Specification
[Docunient Type] Specificatio~i
[Title of the Invention] HOT-DIP GALVANIZED STEEL SHEET AND
MANUFACTURING METHOD THEREOF
[Teclmical Field of the Inventiot~]
[OOOl]
The present invention relates to a hot-dip galvatiized steel slieet \vliicli has
tensile strength (TS) of equal to or greater than 980 MPa and has excellent plating
adlicsiotl and delayed fracture resistatice. The hot-dip galvanized steel sheet
according to the presetit invention is suitable for a structural member, a reinforcing
nie~iiber,a nd a suspensio~tli ~cnibefro r a vehicle. The hot-dip galvanized steel shcct
according to the present invention indicates a hot-dip galvanized steel sheet ant1 a
galvannealed steel sheet. Priority is claiti~edo n Japanese Patent Applicalion No.
201 1-218046, filed on September 30,201 1 atid Japancse Patent Application No. 201 1-
217105, liletl on September 30,201 I, the contents orwliich are incorpot.ated liereill by
reference.
[Related Art]
[0002]
Weight saving of mcnibers of a vehicle such as a cross tneniber or a sidc
nle~i~bacrrc revic\ved to cope with recent trctids regarding rcductio~o~f file1
cot~su~nptioann, d higli-stre~iglhe~~oif~ tiigle steel slieets is in progress fiat11 a vie\vpoint
of securing stret~gtlai nd collision safety even if a material may be thinned, that is,
although steel sheets niay be used,. Alnotig them, for strt~cturalm embers such as a
bumper reinforcement or a center pillar, a steel sheet having tensile strength of 980
MPa class (I~avingte nsile strength ofequal to or greater tllan 980 MPa) is used, and
tlcvclop~nento f s stcel sheet l~n\,inga 11igIicr strcngth is desired in t11c ft~torc.
Ho\\lever, when considering application of the steel sheet having tensile strength of 980
MPa class or greater to a member for a vehicle, delayed fracture resistance is required
in addition to properties such as stretlgtli and workability. The delayed fracture is
ca~~sebyd stress applied to the steel or hydrogen embrittlement, and is a phenomenon
in wIiic11 fracture of a structure occurs due to diffiision and accumolation of hydrogen
in a stress concentration portion of the steel used as tlie structure. As a phenomenon
catised by the delayed fractore, there is, for example, a phenomenon in wl~iclia
mentber such as a pre-stressed coucxete steel \\,ire (PC steel wire) or a bolt used in a
state \vl~creh igh stress is operated, sl~ddenlyfr actures.
[0003]
I11 the related art, a problem of a steel sheet with respect to hydrogen
embrittlement \\.as slight because, (I) although hydrogen enters, the hpdrogen is
released in a short time since the sheet thickness is small, and (2) a stccl sheet having
tensile strength of equal to or greater than 900 MPa is s~~bstatitialnlyo t used to
prioritize \\forkability Ho\vevel; as rapid al~plicationo f a Ilig11-strengtli steel sheet is
reqoiretl, it is required to develop a high-strength steel sheet having excellent hydrogen
embrittlcment resistance.
[0004]
It is foin~ttlh at tlie delapetl fracturc has a close relationship \\,it11 hydmgcn
which enters the steel Porn an environment. As tlie hydrogen \\,Iiich enters the steel
fiom an e~lvironnlentt,l iere are various kinds of hydrogen such as hydrogen contained
in all atmospliere or llytlrogeri generated under a corrosive environment. I n all cases,
when the i~ydrogene nters a steel, this may cause the delayed fracture. Accordingly,
regarding a usage environment of tlie steel, it is preferable to nse the steel sheet in an
environlncnt \\.it11 no liydro~en. Ho\~evcrw. hcn consitlcring tlic application of the
steel to a structure or a vehicle, since the steel is used outdoors, the entering of tlie
hydrogen is not avoidable.
