak artifacts.It is logical
Optimization Ti contents are crossed, the generation of titanium streak artifacts can be prevented.
From the foregoing, it will be observed that can be produced in weld part also has good corrosion resistance without to hot-roll annealing acid-cleaning plate
The cold rolled annealed acid-cleaning plate of the excellent surface quality of surface grinding is carried out, compared with the austenite stainless steel of Ni systems, can be obtained
To cheap ferrite-group stainless steel.
The present invention is completed based on above opinion, and its purport is as follows.
[1] a kind of ferrite-group stainless steel, it is characterised in that contain C in terms of quality %：0.003~0.015%, Si：
0.05~0.30%, Mn：0.10~0.35%, P：Less than 0.06%, S：Less than 0.02%, Cr：17.0~19.0%, Ni：Greatly
In 0.10% and less than 0.30%, Ti：0.10~0.40%, Nb：0.005% less than 0.050%, Mo：It is less than
0.20%th, N：0.005~0.015%, Cu：0.30~0.50%, Mg：Less than 0.0005%, surplus is by Fe and inevitably
Impurity is formed.
[2] ferrite-group stainless steel described in [1] as described above, it is characterised in that also contain Al in terms of quality %：0.02~
0.50%.
[3] ferrite-group stainless steel described in [2] as described above, wherein, the Al in terms of quality %：0.10~0.50%.
[4] ferrite-group stainless steel any one of [1] to [3] as described above, it is characterised in that in terms of quality % also
Contain Sb：0.005~0.30%.
[5] ferrite-group stainless steel any one of [1] to [4] as described above, it is characterised in that in terms of quality % also
Contain Zr：0.05~0.60%, V：One or both of 0.02~0.50%.
Invention effect
Even if the ferrite-group stainless steel of the present invention welds with austenite stainless steel, the corrosion resistance and table of weld part
Face character is also excellent, therefore, suitable for cooking apparatus, building built-in material, industrial machine, automobile component etc..
Embodiment
Hereinafter, the restriction reason of each inscape of the present invention is illustrated.
1. formed on composition
First, the reason for composition composition of the steel of the regulation present invention, is illustrated.It should be noted that composition % is whole
Refer to quality %.
C：0.003~0.015%
C easily with Cr with reference to and form Cr carbide, in heat affected zone (Heat Affected Zone) formation during welding
During Cr carbide, the reason for intercrystalline corrosion can be turned into, therefore C is more low more preferred.Therefore, C is set as less than 0.015%.Separately
On the one hand, the substantial amounts of time is needed in refining when C content is too low, therefore, C content is set as to 0.003~0.015% model
Enclose.From the viewpoint of the corrosion resistance of weld part, preferably 0.003~0.012% scope.More preferably 0.003~
0.010% scope.
Si：0.05~0.30%
Si is the element useful as deoxidier, therefore, is set as more than 0.05%.When on the other hand, more than 0.30%,
The pickling of cold-reduced sheet in the high speed acid washing method for making to use in carbon steel production line is deteriorated, and productivity ratio reduces.Thus, Si amounts
It is set as 0.05~0.30% scope.Preferably 0.05~0.20% scope.
Mn：0.10~0.35%
Mn has deoxidation, therefore contains more than 0.10%.Further, since Mn, which is austenite phase, promotes element
(austenite former element), therefore, promote and (the hereinafter referred to as different steel grade weldering of the weld part of austenite stainless steel
Socket part) martensitic phase formation.But in the case of being excessively added, Mn can be combined with S present in steel, formation is used as can
The MnS of dissolubility sulfide (soluble sulfides), reduces corrosion resistance, therefore, Mn contents are set as 0.10~
0.35% scope.Preferably 0.10~0.25% scope.
P：Less than 0.06%
P is not only harmful to when more than 0.06% to corrosion resistance, and due to solution strengthening (solid solution
Strengthening) processability is reduced.Thus, P amounts are set as less than 0.06%.From the viewpoint of corrosion resistance, preferably
For less than 0.04%.
S：Less than 0.02%
S is the element being harmful to corrosion resistance.Particularly with Mn it is simultaneous in the case of, MnS can be formed and turned into
The starting point of spot corrosion, makes corrosion resistance be deteriorated.It is such to become notable when acting on more than 0.02%.Therefore, S amounts are set as
Less than 0.02%.From the viewpoint of corrosion resistance, preferably less than 0.01%.More preferably less than 0.006%.
