CN107709599A - Steel - Google Patents
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- CN107709599A CN107709599A CN201780002094.8A CN201780002094A CN107709599A CN 107709599 A CN107709599 A CN 107709599A CN 201780002094 A CN201780002094 A CN 201780002094A CN 107709599 A CN107709599 A CN 107709599A
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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
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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
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- 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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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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
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
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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
Abstract
The chemical composition of the steel includes C in terms of quality %：0.01~0.20%, Si：0.02~0.70%, Mn：0.30~2.50%, Ti：0.003~0.024%, B：0.0010~0.0050%, N：0.0010~0.0090%, O：0.0010~0.0050%, Insol.Zr：0.0005~0.0100%, P：Less than 0.050%, S：Less than 0.0080%, Al：Less than 0.005%, Sol.Zr：Less than 0.0010%, Ca and REM content is total：Less than 0.0005%, remainder includes Fe and impurity, BasBNB represented by=(N (Ti (O Insol.Zr × (32/91.224)) × (95.734/48)) × (14/47.867)) × (10.811/14)asBNFor more than 0.0005, and BF=B BasBNRepresented BFFor more than 0.0005, there is 50/mm2Equivalent diameter above is more than 0.5 μm of oxide containing Zr.
Description
Technical field
The present invention relates to steel, and (below, " HAZ " is sometimes referred to as more particularly to welding heat affected zone.) tenacity excellent
Steel.
The application was incited somebody to action based on 04 19th, the 2016 Patent 2016-083595 CLAIM OF PRIORITYs in Japanese publication
Its content is incorporated herein.
Background technology
As the purposes of steel, can include：Ship, high-rise, other buildings, bridge, marine structure,
The welded structures such as LNG storage tank, other large tanks, line pipe.In recent years, due to the high stratification of building structure, packaging
The Weight Loaded increase of case ship, therefore advance the maximization of welded structure.It is accompanied by this, thickness of slab, which thickens, is required to steel
Change, high intensity.In addition, for welded structure as described above, it is also required to ensure further to pacify for weld part
Quan Xing, reliability, the toughness of welding heat affected zone is (below, sometimes referred to as " HAZ toughness ".) raising turn into problem.
In addition, welding procedure expense shared in the building expense entirety of welded structure is larger, in order to cut down the expense,
It is required that efficiently welded.Specifically, welded with the input of big heat, it is effective to reduce welding road number.However,
In the case where carrying out the welding of big heat input, the HAZ of steel tissue meeting coarsening, the deterioration of toughness can not be avoided.
In the past, it is known that crystal particle diameter, phase-change organization, HAZ hardness, the thick hard of austenite (γ) are equal can be to height
The HAZ toughness of power steel plate causes big influence, and proposes the various countermeasures for improving HAZ toughness.Wherein, HAZ is organized
Raising of the miniaturization to HAZ toughness is maximally efficient, and proposes many methods that HAZ is organized to miniaturization using field trash.
The miniaturization organized for the HAZ that make use of field trash, there are as below methods：Pressed down by the pinning effect of field trash
The method of grain growth processed；Austenite crystal intragranular with heat affecting when because of welding and coarsening, make using field trash as core
Ferrite generates (transgranular phase transformation) and makes the method for tissue miniaturization.On organizing miniaturization as caused by transgranular phase transformation, so far
Untill the present, it is proposed that by the use of the nitride such as TiN, MnS sulfides or at high temperature also chemically stable oxide etc. as
Ferrite generates the technology in site.
For example, proposing a kind of method in patent document 1, it is in the molten steel for do not contain substantially Al while added
Ti and Zr, fine Ti and Zr composite oxides are generated, hot shadow will be welded by the composite oxides of the fine Ti and Zr
Ring the tissue miniaturization in area.Fine Ti and Zr composite oxides have been recorded in patent document 1 to be turned into radial generation
The core of fine ferritic transgranular phase transformation.
In addition, proposing a kind of method in patent document 2, it is to improve HAZ by the field trash comprising REM and Zr
Toughness.
A kind of method is proposed in patent document 3, it is in the steel for do not contain substantially Al, is made using Ti as mainly
The oxide of composition disperses with TiN, MnS and BN miscible precipitate.Patent Document 3 discloses：According to this method, except
Suppress beyond the transgranular phase transformation that is brought by Ti oxides, the ferritic generation from crystal boundary, HAZ toughness are also suppressed by B
Improve.
In addition, patent document 4 proposes a kind of method, it is pinning effect by being brought by TiN and brought by BN
Transgranular phase transformation suppresses HAZ softening by HAZ miniaturizations, and then by using the raising for the quenching degree brought by B, so as to improve
Toughness.
For the technology of patent document 1~4, certain HAZ toughness raising is can obtain in the case where heat input is small
Effect.However, heat input is being carried out to improve the efficiency of welding more than big heat input welding as 40kJ/mm
When, it is difficult to the HAZ toughness of steel is stably improved.As its reason, it is believed that be：The field trashes such as oxide hold in molten steel
Easily cohesion, is difficult to be uniformly dispersed in steel；Make to be mingled with because being exposed for a long time at high temperature when big heat is inputted and welded
Thing goes bad, it is difficult to is controlled in a manner of easily being worked using the core as transgranular phase transformation.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 1-159356 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-291347 publications
Patent document 3：Japanese Unexamined Patent Publication 3-162522 publications
Patent document 4：Japanese Unexamined Patent Publication 2007-177327 publications
The content of the invention
Invent problem to be solved
The present invention is in view of such actual conditions, its problem are, there is provided has excellent HAZ toughness, particularly in heat
Amount input has the steel of excellent toughness in the HAZ for more than 40kJ/mm big heat input welding.