[OOOS]
As the stress acting on thc steel used as the structure, there is stress applied to
tlie structure, or residual stress which is some of tlie stress generated \vIien the structure
is fomied remaini~igi nside of the steel. In particular, io a struch~resu ch as tlie steel
sheet for a vehicle which is used as a member after being fornied, the residual stress is
a significant proble~iic, oilipal-ed to a plate or bar steel which is used as it is
substantially \vitlioc~t leforination with respect to a product such as a bolt or a plate.
Accordingly, \\4ieli for~iiitigtl ie steel slieet having tlie problecii of delayed fracture, it is
desirable to use a method of for~ninga steel sheel such that no resitlual stress remains
therein.
[0006]
For esample, Patent Doci~mcnt I discloses a hot press forniing method of a
~iietasll ieet, including once heating a steel slieet at a liigli temperature to perform
processing, and then pcrfomiing qoe~lcliirigo f the steel slieet using a die to realize high
strengthening. In tllis method, a steel is processed at a high temperature.
Accorditigly, dislocation introduced at thc time of processing \\thicli causes the residual
stress is rccovercd, or transforniation occilrs after tlic processing to reduce tlie residual
stress. As a result, substantially no residual stress remains. Accortlingl>: as
described above. liot processilig is performed, tlie steel sheet is then strengthened \vitIi
quenching, ant1 therefore the tlelaycd frachlre resistance is inlproved.
Howcver, in the technology of Patent Docu~iie~1it, it is necessary to heat the
steel sheet to be processed by heat treatnient, and productivity is degraded. 111
adtlitio~is,i ncc it~isn ecessary to illstall a llcatin~f l~r~iaciet ,i s not ccor~o~iiical.
[0007]
111 addition, in a niechanical process sucli as cutting or punching, since the
residual stress is on a cut surface, this may cause delayed fracture. Accordingly,
when processiilg the high-strei~gths teel sheet having tcnsile stsengtli of equal to or
greater than 980 MPa class, tlie generation of residual stress is avoided by 11si1lga
nietliod of nsuig a laser for cutting in which a direct mechanical process is not
perfor~nled. Ho\vevel; laser cutting is expensive, compared to shear cutting or
puncliitig.
[OOOS]
Regarding tlic problems, in fields of steel bars or rod steel, and a steel plate, a
steel capable of avoitling tlelayed fracture has been developed by improving hydrogen
cmbrittlement resistance. For example, Non-Patent Doct~nient 1 discloses a liiglistrength
bolt obtained by perforniing qucnclling of a steel wit11 an austenite singlephase
at a liigli temperatore to sct the steel to have a martensite sin_gle-phrase str~~cture,
and then pcrloruiiing a tenlpering treatmetlt, to coherently precipitate a fine precipitate
of an atltlitive element snch as Cr, Mo, or V slnowing resistance to tennper softcnicng
into tlic martensite, and to improve hpdroge~ei mbrittlcmcnt resistance of tlie steel. hi
this higli-strcngth bolt, tile liydrogen which enters thc stcel is suppressed diff~~sinatgid
concentrating at a pa~\tv lnicIi is a delaycd rracture origin at \\4iicli stress is concentrated,
using a l)lnenomenon \\iliich the llydrogen that enters tlie steel is t~.al)peda round VC or
the like, \vIiich cohere~itlyp recipitate into the martensite. 11 steel sheet having high
strength and excellent delayed fiact~~rrees istance has been developetl in tlie related art,
using sucli a mechanism.
[0009]
Tlic i~npl-o\.omcnot f tlic tlcla!.ctl fsactose rcsistancc using a tmp site of
liydroge~si uch as VC or tlie like is realized by coherent precipitation of these
precipitates into tlie niartensite structure. Accordingly, it is essential to colierelitlp
precipitate such precipitates into tlie structure. Ho\vever, tlie precipitation of such
precipitates results in a problem in nianufacturability since it is tiecessaly to perforni a
precipitation heat treatment for several hours or longer, That is, in the steel sheet
manufactured using general nianufactoring eqoipnient of the steel sheet sucli as
continuous annealing equipment or continuous galvanizing equipment, since
microstructure colitrol is perfoniied for a short tinie, such as al~prosimatelys everal
tens of minutes, it is diflic~~tol to btain an effect of improving tlie delayed frachlre
rcsistance \vith tlie prccipitates.