Cr：17.0~19.0%
Cr forms passivation envelope on the surface of stainless steel, is the element integral to improving the corrosion resistance of mother metal.
In order to obtain good corrosion resistance, it is necessary to add more than 17.0%.But the addition more than 19.0% is in the different steel with SUS304
Kind weld part does not generate martensite, it is impossible to prevents corrosion resistance from reducing.Therefore, Cr contents are set as 17.0~19.0% model
Enclose.Preferably 17.5~18.5% scope.
Ni：More than 0.10% and less than 0.30%
Ni contributes to improve the element of crevice corrosion resistance (crevice corrosion resistance).In addition,
Same with Mn is that austenite phase generation promotes element, therefore, can promote the formation of the martensitic phase of different steel grade weld part.But
When addition is more than 0.30%, SCC sensitiveness improves, in addition, Ni is also the high element of price.Therefore, Ni amounts are set greater than
0.10% and less than 0.30% scope.Preferably 0.20~0.30% scope.
Ti：0.10~0.40%
Ti can not be owed in order to ensure the corrosion resistance with the different steel grade weld part of austenite stainless steel as described above
Scarce element.But when being excessively added, TiN amount of precipitation increase, titanium streak artifacts become notable, if moved back without hot rolling
Surface grinding of fiery acid-cleaning plate etc., then can not on sheet (cold rolled annealed acid-cleaning plate) holding surface character well.Therefore,
Ti amounts are set as 0.10~0.40% scope.From the viewpoint of the corrosion resistance of different steel grade weld part, it is preferably set to
0.20~0.40% scope.
Nb：0.005% less than 0.050%
Nb micro addition is also one of important key element for the purpose of the present invention.Nb more preferentially forms carbon nitrogen than Cr, Ti
Compound.Especially in the molten bath of different steel grade weld part (weld metal) and heat affected zone, than generation Ti carbonitrides
Start the generation of Nb carbonitrides at the higher temperature of temperature.In cooling procedure afterwards, reason is still not clear, the nitridation of Nb carbon
The carbonitride for the Ti that thing largely contains as nucleating point, generation.That is, by adding micro Nb, promote Ti carbon nitrogen
The generation of compound, therefore, compared with the situation for not containing Nb, the molten bath of different steel grade weld part, the Ti of heat affected zone C, N consolidate
Capability becomes strong, more efficiently prevents from being sensitized.Therefore, it is more than 0.005% by the lower limit set of the Nb amounts of the present invention.Separately
On the one hand, when Nb is excessively added, recrystallization temperature (recrystallization temperature) rise of cold-reduced sheet, because
This, in order to obtain sufficient engineering properties, it is necessary to anneal at high temperature.Therefore, compared with no addition Nb situation, final
The oxide film thereon generated when annealing (finishing annealing) grows thicker.Therefore, make in above-mentioned carbon steel production line
The pickling of cold-reduced sheet in the middle high speed acid washing method used is deteriorated, and reduces productivity ratio.Thus, Nb amounts are set as 0.005%
Less than 0.050% scope.From the viewpoint of the corrosion resistance of different steel grade weld part, preferably more than 0.010%
And the scope less than 0.050%.
Mo：Less than 0.20%
Mo makes passivation envelope (passivation film) strong, significantly improves corrosion resistance.But Mo is ferritic phase
Generation promotes element, even if by micro addition, horse will not be also generated in the different steel grade weld part with austenite stainless steel
Family name's body phase.Therefore, different steel grade weld part forms ferritic phase, is sensitized.Thus, Mo amounts are set smaller than 0.20%.In addition,
Mo is due to reducing hot rolled plate Tough, it is therefore preferable that less than 0.10%.It should be noted that Mo lower limit set is 0.
N：0.005~0.015%
N easily with Cr with reference to and form Cr nitride.During welding Cr nitrogen is formed in different steel grade weld part and heat affected zone
During compound, the reason for intercrystalline corrosion (intergranular corrosion) can be turned into, therefore N is more low more preferred.In addition, it is
The amount of precipitation for the TiN for causing titanium streak artifacts is reduced, is reduced as far as possible preferably.But even if too low be also required in refining
Substantial amounts of time, therefore, N amounts are set as 0.005~0.015% scope.From the viewpoint of the corrosion resistance of different steel grade weld part
Set out, preferably 0.005~0.012% scope, more preferably 0.005~0.010% scope.