Means for solving the problems
The inventors of the present invention are conceived to as the Intragranular Acicular Ferrite generation site for the tissue miniaturization in HAZ
Oxide containing Zr (includes the composite oxides containing Zr and Ti.It is same as below.) and boron nitride and have made intensive studies.Its
As a result, following (A)~(F) neodoxy is mainly obtained.
(A) it is 50/mm in the individual number density for the oxide containing Zr that equivalent diameter is more than 0.5 μm2Situation above
Under, Intragranular Acicular Ferrite is fine in HAZ and generates in large quantities, and HAZ toughness improves.
(B) there is the tendency that HAZ toughness more improves in the Sol.Zr in steel more at least, and being limited in below 0.0010 mass % is
Important.Wherein, Sol.Zr is acid-solubility Zr, equivalent to can be solid-solution in steel with measure such as electroextraction Residue Analysis
In Zr.
(C) by adding Zr, Ti and B, so as to which boron nitride is separated out using oxide containing Zr as core in steel.It is such
The oxide containing Zr for having separated out boron nitride generates site as Intragranular Acicular Ferrite and further effectively plays function.
To in the case of the effect, it is necessary to which more than 0.0005% will be set as the B content (quality %) of boron nitride.
(D) in order to suppress the generation of Ti nitride and generate boron nitride, it is necessary to be based on ZrO2、Ti2O3, TiN, BN
Molecular weight controls the B (B as boron nitrideasBN) content (quality %).Specifically, following formula is worked as<1>Value be
When more than 0.0005, the HAZ toughness improvements brought by boron nitride are obtained.
BasBN=(N- (Ti- (O-Insol.Zr × (32/91.224)) × (95.734/48)) × (14/47.867)) ×
(10.811/14)<1>
Wherein, N, Ti and O in formula are the content (quality %) of each element (N, Ti, O) included in steel, and Insol.Zr is
The insoluble Zr of acid content (quality %).
(E) it is segregated by being dissolved B in original austenite crystal prevention, suppresses the generation of thick grain boundary ferrite, so as to contributes to
The improvement of HAZ toughness.Therefore, in addition to the above-mentioned B amounts separated out as boron nitride, it is also necessary to ensure to be used to be dissolved
B B amounts.Specifically, when by following formula<2>Represented BFFor more than 0.0005 when, it can be ensured that the solid solution B of ormal weight, obtain
To grain boundary ferrite inhibition.
BF=B-BasBN<2>
Wherein, the B in formula is the B content (quality %) that includes in steel, BasBNFor by formula<1>The value obtained.
(F) if excessively containing the Al to be worked as strong deoxidant element, the generation of Zr, Ti oxide in steel
It is hindered.In order to ensure the dissolved oxygen content in molten steel, oxide containing Zr is generated in steel, Al content is limited in 0.005 matter
It is important to measure below %.In addition, the deoxidation power as Ca, REM, which is even more than the total of Al element, is limited in 0.0005 matter
It is important to measure below %.
The present invention is completed based on above-mentioned opinion, and its purport is as described below.
(1) chemical composition of the steel of a scheme of the invention includes C in terms of quality %：0.01~0.20%, Si：
0.02~0.70%, Mn：0.30~2.50%, Ti：0.003~0.024%, B：0.0010~0.0050%, N：0.0010~
0.0090%th, O：0.0010~0.0050%, Insol.Zr：0.0005~0.0100%, P：Less than 0.050%, S：
Less than 0.0080%, Al：Less than 0.005%, Sol.Zr：Less than 0.0010%, Ca and REM content is total：0.0005%
Hereinafter, remainder includes Fe and impurity, following formula<1>Represented BasBNFor more than 0.0005, and following formula<2>Institute's table
The B shownFFor more than 0.0005；With 50/mm2Equivalent diameter above is more than 0.5 μm of oxide containing Zr.
BasBN=(N- (Ti- (O-Insol.Zr × (32/91.224)) × (95.734/48)) × (14/47.867)) ×
(10.811/14)<1>
BF=B-BasBN<2>
Wherein, N, Ti, O and B in formula are N, Ti, O, B contained in the steel content in terms of quality %, and Insol.Zr is
The insoluble Zr of the acid content in terms of quality %, Sol.Zr are the acid-solubility Zr content in terms of quality %.
(2) steel according to above-mentioned (1), above-mentioned chemical composition can also further be contained in terms of quality % to be selected from
Cu：Less than 1.50%, Ni：Less than 3.00%, Cr：Less than 1.00%, Mo：Less than 1.00%, V：Less than 0.100% and Nb：
It is one kind or two or more in less than 0.035%.
(3) steel according to above-mentioned (1) or (2), above-mentioned chemical composition can also further be contained in terms of quality %
Selected from W：Less than 1.00% and Sn：1 kind in less than 0.50% or 2 kinds.
Invention effect
According to the such scheme of the present invention, using the teaching of the invention it is possible to provide have the steel of excellent toughness in the HAZ of big heat input welding
Material.If efficient to be welded into possibility using the steel, the construction cost of welded structure can be reduced by leaps and bounds.
It and then can improve the security of welded structure, reliability.
Embodiment
Known Ti oxides, boron nitride are scattered in welding metal, HAZ, have the effect for making it organize miniaturization.With
This is relative, and Zr is not the element being typically added in steel, and on the effect brought by adding Zr, the research that the past is carried out is very
It is limited.