[OOI 01
In addition, in a case of using the precipitates precipitated in a Iiot rolling
process, altliough the precipitatcs arc precipitated in tlie Iiot rolling process, the steel
sheet is processetl at tlie tinie of cold rolling after that, and ~ecrpstallization is
tlr\,cloped at tlie time of continuous annealing, and accordingly, an orientation
rclationsliip bett\recn tlic prccipitates anct tlie ferrite a~ittlh e ~iiartensite\v liicIi are a
parent phase is lost. That is, the prccipitates torti out not to bc coherent precipitatcs.
As a result. tlie delayed fracture resistance ofthe obtained stcel sheet is significantly
reduced.
[OOI I ]
111 general; the steel slieet structure of the high-strength steel sheet in \vliich
dclayed fracture may occur is a structt~reli aving martensite as a main constituent.
Since a teniperaturc at vhich the martensitc structure is fornied is a low temperature,
tlie prccil~itatesto be tlie trap sites of hydrogen s~~calsl V C and the like cannot be
1)rccipitatcd at a tclill)erattcre I.ansc ill \\liicli tlic martcnsite structure is fornietl That
is, in a case \\rlte~-teh e improvement of the delayed fracture resistance by the hytlrogen
trap of the coherent precipitates st~cha s VC or the like is intended in the steel sheet,
after forn~inga structure of the steel once with the continuous ant~ealinge quipment or
continuous galvanizing equipment, it is necessa~yto additionally perfor111 thc heat
treatment and to precipitate the precipitates, and therefore ~ua~ufacturincgos ts are
significantly increased. In addition, if the heat treatment is additionally perronned in
the structure itrcluding martensite as a olain constituent, the struchlre is softened and
the strength is decreascd. Accordinglj: it is difficult to use the cohcrcnt precipitates
suclt as VC in ostler to improve the delayed fracture resistance with respect to the Iligbstrength
steel sheet. Fulther, the stecl disclosed in Non-Patent Docllnlent 1 has a C
content of equal to or Sreater than 0.4% and contains a large nuntber of alloy elements,
and accordinglp \vorkabiljty or \\,eldability thereof is not sulficient for a steel sheet.
[OOI 21
Patent Document 2 discloses a steel plate in \vhicll I~ydrogen tlefects are
retll~cetl by ositles having Ti and htIg as iliain constituet~ts. Ho\vevel; in the disclosed
stcel plate, the l~ydrogcnd efccts gcneratetl by hydrogen trapped in the stecl at the tinic
of manufacturing are ~t~crcrlepd uced, ant1 Iiydrogen embrittlement resistance (delayed
fracture resistance) is not considered at all. 111 adtlition, compatibility of 11igh
formability and hpdrogen cmbrittlement rcsistancc (delayed fracture resistance)
requiretl for the steel sheet is not considered at all.
[00 131
Regarding the hydrogen cmbriltle~ne~oift the steel sheet: for example,
promotion of hydrogen etnbrittlement caused by strain induced transforn~ationo f a
residt~ala ustenite amount is reported in Non-Patent Document 2. In this docun~enitt
is consitlcrctl to fornt thcstccl shcet, but this docutnet~dt iscloses a regulation of-the
residual at~stenitea n~ounfto r not degrading the hydrogen el~ibrittletiie~riets istance.
That is, this relates to a high-strength steel sheet having a specified structure and it
cannot be said that this is a fi~ndamentaml easure for in~provemento f l~ydrogen
cmbrittle~nentr esistance.