Cu：0.30~0.50%
Cu is to improve corrosion resistance, the member of corrosion resistance particularly in aqueous or when being attached with weakly acidic water droplet
Element.This is because, Cu in the aqueous solution or water droplet Yi Dan dissolving after, be reattached on fe-based surface, so as to inhibit iron-based
Dissolving.But Cu amounts more than 0.50% when, generate and be referred to as on hot rolling steel billet in addition to hot-workability reduces, during hot rolling
The starch sugar pulpous state oxide due to Cu of red rust, also as surface defect the reason for.Thus, Cu amounts be set as 0.30~
0.50% scope.From the viewpoint of hot-workability, preferably 0.30~0.40% scope.
Mg：Less than 0.0005%
Mg is mainly by the mixed impurity of brick in converter.In addition, Mg turn into diversified field trash starting point, also into
For the nucleating point of other field trashes.In addition, being also difficult to be dissolved again even if anneal etc., therefore, make hot-roll annealing acid-cleaning plate, system
The surface texture of product plate (cold rolled annealed acid-cleaning plate) is deteriorated.Thus, Mg amounts are set smaller than 0.0005%.In order to keep good
Surface texture, preferably smaller than 0.0003%.
It is made up of above for the basic chemical composition of the present invention, surplus Fe and inevitable impurity, in addition, being welded from TIG
From the viewpoint of the gas shield that connects and the sensitization for preventing different steel grade weld part, Al, Sb alternatively element can be added.This
Outside, in order to improve the corrosion resistance of different steel grade weld part, Zr, V alternatively element can be added.It should be noted that conduct
Inevitable impurity, such as Ca can be allowed：Less than 0.0020%, but it is not limited to this.
Al：0.02~0.50%
Al is the element especially important in the case where the gas shield of TIG weld is insufficient.As described above in TIG weld
In the case of, gas shield generally is carried out to the back side to implement to weld.But in the complex-shaped situation of different steel grade weld part
Under, gas shield is insufficient, and the N in air is mixed into molten bath sometimes.In this case, C, N amount exceed the solid solution of martensitic phase
When limiting (solid solubility limit), only it can not fully prevent from being sensitized by Ti.Under such circumstances, addition in advance
Al is to preventing that sensitization from being effective.This is because, Al fixes the N for being mixed into molten bath in the form of AlN.The effect by containing
More than 0.02% Al and obtain.But when containing Al more than 0.50%, nonmetallic system's field trash is generated in the steel billet stage, into
The reason for being deteriorated for the surface texture of hot rolled plate, cold-reduced sheet.Thus, in the case of containing Al, Al amounts preferably 0.02~
0.50% scope.Preferred lower limit is 0.10%, more preferably 0.15%.The preferred upper limit is 0.30%.
Sb：0.005~0.30%
Sb is same with Al, it may have the mixed N in being caught in the case that the gas shield of TIG weld is insufficient by air
Effect, be the element that had better be added in the case of structure with complex shape.But during excessively addition Sb,
Nonmetallic system's field trash is generated in the steel billet stage, turn into hot rolled plate, cold-reduced sheet surface texture be deteriorated the reason for.Thus, exist
In the case of adding Sb, Sb amounts are preferably set to 0.005~0.30% scope.From sheet (cold rolled annealed acid-cleaning plate)
From the viewpoint of surface texture, more preferably 0.005~0.10% scope.
Zr：0.05~0.60%
Zr is same with Ti more preferentially to form carbonitride than Cr, makes identical steel grade weld part, different steel grade weld part
The element that corrosion resistance improves.But Zr and Ti comparative prices are high, in addition, during excessively addition Zr, intermetallic can be generated
Thing, make the degraded toughness of hot rolled plate.Thus, in the case of adding Zr, Zr amounts are preferably 0.05~0.60% scope.More preferably
For 0.15~0.35% scope.
V：0.02~0.50%
V is also same with Ti more preferentially to form carbonitride than Cr, makes identical steel grade weld part, different steel grade weld part
The element that corrosion resistance improves.But its effect is less than Ti.In addition, and high price element.Therefore, in the case of adding V, V
Amount is preferably 0.02~0.50% scope.More preferably 0.02~0.05% scope.