Particularly, so far, can be to steel for the boron nitride of the further compound precipitation on oxide containing Zr
The miniaturization of HAZ tissues and HAZ toughness, which improve, produces that influence how is not investigated also.
As organizing the Intragranular Acicular Ferrite of miniaturization to generate site for HAZ, the inventors of the present invention are conceived to containing Zr
Oxide and boron nitride simultaneously have made intensive studies.As a result, following (a)~(f) neodoxy is mainly obtained.
(a) the inventors of the present invention improve the method for HAZ toughness actually to making oxide containing Zr be scattered in steel
Studied.As a result, it specify that：50/mm is dispersed with the oxide containing Zr that equivalent diameter is more than 0.5 μm2
In the case of above, compared with the situation that the oxide for the Ti simple substance for making to use disperses in the past, Intragranular Acicular Ferrite is fine and a large amount of
Ground generates, and can improve HAZ toughness by the miniaturization of tissue.
(b) in order to obtain more than regulation number contributing to HAZ to organize the oxide containing Zr of miniaturization, it is necessary to by Zr contents
It is set as more than a certain amount of.On the other hand, it is not that all Zr in steel form oxide, a part of Zr does not form oxidation
Thing and remain in steel.The Zr (Sol.Zr) for not forming oxide not only deteriorates HAZ but also makes the toughness of steel itself
Significantly deterioration.Therefore, not only to ensuring HAZ, also for ensuring the toughness of steel itself, it is necessary to reduce the Sol.Zr in steel.
There is the tendency that toughness more improves in Sol.Zr, in order to obtain the steel of HAZ tenacity excellents, Sol.Zr is limited in more at least
Below 0.0010 mass % is important.In order to further improve HAZ toughness, Sol.Zr is preferably limited in 0.0003 matter
Measure below %.
(c) know：In the steel of the oxide containing Zr is dispersed with, even if the number increase of field trash, there is also as iron element
Body generation site plays the field trash of function and the field trash of function is played not as generation site.
In addition, the inventors of the present invention in order to more effectively promote ferrite to generate, are studied various elements.
Its result is found：By the way that containing a certain amount of B above, so that in casting, hot rolling or welding, boron nitride is with oxide containing Zr
Separated out as core, the miscible precipitate generates site as Intragranular Acicular Ferrite and further effectively plays function.
That is, boron nitride is passed through, making it difficult to play being aoxidized containing Zr for function separately as Intragranular Acicular Ferrite generation site
Thing also turns into ferrite generation site, the miniaturization for more effectively contributing to HAZ to organize.In order to obtain these effects, it is necessary to will
For the index (B for the B content (quality %) for separating out boron nitrideasBN) it is set as more than 0.0005, and B content is set as
The BasBNMore than.
(d) however, Ti also serves as nitride forming element and worked in addition to B in steel.Therefore, in order that boron nitride has
Effect ground is separated out, it is necessary to suppress the generation of Ti nitride.The inventors of the present invention are in order to understand including oxide, nitride
The generting machanism of field trash, understand for generating the condition of boron nitride and studied.
It is believed that：In the molten steel comprising Ti, Zr, B, the deoxidation power Zr stronger than Ti preferentially turns into oxide first, remaining
Oxygen combined with Ti, turn into Zr and Ti composite oxides.Then, do not form oxide and remaining Ti and nitrogen with reference to and shape
Into nitride.Then, not with Ti with reference to and remaining nitrogen formed boron nitride.
Due to thinking that Zr forms ZrO2, Ti formed Ti2O3BN is formed with TiN, B, therefore based on their atomic weight or molecule
Amount, uses following formula<1>, the B (B as boron nitride can be obtainedasBN) content (quality %).It is believed that：The value is
More than 0.0005 and the value of B content be BasBNDuring the above, the available HAZ toughness improvements brought by boron nitride.
BasBN=(N- (Ti- (O-Insol.Zr × (32/91.224)) × (95.734/48)) × (14/47.867)) ×
(10.811/14)<1>
Wherein, N, Ti and O in formula are the content (quality %) of each element (N, Ti, O) contained in steel, and Insol.Zr is
The insoluble Zr of acid content (quality %).
To with meeting above-mentioned formula<1>The steel billet of composition carry out obtained from hot rolling in steel, it is scattered fine to contain
Zr oxides (the mainly composite oxides containing Zr and Ti).In addition, on a part of oxide containing Zr, boron nitride enters one
Walk compound precipitation.
If boron nitride is heated beyond 1200 DEG C of temperature province in welding, can be dissolved again, but oxygen containing Zr
Compound also can stably be present even if being heated to 1400 DEG C.Therefore, in the heating of welding, boron nitride is dissolved, and solid solution B is not
It is uniformly present in around oxide containing Zr.It is believed that：It is used as in the cooling procedures of solid solution B after welding and is made with oxide
Separated out again for the boron nitride of core.
(e) generation of thick grain boundary ferrite is suppressed when the solid solution B that the original austenite crystal prevention of steel is segregated is in welding,
Improve HAZ toughness.Therefore, in order to ensure the B content separated out as boron nitride, and also for ensure be dissolved B, it is necessary to contain
An adequate amount of B.
In order that boron nitride is fully separated out, it is necessary to which B content is set as into BasBN(B-B aboveasBN>=0), but it is terrible
To grain boundary ferrite inhibition, it is necessary to further increase B content and by following formula<2>Represented solid solution B (BF) be set as
More than 0.0005 (B-BasBN≥0.0005)。
BF=B-BasBN<2>
Wherein, the B in formula is B contained in steel content (quality %), BasBNFor by formula<1>The value obtained.