[Prior Art Documeiit]
[Patent Documeiit]
[OO 141
[Patent Document 11 Japanese Unexan~ined Patent Application, First
Publication No. 2002-18531
[Patent Document 21 Japanese Unesamincd Patent Application, First
Publication No. 111 1-293383
[Non-Patent Document]
[0015]
[Non-Patent Doconlent I ] New developnients in delayed fracture clarification,
'flie iron and Steel Institute of Japan, ptrblished January 1997
[Non-Patent Documcnt 23 CAMP-ISIJ, vol. 5, No. 6, pages 1839-1842,
Yamazaki et al., October 1992, publisl~edb y Tlic Iron and Steel institute of Japan
[Non-Patent Doci~ii~c3n1t Materia, Japan Institute of Metals Bulletin,
Volunie 44. No. 3 (2005) p 254-256
[Disclosure of tlie Invention]
[Problenis to be Solvetl by tlie Invention]
[00 161
The present invention lias been made \\,bile taking tlie aforementioned
problems into consitleration. That is, all olject of the invention is to provide a hot-dip
galvanizctl slccl sllcet \\l~icllii as a tensilc strciigrli (TS) of equal to or grcatcr than 980
MPa and has excellent plating adhesion and delayed fracture resistance, and a
manufacturing i~~etliothde reof. The hot-dip galvanized steel sheet also has
for~iiability(e loligation, bendability, hole expandability) pa~ticularlys uitable for a
stroctural member, a reinforcing member, ant1 a suspension ~iietiiberf or a vehicle.
In a case of applying the steel sheet to the menibers described above, TS x EL
is desirably equal to or illore than 10000 MPa.% and TS x h is desirably equal to or
more tthal~2 0000 MPa.%.
In addition, in a case of applying the stcel sheet to a member in whicli
elongatio~is particularly required, TS x EL is desirably equal to or inore tlian 14000
MPa.%, is more desirably equal to of niore than 15000 MPa,%, and is even more
desirably equal to or nlore than I6000 MPa,%.
Furtliel; in a case of the steel sheet applied to a member such as a bumper
rcinforce~ncnti ll \trl~icthh e bendability is pa~lict~larrleyq uired, TS x 1, correlated witll
the bentlability is desirably equal to or more tlia~3~00 00 MPa.%. TS x Ibisn iore
desirably equal to or inore than 40000 kIPa.% and even more.desirably equal to or
morc than 50000 MPa.%.
[A~lcansfo r Solving the Problem]
LOO 171
As a result of investigation, the present inventors have fo~~nthdat delayed
fracture resistance can be ilnproved by perrorming plating as \\'ill be described later on
a surface of a steel sheet, as a mcthotl of i~nprovingth e delayed fracture resistance
without affecting a inaterial of a steel. specific all^; the inventors liave found that, by
dispersing oxides containing one or Inore selected front Si, Mn, and A1 in a plated layer,
hydrogen entering the steel sheet from an environment is trapped by the oxides in the
plated layer. and tliffiisiou of the hydropen to a stress concentration portion and .
delayed fracture due thereto can be delayed.
[0018]
(1) Allot-dip galvanized steel sheet according to one aspect of the present
iiivetltioli includes: a steel sheet; and a plated layer on a surface of tlie steel sheet. 111
additio~it, he steel sheet contains, by mass%, C: equal to or more than 0.05% and less
than 0.40%, Si: 0.5% to 3.0%, MIX: 1.5% to 3.0%, 0: lililited to 0.006% or less, P:
limited to 0.04% or less, S: limited to 0.01% or less, Al: limited to 2.0% or less, N:
liniited to 0.01% or less, and the re~i~ai~i~ncdleudr iog Fe and unavoidable impurities, a
~iiicrostructt~roef the steel sheet contains, by voluliie fraction, equal to or more than
20% and equal to or less than 99% in total of one or t\vo of a marte~isitea nd a bainite,
a residual structure iincluding a ferrite, and one or t\vo of a residual austenite of less
than 8% by volome fraction, and a pearlite of equal to or less than 10% by volume
fiactiol~a, nt1 a tensile strc~igtho f the stccl sl~eeits equal to or grcater than 980 MPa.