2. on manufacturing condition
Then, the preferable production process of steel of the present invention is illustrated.By the steel that above-mentioned preferred component forms by converter,
Method known to electric furnace, vacuum melting furnace etc. carries out melting, and steel former material (steel billet) is made by continuous metal cast process or ingot casting-cogging method.
Carry out the heating of 1~24 hour at 1100~1250 DEG C to the steel former material afterwards, or do not heat and directly carry out hot rolling, make
Into hot rolled plate.
The hot rolled plate implemented 1~10 minute generally at 800~1100 DEG C to hot rolled plate is annealed, but can also be according to purposes
Omit hot rolled plate annealing.Then, after hot rolled plate pickling, cold-reduced sheet is made by cold rolling, then, implements final annealing, obtains
Sheet.From the viewpoint of extensibility, bendability, press formability and shape correction, cold rolling is preferably more than 50%
Carried out under rolling rate.Generally in the case of JIS G0203 Surface Finishing No.2B finished goodses, from ensuring good machine
From the viewpoint of tool property and pickling, the final annealing of cold-reduced sheet is preferably annealed at 800~950 DEG C.
But utilizing tandem rolling-CAL (tandem cold rolling and continuous annealing
Line in the case of large-duty cold rolled article), most preferably by using make use of the above-mentioned carbon steel of carbon steel production line to move back
The inexpensive process of the high speed pickling (referenced patent document 2) of fiery pickling lines is manufactured, and annealing temperature now preferably exists
Carried out at 800~900 DEG C.In addition, the component at the position for further requirement gloss, is to have using the BA final annealings annealed
Effect.In addition, as described above, after cold rolling and processing after, in order to obtain better surface texture, though implement grinding
Deng also without any problem.
Embodiment 1
Hereinafter, based on embodiment, the present invention is given the account in greater detail.
The steel of composition with example No.1~8 shown in table 1 and 33, comparative example No.9~12 is small-sized with 50kg
Vacuum melting furnace carries out melting.After these steel ingots are heated into 1150 DEG C in the stove after being swept with Ar air-blowings, implement hot rolling, be made
Thickness of slab 4.0mm hot rolled plate.
Then, after the hot rolled plate implemented 1 minute to these hot rolled plates at 950 DEG C in an atmosphere is annealed, surface is carried out
The bead of bead, afterwards, after being impregnated 120 seconds in 20 mass % sulfuric acid solutions of 80 DEG C of temperature, by 15 mass %
Impregnated 60 seconds in the mixed acid for 55 DEG C of the temperature that nitric acid and 3 mass % hydrofluoric acid are formed, thus carry out pickling, carry out deoxidation
Skin.
In addition, obtaining thickness of slab 1.0mm cold-reduced sheet by cold rolling, in atmosphere opening stove, carried out at 900 DEG C 1 minute
Annealing, obtains cold rolled annealed plate.By the cold rolled annealed plate in 80 DEG C of temperature, 20 mass %NaSO4Middle progress is made with steel plate three times
For the 3A/dm of anode2Under, the cathodic pickling of 10 seconds, then, in the temperature being made up of 5 mass % nitric acid and 3 mass % hydrofluoric acid
Impregnated 30 seconds in 55 DEG C of mixed acid, thus carry out descale, obtain cold rolled annealed acid-cleaning plate.
First, the judgement of the surface texture of the cold rolled annealed acid-cleaning plate obtained by visually carrying out.
Then, using resulting cold rolled annealed acid-cleaning plate as material to be tested, as mother metal corrosion resistance sample for evaluation,
Make the pickling state material of the cold rolled annealed acid-cleaning plate after descale and surface is ground with the pouncing paper of No. #600
Two kinds of samples of grinding-material afterwards.
In addition, the TIG weld portion that identical material is carried out for identical material to be tested is tested.In this experiment, will be from
2 plates cut in each material to be tested are engaged by TIG weld, and their surface is carried out with the pouncing paper of No. #600
Grinding, obtain same steel grade corrosion resistance at welded part evaluation sample.