(f) on the other hand, because Al works in steel as strong deoxidant element, so if containing in large quantities in steel
Have, then hinder Zr, Ti oxide generation.Oxide containing Zr, Al are generated in steel in order to ensure the dissolved oxygen content in molten steel
Content to be limited in below 0.005 mass % be important.More preferably Al content is limited in below 0.003 mass %.Picture
Total be limited in below 0.0005 mass % of Ca, REM like that than the deoxidant element of Al strength is important.
Meet the oxide containing Zr of given size more than the steel generation regulation number of these conditions.In addition, this contains Zr
Oxide is the composite oxides containing Zr and Ti mostly, and boron nitride is separated out using oxide as core.Then, understand fully：
If actual attempt the steel to carry out big heat input welding, the particle of oxide is given birth in HAZ as Intragranular Acicular Ferrite
Function is effectively played into site, improves HAZ toughness by the HAZ miniaturizations organized.
Hereinafter, the steel (steel of present embodiment) of an embodiment of the invention are described in detail.
First, the restriction reason of the chemical composition of the steel of present embodiment is illustrated.In the following description, respectively
" % " in the explanation of element refers to " quality % ".
(C：0.01~0.20%)
C is in order to ensure the element required for intensity.When C content is less than 0.01%, it can not ensure as in general structure
Intensity required by part.Therefore, it is 0.01% by the lower limit set of C content.The preferable lower limit of C content is 0.03%.Separately
On the one hand, if C content is more than 0.20%, mother metal, HAZ become to be difficult to ensure that toughness.Therefore, the upper limit of C content is set
It is set to 0.20%.The preferable upper limit is 0.15%.
(Si：0.02~0.70%)
Si is the element for improving the quenching degree of steel, contributing to steel strength to rise.In order to obtain the effect, by Si contents
Lower limit set is 0.02%.It is preferred that it is 0.05% by the lower limit set of Si contents.On the other hand, because the reactivity of Si and oxygen is high
And there is deoxidation, therefore the formation to the oxide containing Zr impacts.If Si contents more than 0.70%, oxide
Composition can change, and can not reach the miniaturization of HAZ tissues, and HAZ toughness reduces.Therefore, the upper limit of Si contents is set as
0.70%.The upper limit of preferred Si contents is 0.50%, and the further preferred upper limit is 0.40%.
(Mn：0.30~2.50%)
Mn has the effect for the quenching degree for improving steel, is to ensure effective element to intensity and toughness.Mn contents are less than
When 0.30%, intensity and toughness as structure member can not be obtained because of the deficiency of quenching degree.Therefore, by the lower limit of Mn contents
It is set as 0.30%.The preferable lower limit set of Mn contents is 0.60%.On the other hand, if Mn contents are more than 2.50%,
Mn during because of solidification, which is segregated, causes the toughness in center segregation portion to reduce, and quenching degree excessively improves and the equal hardness increasing of mother metal, HAZ
Greatly so as to which toughness deteriorates.Therefore, the upper limit of Mn contents is set as 2.50%.The preferable upper limit is 2.00%.
(Ti：0.003~0.024%)
Ti is the element that composite oxides are formed together with Zr.The composite oxides are given birth to as the Intragranular Acicular Ferrite in HAZ
The miniaturization for playing function into site and contributing to HAZ to organize.In order to obtain the effect, the lower limit set by Ti contents is
0.003%.The preferable lower limit of Ti contents is 0.005%.On the other hand, Ti generates nitride.If Ti nitride is in large quantities
Generation, then the growing amount of boron nitride is suppressed, and becomes not obtaining in the desired effect of present embodiment.And then mistake
The Ti of amount can form TiC, deteriorate mother metal and HAZ toughness.Thus, the upper limit of Ti contents is set as 0.024%.Preferably
The upper limit is 0.020%.
(B：0.0010~0.0050%)
B be combined in steel with nitrogen, around oxide containing Zr generate boron nitride element.By the way that B content is set
It is set to more than 0.0010% and meets described later on BasBNAnd BFRated condition, so as to improve the Intragranular Acicular Ferrite in HAZ
Generative capacity, contribute to the improvement of toughness by the miniaturization of tissue.In addition, B is dissolved by being segregated in austenite grain boundary, from
And suppress thick grain boundary ferrite generation.Therefore, it is 0.0010% by the lower limit set of B content.In order to further improve HAZ
Toughness, the preferable lower limit of B content is 0.0015%.On the other hand, in the case of B content excess, intensity is not only improved
Effect meeting saturation, and mother metal, HAZ can toughness deteriorations.Therefore, the upper limit of B content is set as 0.0050%.B content
The preferable upper limit is 0.0030%.
(N：0.0010~0.0090%)
N be in order in steel with B with reference to and element required for forming boron nitride.In order to obtain the effect, by N content
Lower limit set be 0.0010%.The preferable lower limit of N content is 0.0020%.On the other hand, in the excessive situation of N content
Under, mother metal and HAZ toughness deterioration.Therefore, the upper limit of N content is set as 0.0090%.The preferable upper limit is 0.0060%.
(O：0.0010~0.0050%)
O (oxygen) is the indispensable element of the generation for the oxide containing Zr.Therefore, it is by the lower limit set of O content
0.0010%.The preferable lower limit of O content is 0.0015%.On the other hand, in the case of O content excess, can excessively give birth to
Cleannes into oxide and steel reduce, the deterioration of the ductility such as base metal tenacity and elongation, drawing.Therefore by the upper of O content
Limit is set as 0.0050%.The preferable upper limit is 0.0040%.