The plated layer is a hot-clip galval~izedl aper \\~hicIic ontains oxides contaitiing one or
two or Illore of Si, Mn, and Al, contains equal to or less than 15 mass% of Fe, and tlie
rcmaintler including Zn, Al, and ~rnavoidablcit i~purities:a nd when a cross section
including the steel sheet and the hot-dip galvanized layer is seen in a sheet thickness
direction, a projectcd area ratio \\'hicl~is au area ratio obtained by dividing a length of
the ositlcs projected to an iliterface bet\vecn the hot-dip galvanized layer and tlie steel
slieet by a length of the interface between tlie hot-dip galvanized layer and the steel
sheet, is equal to or inore than 10% ~IIICeI qual to or less than 90%.
[00 191
(2) A hot-dip galvatiized steel sheet according to aliotller aspect of the
present invention inclutles: a steel sheet; and a plated layer on a surface of tlie steel
shect. tlic stccl~shccct ontains. hy mass%. C: eqnal to or ~iioreth au 0.05% a~idL ess than
0.40%, Si: 0.5% to 3.0%, Mn: 1.5% to 3.0%, 0: litiiited to 0.006% or less, P: limited to
0.04% or less, S: limited to 0.01% or less, Al: litl~itedto 2.0% or less, N: lin~itedt o
0.01% or less, and tlie retnainder iticluding Fe and u~~avoidabilme purities, a
microstrocture of the steel sheet contains, by volu~ilef iaction, equal to or more than
20% aiid equal to or less thau 99% in total of one or t~voo f a martensite and a bainite,
a residual structure iincloditig a ferrite, and one or t\vo ofa residual a~isteniteo f less
tlian 8% by volume fraction, and a pearlite of equal to or less tlian 10% by volu~iie
fraction, and a te~lsiles trength of the steel slieet is equal to or greater than 980 MPa.
The plated layer is a galva~~ticalelady er w\~liicIic o~~taio~xiidse s including one or two or
Illore of Si, Mn, and Al, contains equal to or more than 7 mass% and equal to or less
than 15 mass% of Fe, and (lie re~l~ailitlienrc luding Zn, Al, ancl t~tiavoitlablei ~lipt~rities,
and \\,he11 a cross section including the steel slieet and tlie galvatlneaied layer is seen io
a slicet tliick~iessd irection, a j)ro.jected area ratio \\~liicli s all area ratio obtained by
tlividing a lengtli of the oxides projected to an interface between the galvannealed layer
and tlie steel slieet by a length of the interface between the galva~inealedla yer ant1 the
steel shcct, is equal to or 111ore than 10% and equal to or less that1 90%.
lorno]
(3) 111 the hot-dip galvanized steel sheet according to (1) or (2), the
~nicrostructure may contain, by volume fiaction, 40% to 80% of ferrite.
1002 I]
(4) In tile hot-dip gal\ratiized steel slieet according to (I) or (2), tlie
microstructu~-em ay conlaill, by volume fiaction, more than 60% of one or hvo of
martensite and bainite.
roo221
( 5 ) 111 the hot-clip ~alvanizetsl teel shcct accortliny to ail). one of (I) to (4).
tlie steel sheet may fiuther contain, by mass%, one or two or Illore of Cr: 0.05% to
1.0%, Mo: 0.01% to 1.0%, Ni: 0.05% to 1.0%, Cu: 0.05% to 1.0%, Nb: 0.005% to
0.3%, Ti: 0.005% to 0.3%, V: 0.005% to 0.5%, B: 0.0001% to 0.01%, Ca: 0.0005% to
0.04%, Mg: 0.0005% to 0.04%, and REM: 0.0005% to 0.04%.