In addition, for each material to be tested test with SUS304 different steel grade TIG weld.In this experiment, will be from each
The plate cut in individual material to be tested is engaged with thickness of slab 1.0mm SUS304 plate by TIG weld, by their surface
It is ground with the pouncing paper of No. #600, obtains different steel grade corrosion resistance at welded part evaluation sample.Same steel grade, different steel grade TIG welderings
It is as described below to connect experimental condition, in a manner of sealing run width (width of the back bead) reaches more than 3mm
Welding current is controlled, evaluation face is sealing run face.
Weldingvoltage：10V
Welding current：90~110A
Speed of welding：600mm/ minutes
Electrode：1.6mm tungsten electrode
Protective gas：Surface weld side (front bead side) Ar 20L/ minutes
Sealing run side (back bead side) Ar 20L/ minutes
Using resulting mother metal (pickling state material, grinding-material), with steel grade weld part, different steel grade weld part sample
Product, brine spray cyclic test (CCT, neutral salt spray cyclic are carried out according to JIS H8502 (1999)
corrosion test).CCT spray (35 DEG C, 2h) → dry with 5 mass %NaCl solution (60 DEG C, 4h, relative humidity 20~
30%) → moistening (40 DEG C, 2h, relative humidity more than 95%) implements 15 circulations as 1 circulation.By resulting result
It is shown in table 2.
It should be noted that the determinating reference respectively tested is as follows.
(a) outward appearance after cold rolled annealed pickling：By the way that with surface defect, (squamous folds (scab), stomata (pin
Hole), linear squamous folds (linear scab), titanium streak artifacts, the color exception of white muscle lines (white streak))
The length of part judged that ratio of defects is determined as ◎, ratio of defects more than 5% less than 5% relative to the ratio of plate total length
And it is determined as zero less than 10%, and ratio of defects 10% is determined as △ less than 20%, ratio of defects more than 20% is determined as ×, will
It is qualified that ◎ and zero is determined as, by △ and × be determined as it is unqualified.
(b) the CCT results of pickling state material and #600 grinding-materials：Rust area after 15 cyclic tests
Scale rate (Rust area ratio) is determined as ◎ less than 10%, and scale rate 10% is determined as zero less than 20%, got rusty
Rate 20% is determined as △ less than 30%, scale rate more than 30% is determined as ×, it is qualified that ◎ and zero are determined as, by △ and
× be determined as it is unqualified.
(c) with steel grade corrosion resistance at welded part result of the test：TIG butt welding is carried out in same steel grade, with No. #600 grind
After grinding the tempering colour that paper removes weld part, the scale rate of the weld part after CCT15 circulation is determined as ◎, scale rate less than 10%
10% is determined as zero less than 20%, and scale rate 20% is determined as △ less than 30%, and scale rate more than 30% is sentenced
Be set to ×, it is qualified that ◎ and zero are determined as, by △ and × be determined as it is unqualified.
(d) different steel grade corrosion resistance at welded part result of the test：TIG butt welding is carried out with SUS304, with the grinding of No. #600
After paper removes the tempering colour of weld part, the scale rate of the weld part after CCT15 circulation is determined as ◎, scale rate less than 10%
10% is determined as zero less than 20%, and scale rate 20% is determined as △ less than 30%, and scale rate more than 30% is sentenced
Be set to ×, it is qualified that ◎ and zero are determined as, by △ and × be determined as it is unqualified.
As No.1~8 of example and 33 composition composition within the scope of the invention, for any one scoring item
Mesh, corrosion resistance, surface texture are excellent.
On the other hand, the comparative example No.9 of Cr amounts as little as 16.2% rust area is more, and corrosion resistance is deteriorated.
In addition, the rust area that Cr amounts are up to 19.4% comparative example No.10 different steel grade weld part is more, corrosion resistance becomes
Difference.This, which can consider, is due to, the Cr amounts height for promoting element is generated as ferrite, therefore, horse does not occur for different steel grade weld part
Family name's body.
In addition, the rust area of the comparative example No.11 of Ti amounts as little as 0.07% different steel grade weld part is more, corrosion resistance becomes
Difference.
In addition, Si amounts and Nb amounts exceed in the comparative example No.12 of the scope of the invention, confirmed on the surface of mother metal some
Oxide skin remains, and the corrosion resistance after cold rolled annealed pickling is deteriorated.