(Insol.Zr：0.0005~0.0100%)
Insol.Zr represents acid insoluble Zr, i.e., the Zr being present in as oxide in steel.Insol.Zr independently forms oxygen
Compound forms composite oxides together with Ti.The oxide plays function as the Intragranular Acicular Ferrite generation site in HAZ,
The miniaturization for contributing to HAZ to organize.
In order to obtain the effect above, it is necessary to be 0.0005% by Insol.Zr (the insoluble Zr contents of acid) lower limit set.
Preferable lower limit is 0.0010%.On the other hand, in the case of Insol.Zr excess, oxidation can be generated in large quantities in steel
Thing, the deterioration of HAZ toughness.Therefore, the Insol.Zr upper limit is set as 0.0100%.The preferable upper limit is 0.0075%.
(P：Less than 0.050%)
P is to be inevitably present in the element in steel as impurity.P content is more few more preferred, but if P content surpasses
0.050% is crossed, then P is segregated in austenite grain boundary and toughness significantly reduces.In addition, led when the P of cyrystal boundary segregation turns into welding
The reason for causing heat cracking.Therefore, P content is limited in less than 0.0050%.Preferably less than 0.030%.Because P content is got over
It is few more preferred, therefore lower limit does not have special provision, but from the viewpoint of manufacturing cost, or more than 0.001%.
(S：Less than 0.0080%)
S is to be inevitably present in the element in steel as impurity.If S contents are more than 0.0080%, in
The MnS of extension, mother metal and HAZ toughness, ductility deterioration are generated in heart segregation portion in large quantities.Therefore, S contents are limited in
Less than 0.0080%.Preferably less than 0.0050%.Because S contents are more few more preferred, therefore lower limit does not have a special provision, but from
From the viewpoint of manufacturing cost, or more than 0.0001%.
(Al：Less than 0.005%)
Al is the element energetically added generally as deoxidant element.But because Al easily preferentially reacts with oxygen, because
This is in the case of its content excess, and the formation of the desired oxide containing Zr becomes insufficient, the effective ferrite in HAZ
Site is generated to reduce.
And then if Al content becomes excessive, then encourage thick tufted aluminum oxide (Al2O3) be field trash formation, it is female
Material and HAZ toughness deteriorate.Thus, Al content preferably reduces as far as possible.The Al content that can be allowed is less than 0.005%,
It is preferably set to less than 0.003%.
(Ca and REM's is total：Less than 0.0005%)
Ca and REM is to be easier the preferentially element with oxygen reaction than Al.In order to form desired oxide containing Zr, by Ca
And the total of REM content is limited in less than 0.0005%.More preferably Ca contents are less than less than 0.0003% and REM contents
0.0003%, and its content adds up to less than 0.0005%.
(Sol.Zr：Less than 0.0010%)
Sol.Zr represents acid-solubility Zr, that is, the Zr being solid-solution in steel.If Sol.Zr content increase, HAZ toughness
Significantly deterioration.Therefore, its content is limited in less than 0.0010%.Because Sol.Zr is more few more preferred, therefore lower limit is without spy
Do not provide, or 0%.
Above-mentioned Insol.Zr and Sol.Zr can be measured by electroextraction Residue Analysis.Electroextraction residue
Analytic approach is following method：By dissolving parent phase electrolysis of the steel in nonaqueous solvents (acetylacetone,2,4-pentanedione-methanol solution etc.),
Extraction separation is carried out to residue (precipitate, field trash) by 0.2 μm of filter of aperture.After separation, contained Zr in solution
Measure the content for Sol.Zr, in residue contained Zr amounts for Insol.Zr content.
Sol.Zr's and Insol.Zr adds up to Zr contents contained in steel.The lower limit of Zr contents is same with Insol.Zr
For 0.0005%, preferably 0.0010%.The upper limit of Zr contents be Insol.Zr the upper limit and Sol.Zr the upper limit it is total i.e.
0.0110%, preferably 0.0075%.
The steel of present embodiment include Fe and impurity as substantially to contain above-mentioned each element and remainder.It is so-called
When impurity refers to industrially manufacture steel, by raw materials such as ore, waste material or will be because of mixed composition, and not by other
The composition allowed in the range of being had undesirable effect to characteristic.
But among impurity, for P, S, it is necessary to limit the upper limit as described above.Further, since Al, Ca and REM exist
Worked in steel as strong deoxidant element, hinder Zr, Ti generation oxide, therefore preferably reduce as far as possible.
In the steel of present embodiment, for the further purpose for improving intensity, it can also contain in scope described later
Have in Cu, Ni, Cr, Mo, V and Nb one kind or two or more replaces a Fe part.It is in addition, corrosion proof for improving
Purpose, a kind or 2 kinds in W and Sn can also be contained in scope described later.
(Cu：Less than 1.50%)
Cu is with the intensity for improving steel and the element of corrosion proof effect.In order to obtain these effects, preferably Cu is contained
Amount is set as more than 0.10%.More preferably more than 0.20%.On the other hand, even if containing Cu more than 1.50%, also do not meet with
Rise the performance improvement that matches to cost of alloy, the reason for turning into steel surface crackle sometimes on the contrary.Therefore, even in containing
In the case of having, Cu contents are also set as less than 1.50%.It is preferred that Cu contents are set as into less than 1.00%, more preferably set
Less than 0.70%, to be further preferably set as less than 0.50%.