Embodiment 2
Then, the ferrite composition with example No.13~18 shown in table 3, comparative example No.19~22 formed
It is after stainless steel carries out melting in 150 tons of VOD (Vacuum Oxygen Decaburization, vacuum-oxygen decarbonizing) stove,
By continuous Casting into steel billet.1150 DEG C of temperature is heated to, hot rolling is carried out, obtains thickness of slab 4.0mm coils of hot rolled.Connect
, annealing is carried out 1~5 minute in the coke-stove gas combustion atmosphere of 950 DEG C, air than 1.3, surface is carried out at iron ball shot-peening
After managing (shot blasting), after being impregnated 120 seconds in 20 mass % sulfuric acid solutions of 80 DEG C of temperature, by 15 mass % nitre
Impregnated 60 seconds in the mixed acid for 55 DEG C of the temperature that acid and 3 mass % hydrofluoric acid are formed, thus carry out pickling, carry out descale,
Obtain hot-roll annealing pickling coiled material.And then thickness of slab 1.0mm cold-reduced sheet is obtained by cold rolling, at 900 DEG C, air is than 1.3
Annealed 2 minutes in coke-stove gas combustion atmosphere, in 80 DEG C of temperature, 20 mass %NaSO4Middle progress is used as anode using steel plate three times
3A/dm2Under, the cathodic pickling (electrolytic descaling) of 10 seconds, then, by 5 mass % nitric acid and 3 matter
Impregnated 30 seconds in the mixed acid for 55 DEG C of the temperature that amount % hydrofluoric acid is formed, thus carry out descale, obtain cold rolled annealed pickling
Plate.
First, the judgement of the surface texture of the cold rolled annealed acid-cleaning plate visually so obtained.
Then, mother metal is made similarly to Example 1, with steel grade weld part, different steel grade weld part sample, with embodiment 1
Brine spray cyclic test (CCT) is similarly carried out according to JIS H8502 (1999), carries out corrosion resistance evaluation test.By institute
Obtained result is shown in table 4.It should be noted that the determinating reference respectively tested is similarly to Example 1.
As example No.13~18 composition composition within the scope of the invention, for any one assessment item,
Corrosion resistance, surface texture are excellent.
On the other hand, the Mo amounts as the No.19 of comparative example are 0.40%, higher than the scope of the invention, equally, as comparing
The No.20 of example Cr amounts are 19.5%, and higher than the scope of the invention, therefore, the rust area of different steel grade weld part is more, corrosion resistance
It is deteriorated.This, which can consider, is due to, is generated as ferritic phase and promotes the Mo amounts of element and Cr amounts high, therefore, different steel grade welding
Formation of martensite does not occur for portion.
In addition, it is 0.003% that comparative example No.21 Si amounts, which are 0.33%, Nb amounts, outside the scope of the present invention, together
Sample, comparative example No.22 Si amounts are that 0.45%, Mg amounts are 0.0010%, more than the scope of the invention, thus, it is seen that some
Oxide skin remains, and the corrosion resistance after cold rolled annealed pickling is deteriorated.
Embodiment 3
The steel that composition with example No.23~28 shown in table 5, comparative example No.29~32 is formed is small with 50kg
Type vacuum melting furnace carries out melting.After these steel ingots are heated into 1150 DEG C in the stove after being swept with Ar air-blowings, hot rolling is carried out, is obtained
To thickness of slab 4.0mm hot rolled plate.
Then, after these hot rolled plates are implemented with the hot rolled plate annealing of 1 minute at 950 DEG C in an atmosphere, surface is carried out
The bead of glass microballoon, after being impregnated 120 seconds in 20 mass % sulfuric acid solutions of 80 DEG C of temperature, by 15 mass % nitric acid
Impregnated 60 seconds in the mixed acid of 55 DEG C of the temperature formed with 3 mass % hydrofluoric acid, thus carry out pickling, carry out descale.
And then thickness of slab 1.0mm cold-reduced sheet is obtained by cold rolling, in reducing atmosphere (H2：5 volume %, N2：95 bodies
Product %, -40 DEG C of dew point) in, the annealing of 1 minute is carried out at 900 DEG C, obtains cold rolled annealed plate.By the cold rolled annealed plate in temperature
Carry out being used as the electrolysis of anode using steel plate twice in 50 DEG C of degree, the solution being made up of 15 mass % nitric acid and 0.5 mass % hydrochloric acid
(10A/dm2Lower 2 seconds), descale is carried out, obtains cold rolled annealed acid-cleaning plate.