(Ni：Less than 3.00%)
Ni is the element with the effect for improving hardness of steel.In addition, Ni is that have the matrix for improving steel under solid solution condition
The element of the effect of (matrix) toughness.In order to obtain these effects, Ni contents are preferably set as more than 0.10%.The opposing party
Face, even if containing Ni more than 3.00%, the raising for the characteristic that cannot also match with the rising of cost of alloy.Therefore, even in
In the case of containing, Ni contents are also set as less than 3.00%.It is preferred that Ni contents are set as into less than 2.00%, more preferably set
It is set to less than 1.00%.
(Cr：Less than 1.00%)
Cr is by improving quenching degree and the useful element of the raising to intensity.In addition, Cr is also to improve corrosion proof member
Element.In order to obtain these effects, Cr contents are preferably set as more than 0.10%.On the other hand, even if exceeding containing Cr
1.00%, also have not only improve corrosion proof effect saturation and also HAZ solidification and toughness deterioration situation.Therefore, even in
In the case of containing, Cr contents are also set as less than 1.00%.It is preferred that Cr contents are set as less than 0.50%.
(Mo：Less than 1.00%)
Mo is the element with the intensity for improving mother metal and the effect of toughness.In order to obtain the effect, preferably by Mo contents
It is set as more than 0.05%.On the other hand, if Mo contents are more than 1.00%, particularly HAZ hardness improves, and has HAZ
The situation of toughness deterioration.Therefore, even in containing in the case of, Mo contents are also set as less than 1.00%.It is preferred that Mo is contained
Amount is set as less than 0.50%, is more preferably set as less than 0.30%.
(V：Less than 0.100%)
V is with the element for mainly making effect that strength of parent is improved by Carbonitride Precipitation during annealing.
In order to obtain the effect, V content is preferably set as more than 0.010%.On the other hand, if V content is more than 0.100%,
Have not only effect saturation but also hardness raising, the situation of toughness deterioration.Therefore, even in containing in the case of, also V is contained
Amount is set as less than 0.100%.It is preferred that V content is set as less than 0.050%.
(Nb：Less than 0.035%)
Nb is to make the element that the intensity of mother metal and toughness are improved by crystal grain refinement and Carbide Precipitation.In order to obtain
These effects are obtained, Nb contents are preferably set as more than 0.005%.On the other hand, can if Nb contents are more than 0.035%
There is the situation that not only the effect above saturation but also HAZ toughness reduce.Therefore, even in containing in the case of, also Nb contents are set
It is set to less than 0.035%.It is preferred that Nb contents are set as less than 0.025%.
(W：Less than 1.00%)
W be dissolving and with oxygen acid ion WO4 -Form be adsorbed in that rust is upper, suppresses the saturating of chloride ion in rusty scale
Cross, improve corrosion proof element.In order to obtain the effect, W content is preferably set as more than 0.01%.On the other hand, if W
Content then has the situation of not only the effect above saturation but also mother metal and the reduction of HAZ toughness more than 1.00%.Therefore, even in
In the case of containing, W content is also set as less than 1.00%.It is preferred that W content is set as less than 0.75%.
(Sn：Less than 0.50%)
Sn is that have to turn into Sn2+And dissolve and acted on by the inhibitor in acidic chloride solution to suppress the work of corrosion
Element.In addition, for Sn there is the anodic solution for suppressing steel to react and improve corrosion proof effect.In order to obtain these effects
Fruit, Sn contents are preferably set as more than 0.03%.On the other hand, if containing Sn more than 0.50%, not only its effect is satisfied
With, and become easily to produce the rolling crack of steel plate.Therefore, in the case of containing Sn, also its content is set as
Less than 0.50%.
For the steel of present embodiment, on the basis of the content of each element is controlled as described above, it is also necessary to
Following formula<1>Represented BasBNFor more than 0.0005 and following formula<2>Represented BFFor more than 0.0005.Hereinafter, for each
From the reasons why illustrate.
BasBN=(N- (Ti- (O-Insol.Zr × (32/91.224)) × (95.734/48)) × (14/47.867)) ×
(10.811/14)<1>
BF=B-BasBN<2>
Wherein, formula<1>In N, Ti, O and B be respectively N, Ti, O and B contained in steel content (quality %),
Insol.Zr is the insoluble Zr of acid content (quality %).
As described above, in the steel of present embodiment, by making boron nitride be separated out on the top layer of the oxide containing Zr, from
And more effectively promote the generation of the Intragranular Acicular Ferrite in the cooling after welding than the simple substance of oxide containing Zr, by organizing miniaturization
To improve HAZ toughness.
In order to obtain these effects, it is necessary to will be helpful to the i.e. above-mentioned formula of index for the B content that boron nitride separates out<1>Institute
The B of expressionasBNIt is set as on the basis of more than 0.0005, B content is set as BasBNMore than.More preferably BasBNFor
More than 0.0010.On the other hand, if BasBNMore than 0.0030, then not only the effect above saturation, and also surface when casting is split
Line becomes prone to produce.Accordingly, it is preferred that BasBNThe upper limit be less than 0.0030.
In BasBNIn the case of more than 0.0005, Ti is contained in steel, also becomes to be formed more than certain amount
BN.Because Ti is the element that is preferentially combined compared with B with N, therefore in this case, Ti in steel all as Ti oxides or
Ti nitride is present, and is not in solid solution Ti in steel.