First, the judgement of the surface texture of the cold rolled annealed acid-cleaning plate obtained by visually carrying out.
Then, using cold rolled annealed acid-cleaning plate as material to be tested, the cold rolling after descale is made similarly to Example 1
The pickling state material of annealing and pickling plate and both mother metals are resistance to the grinding-material after surface grinding with the pouncing paper of No. #600
Erosion analysis sample.
In addition, when making the different steel grade welding sample with steel grade and with SUS304, it is assumed that gas shield during TIG weld
Incomplete situation, surface weld side, sealing run side are carried out to use Ar+20 volumes %N2Protective gas welding examination
Test.
Welding condition is as follows, and evaluation face is sealing run face.
Weldingvoltage：10V
Welding current：90~110A
Speed of welding：600mm/ minutes
Electrode：1.6mm tungsten electrode
Protective gas：Surface weld side Ar+20 volumes %N220L/ minutes
Sealing run side Ar+20 volumes %N220L/ minutes
Using resulting mother metal, with steel grade weld part, different steel grade weld part sample, entered according to JIS H8502 (1999)
Row brine spray cyclic test (CCT).CCT spray (35 DEG C, 2h) → dry with 5 mass %NaCl solution (60 DEG C, it is 4h, relative
Humidity 20~30%) → moistening (40 DEG C, 2h, relative humidity more than 95%) as 1 circulation, carries out 15 circulations.By gained
To result be shown in table 6.It should be noted that determinating reference is similarly to Example 1.
As No.23~28 of example, for any one assessment item, corrosion resistance, surface texture are excellent.Add
Al, Sb are added, in the different steel grade weld part with SUS304, corrosion resistance is also very excellent for Zr, V No.25~28.
On the other hand, the Cr amounts as the No.29 of comparative example are 16.7%, less than the scope of the present invention, therefore, face of getting rusty
Product is more, and corrosion resistance is deteriorated.
In addition, comparative example No.30 Cr amounts are 19.7%, higher than the scope of the present invention, therefore, the life of different steel grade weld part
The area that becomes rusty is more, and corrosion resistance is deteriorated.This, which can consider, is due to, is generated as ferritic phase and promotes the Cr amounts of element high, therefore,
Formation of martensite does not occur for different steel grade weld part.
In addition, it is 0.40% that comparative example No.31 Si amounts, which are 0.36%, Mo amounts, more than the scope of the invention, in mother metal
Some oxide skin residuals are confirmed on surface, the corrosion resistance after cold rolled annealed pickling is deteriorated, and particularly in gas shield
Corrosion resistance is also deteriorated when insufficient and in SUS304 different steel grade weld part.
In addition, it is 0.10% that comparative example No.32 Si amounts, which are 0.50%, Nb amounts, more than the scope of the invention, in mother metal
Oxide skin residual is confirmed on surface, the corrosion resistance after cold rolled annealed pickling is deteriorated.
From the foregoing, it will be observed that in example of the present invention, the corrosion resistance of mother metal, with the corrosion resistance of steel grade weld part, with SUS304's
The good ferrite series stainless steel plate of the corrosion resistance of different steel grade weld part, the surface texture of cold rolled annealed acid-cleaning plate, can not
Grinding is carried out to hot-roll annealing acid-cleaning plate and obtained.
Industrial applicability
It is suitable as with utensil, cooking apparatus, Discussion on architecture package material, structural metal part, lift/escalator
Centered on package material, household electrical appliances, automobile component etc., require the part of corrosion resistance.
Claims (4)
- A kind of 1. ferrite-group stainless steel, it is characterised in that in terms of quality %, C：0.003~0.015%, Si：0.05~ 0.30%th, Mn：0.10~0.35%, P：Less than 0.06%, S：Less than 0.02%, Cr：17.0~19.0%, Ni：It is more than 0.10% and less than 0.30%, Ti：0.10~0.40%, Nb：0.010% less than 0.050%, Mo：Less than 0.12%, N：0.005~0.015%, Cu：0.31~0.50%, Mg：Less than 0.0005%, surplus is by Fe and inevitable impurity structure Into.