In addition, for the steel of present embodiment, the miniaturization of the tissue brought by the generation of Intragranular Acicular Ferrite, with this
Suppress grain boundary ferrite generation thick as caused by the solid solution B being segregated in austenite grain boundary simultaneously, improve HAZ toughness.
In order to obtain the effect, it is necessary to which the i.e. above-mentioned formula of B content existing for solid solution B will be used as<2>Represented BFIt is set as
More than 0.0005.More preferably more than 0.0007.As noted previously, as B >=BasBN, therefore BFNot over B content (above formula<2>
B).On the other hand, if BFMore than 0.0020, then not only the effect above saturation, and the quenching degree of steel becomes over, into
For weld part low-temperature cracks Producing reason.Therefore, preferred BFThe upper limit be 0.0020.
Next, oxide possessed by the steel of present embodiment is illustrated.
The steel of present embodiment have 50/mm2Equivalent diameter above is more than 0.5 μm of oxide containing Zr.
In the steel of present embodiment, using oxide containing Zr as core, boron nitride separates out and forms complex inclusion.
Turn into Intragranular Acicular Ferrite generation site during complex inclusion cooling after welding.For oxide containing Zr, comprising Zr and
Ti oxide is main body, in the case of the precipitation core as boron nitride, Zr concentration and Ti concentration in preferred oxides
It is equal or higher than Ti concentration.
(there is the circle of the cross-sectional area identical area of the oxide with observing in the equivalent diameter of the oxide containing Zr
Diameter) be more than 0.5 μm in the case of, the effect can be obtained.In order that oxide is as Intragranular Acicular Ferrite generation site hair
Function is waved, equivalent diameter is preferably the greater, therefore the upper limit does not limit.But if equivalent diameter becomes big, not only
The individual number density of oxide relatively tails off, and thick oxide itself carries as the possibility that the starting point destroyed works
It is high.Therefore, the equivalent diameter of the oxide containing Zr is preferably less than 10.0 μm.
In addition, as the condition to be worked with the generation site of Intragranular Acicular Ferrite, austenite when being heated in welding
In crystal grain, the oxide containing Zr for being dispersed with more than 1 is indispensable.Therefore, it is necessary to above-mentioned size oxide with 50/
mm2Individual number density above is disperseed.Because oxide number density more at most ferrite generation site more increases, therefore it is preferred
, even if scattered more than 500/mm2, its effect also can saturation.
The equivalent diameter of the oxide containing Zr and individual number density can be observed by using scanning electron microscope (SEM)
Steel surface through mirror ultrafinish determines.Specifically, to 10mm × 10mm (100mm2) more than scope surveyed using SEM
Determine equivalent diameter be more than 0.5 μm the oxide containing Zr particle number, divided by the area in the observed visual field and determine
Oxide number density.The photo shot by SEM can also be used.Particle as the measure object of oxide number density leads to
Cross to be used as using the qualitative analysis of energy dispersion-type X-ray analytical equipment (EDX) progress subsidiary SEM and at least detect
Zr and O particle.
As long as the steel of present embodiment method known to such as by molten steel by converter, electric furnace carries out melting, pass through
The steel raw materials such as slab or steel billet are made in method known to continuous casting process, ingot casting method etc., implement hot rolling to manufacture.To steel
Liquid can also implement the processing such as ladle refining, vacuum outgas.Heat can also directly be carried out to the steel raw material after casting, ingot casting
Roll.And then after hot rolling, it is possible to implement heat treatment, cold working.
But in the steel of present embodiment, preferably in melting molten steel, the O work amounts in molten steel are analyzed, compare molten O
Measure to adjust Zr additions, carry out " Insol.Zr and Sol.Zr " adjustment.For example, if the molten O amounts in molten steel are 0.0025
Quality %, the then Zr that about 7g can be added by every 100kg molten steel are satisfied by desired contain to obtain Insol.Zr, Sol.Zr
Measure the steel ingot of scope.
In addition, if the time after making Zr additions untill casting is than will generally go back long-timeization, it is likely that oxide
Coarsening can be condensed, the oxide of desired individual number density can not be obtained, therefore the time untill casting preferably sets
Within such as 60 minutes.
Embodiment
Next, illustrated to embodiments of the invention, but the condition in embodiment be can in order to confirm the present invention
Implementation and effect and the condition example used, the present invention are not limited to a condition example.Without departing from the present invention's
Purport and reach the purpose of the present invention, then the present invention can use various conditions.
Using the high-frequency induction furnace for having used the refractory material of magnesium oxide substrate to form in refractory body, with electrolytic iron
Or the low armos iron of Al content is dissolved as mother metal.Then, added in a manner of as normal concentration granular
Carbon, the stipulated time is maintained in the case where depressurizing inactive gas atmosphere when carrying out sensing heating.Wherein, pressure is set at less than 1
Support, more than the 90% of residual gas is set as argon gas, and the retention time is set as about 10 minutes.In addition, molten steel temperature is set as one
As carry out 1600~1650 DEG C of dissolving of steel.
Then, pressure is set as the inactive gas atmosphere from 100 supports to normal pressure or so, carries out necessary alloy
After the adjustment of composition, cast in the mold commonly used in the trial-production of 50~150kg steel via groove.“Insol.Zr、
Sol.Zr " adjustment is by analyzing the O work amount in molten steel, compareing molten O amounts to adjust Zr amounts to carry out.If for example, steel
Molten O amounts in liquid are 0.0025 mass %, then can by every 100kg molten steel add about 7g Zr come obtain Insol.Zr,
Sol.Zr is satisfied by the steel ingot of the scope of desired content.