- 2. ferrite-group stainless steel as claimed in claim 1, it is characterised in that also contain Al in terms of quality %：0.02~ 0.50%.
- 3. ferrite-group stainless steel as claimed in claim 2, wherein, the Al in terms of quality %：0.10~0.50%.
- 4. ferrite-group stainless steel as claimed any one in claims 1 to 3, it is characterised in that also contained in terms of quality % Zr：0.05~0.60%, V：One or both of 0.02~0.50%.
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| JP2012055308 | 2012-03-13 | ||
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| PCT/JP2013/001462 WO2013136736A1 (en) | 2012-03-13 | 2013-03-07 | Ferritic stainless steel |
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| JP5534119B1 (en) * | 2012-09-25 | 2014-06-25 | Ｊｆｅスチール株式会社 | Ferritic stainless steel |
| KR101809812B1 (en) * | 2013-07-29 | 2017-12-15 | 제이에프이 스틸 가부시키가이샤 | Ferritic stainless steel having excellent corrosion resistance of weld zone |
| ES2713154T3 (en) * | 2014-01-08 | 2019-05-20 | Jfe Steel Corp | Ferritic stainless steel and method to produce the same |
| KR20160105869A (en) * | 2014-01-08 | 2016-09-07 | 제이에프이 스틸 가부시키가이샤 | Ferritic stainless steel and method for producing same |
| JP6137089B2 (en) * | 2014-09-02 | 2017-05-31 | Ｊｆｅスチール株式会社 | Cold rolled steel sheet manufacturing method and cold rolled steel sheet manufacturing equipment |
| CN109312422B (en) * | 2016-06-10 | 2020-06-23 | 杰富意钢铁株式会社 | Stainless steel sheet for fuel cell separator and method for producing same |
| CA3026612A1 (en) | 2016-06-10 | 2017-12-14 | Jfe Steel Corporation | Stainless steel sheet for fuel cell separators, and production method therefor |
| EP3670692B1 (en) * | 2018-12-21 | 2022-08-10 | Outokumpu Oyj | Ferritic stainless steel |
| CN113385897A (en) * | 2021-06-11 | 2021-09-14 | 山西太钢不锈钢股份有限公司 | Preparation method of ferrite stainless steel thin-wall welded pipe |
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| JPH06145906A (en) * | 1992-11-02 | 1994-05-27 | Kawasaki Steel Corp | Ferritic stainless steel excellent in resistance to corrosion by water condensation |
| JP2842787B2 (en) | 1994-06-24 | 1999-01-06 | 川崎製鉄株式会社 | Annealing and descaling of cold rolled stainless steel strip |
| JP3589036B2 (en) * | 1997-08-05 | 2004-11-17 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet excellent in deep drawability and ridging resistance and method for producing the same |
| JP3680829B2 (en) * | 2001-10-31 | 2005-08-10 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet excellent in deep drawability, secondary work brittleness resistance and corrosion resistance, and method for producing the same |
| JP4396676B2 (en) | 2005-08-17 | 2010-01-13 | Ｊｆｅスチール株式会社 | Ferritic stainless steel sheet with excellent corrosion resistance and method for producing the same |
| JP2007119856A (en) * | 2005-10-28 | 2007-05-17 | Nisshin Steel Co Ltd | Hydrophilic stainless steel sheet and its manufacturing method |
| JP5042553B2 (en) * | 2006-08-03 | 2012-10-03 | 新日鐵住金ステンレス株式会社 | Ferritic stainless steel with excellent crevice corrosion resistance and formability |
| CA2650469C (en) * | 2006-05-09 | 2014-02-11 | Nippon Steel & Sumikin Stainless Steel Corporation | Stainless steel excellent in corrosion resistance, ferritic stainless steel excellent in resistance to crevice corrosion and formability, and ferritic stainless steel excellent in resistance to crevice corrosion |
| JP5320034B2 (en) * | 2008-11-14 | 2013-10-23 | 新日鐵住金ステンレス株式会社 | Mo-type ferritic stainless steel for automotive exhaust system parts with excellent corrosion resistance after heating |
| ES2602800T3 (en) * | 2011-11-30 | 2017-02-22 | Jfe Steel Corporation | Ferritic stainless steel |
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