And then forged and hot rolling and obtain thickness of slab be 30mm steel plate, using the steel plate as test steels material.
First, by dissolving parent phase electrolysis of the steel in nonaqueous solvents (acetylacetone,2,4-pentanedione-methanol solution etc.), pass through
Electroextraction Residue Analysis determines the Insol.Zr and Sol.Zr of the steel.It is 0.2 μm of filter to residue using aperture
(precipitate, field trash) is extracted.After separation, determining the amount of contained Zr in solution by chemical analysis, (Sol.Zr contains
Amount) and residue in contained Zr amount (Insol.Zr contents).
In addition, the number for the oxide containing Zr for being more than 0.5 μm by using SEM Observe and measure equivalent diameter
Density.Now, sightingpiston is set as the steel surface through mirror ultrafinish.In addition, confirm the composition of particle using EDX.Observation
As a result, in example, equivalent diameter is among more than 0.5 μm of oxide containing Zr, more than 90% for comprising Zr with
Ti oxide.
Then, the test film of thermal cycling test is acquired from steel.Impart that to have reproduced heat defeated to the test film
Enter the thermal cycle of the welding (big heat input welding) for 40kJ/mm.As specific thermal cycle conditions, it is heated to from room temperature
After 1400 DEG C, keep 10 seconds at 1400 DEG C, hereafter, by the temperature range of transgranular phase transformation i.e. from 800 DEG C untill 500 DEG C
Temperature range control cooled down in 1.0 DEG C/sec of speed.
Three JIS4 Charpy-type test pieces are respectively acquired in steel after thermal cycle is imparted, are entered at -40 DEG C
Row Charpy-type test, determine and absorb energy (vE-40).Charpy-type test is carried out according to JIS Z 2242.
Table 1, table 2 represent the chemical composition of test steels material.Table 3 respectively represents that equivalent diameter is more than 0.5 μm and contained
The individual number density and Charpy-type test result of Zr oxides.In whole examples, without addition Ca, REM, therefore they
Total content is less than 0.0005%.
Table 1
Table 2
Table 3
As shown in table 2, No.1~30 as example of the present invention are respectively provided with more than average out to 100J excellent tough
Property.On the other hand, No.x1~x18 as comparative example is because chemical composition is departing from scope specified in the present invention, therefore tough
Property deteriorates.No.x13 meets the composition range of the present invention.However, due to make Zr add after to cast untill time than other
Example will be changed for a long time so that oxide aggregation coarsening, the number as the oxide required for ferrite generation site are close
Degree is reduced.As a result, toughness deteriorates.
Industrial applicability
The steel of the present invention especially have excellent toughness in the HAZ of big heat input welding.If using the steel,
It is then efficient to be welded into possibility, the construction cost of welded structure can be reduced by leaps and bounds.And then welding knot can be improved
Security, the reliability of structure thing.Therefore, the contribution of the present invention industrially is extremely notable.
Claims (3)
1. a kind of steel, it is characterised in that chemical composition is included in terms of quality %：
C：0.01~0.20%,
Si：0.02~0.70%,
Mn：0.30~2.50%,
Ti：0.003~0.024%,
B：0.0010~0.0050%,
N：0.0010~0.0090%,
O：0.0010~0.0050%,
Insol.Zr：0.0005~0.0100%,
P：Less than 0.050%,
S：Less than 0.0080%,
Al：Less than 0.005%,
Sol.Zr：Less than 0.0010%,
Ca and REM content adds up to：Less than 0.0005%,
Remainder includes Fe and impurity,
Following formula<1>Represented BasBNFor more than 0.0005, and following formula<2>Represented BFFor more than 0.0005；
With 50/mm2Equivalent diameter above is more than 0.5 μm of oxide containing Zr；
BasBN=(N- (Ti- (O-Insol.Zr × (32/91.224)) × (95.734/48)) × (14/47.867)) ×
(10.811/14) <1>
BF=B-BasBN <2>
Wherein, N, Ti, O and B in formula are N, Ti, O, B contained in the steel content in terms of quality %, Insol.Zr for acid not
The dissolubility Zr content in terms of quality %, Sol.Zr are the acid-solubility Zr content in terms of quality %.
2. steel according to claim 1, it is characterised in that the chemical composition is further contained in terms of quality % to be selected from
Cu：Less than 1.50%, Ni：Less than 3.00%, Cr：Less than 1.00%, Mo：Less than 1.00%, V：Less than 0.100% and Nb：
It is one kind or two or more in less than 0.035%.
3. steel according to claim 1 or 2, it is characterised in that the chemical composition is further contained in terms of quality %
Selected from W：Less than 1.00% and Sn：1 kind in less than 0.50% or 2 kinds.
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| CN115349027A (en) * | 2020-08-31 | 2022-11-15 | 日本制铁株式会社 | Steel sheet and method for producing same |
| CN115362274A (en) * | 2020-08-31 | 2022-11-18 | 日本制铁株式会社 | Steel sheet and method for producing same |
| CN115398018A (en) * | 2020-08-31 | 2022-11-25 | 日本制铁株式会社 | Steel sheet and method for producing same |
| CN115398019A (en) * | 2020-08-31 | 2022-11-25 | 日本制铁株式会社 | Steel sheet and method for producing same |
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| CN116752044A (en) * | 2019-06-27 | 2023-09-15 | 日本制铁株式会社 | Steel material and method for producing same |
| JP7469632B2 (en) | 2020-05-12 | 2024-04-17 | 日本製鉄株式会社 | Steel material and its manufacturing method |
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