[0023]
(6) A manufacturing ~uethodo f a liot-dip galvanized steel slieet according~to
one aspect of the present invention includes: casting a molten steel incloding a
chemical components according to (I) to obtain a steel; heating tlie steel to a first
teinperature range of 1100°C to lo\\rer tllan 1300°C, directly or afier coolillg once;
completing a hot rolling of tlie steel at a temperatt~ree qual to or l~iglicrth an an Ar3
transSormation point; coiling the steel in a secontl te~nperatrlrera nge of 300°C to
700°C; pickling the steel; perlornling coltl rolling of the steel with a cumulative rolling
rcd~tctiono f 40% to SO% using a cold rolling mill including a \\cork roll having a roll
diameter or200 nlm to 1400 nim; retaining tlie steel in a third tetnperattlre range of
550°C to 750°C fbr 20 seconds to 2000 seconds tluring heating the steel to an annealing
temperature, \\-lien the steel passcs through a continuotts galvanizing line; maintaining
tlie steel in a fourth teaipcraturc range of75O0C to 900°C for 10 scconds to 1000
secontls, in an NZa lmospliere in which an Hz coiiccntration is cq~~tao lo r less than 20%
and a dew point is equal to or liiglier than 20eC, \vllile pcrforniing an annealing;
perSorii~inga first cooling of cooling tlie steel to a fiRh teniperatore range of 500°C to
750°C at an aver;lgc cooling rate of I "Clsec to 200 'C/scc; perforniing second cooling
of cooling tlie stccl to a sixth teolperattlre range between a temperature \~Iiichis lo\ver
than :I liot (lip galvanizing bath te~nperatureb y 40 "C and a temperah~re\v hicli is higher
than tlie hot dip galvanizing bath temperature by 50°C, at an average cooling rate
- \\4iicli is I "Clscc to 200 "Clsec and isfaster than the a\;erasc cooliris rate oftl~cfi rst
cooling; galvanizing the steel by immersing the steel in a hot dip galvaniziitg bath
~vliichfl ows at a flow velocity of 10 mlmin to 50 mlmin after setting a plating bath
immersion sheet temperatore which is a tenlperat~~\rvel ~enim mersing the steel in the
hot dip galvanizing bath, as the sixth temperature range; and cooling the steel to a
temperature equal to or lomer than 40°C.
[0024]
(7) A ~ttanufach~rinngte thod of a hot-dip galvanized steel sheet according to
another aspect of the present invention includes: casting a moltcn steel including a
chenlical coi~lpo~ietiatsc cording to (2) to ~llanufactures teel; hcating the steel to a
scvcntli temperature range of 1100°C to lo\ver than 130O0C, directly or after cooling
once; completing a hot rolling of the steel at a temperature equal to or higher than an
Ar3 transforntation point; coiling the stcel in an eighth temperature range of 300°C to
700°C; pickling the steel; perforn~ingc old rolling of thc steel with a cunitllative rolling
reduction of 40% to 80% using a cold rolling mill inclutling a \vorIi lull having a roll
diameter of 200 mm to 1400 mm; retaining the steel in a ninth temperatare range of
550°C to 750°C for 20 secontls to 2000 seconds during heating thc steel to an aruiealing
temperature, \\.hen the steel passcs through a continuous galvanizing line; ntaintaining
the stcel in a tenth tcniperature range of 750°C to 900°C for 10 scconds to 1000
seconds, in an 1\'2 atmosphere in \\~hicha n Hz concentration is equal to or less than 20%
ant1 a dew point is equal to or liigller than 20°C. ivhile performing an annealing:
performing a third cooling of cooling the steel to an eleventh temperature range of
500°C to 750°C at all average cooling rate of equal to or more t11an I "Clsec and 200
"C/sec; perfomling a fourth cooling of cooling tile steel to a t\velfth tentyerature range
of 500°C to 25"C, at an average cooling rate which is 1 "Clsec to 200 "Clsec and is
. . faster Illan thc avcrasc coolin: rate of the third~coolinh~c:a ting tltc steel again ton . .
tliirteentli temperature range of 350°C to 500°C, in a case where a cooling stop
temperature of the fourth cooling is lo\ver tlian 350°C; retaining the steel in tlie
tliisteeiitli teiiiperature range; galvanizing the steel by i~nniersingth e steel in a liot dip
galvanizing bath \\~liiclif lows at a flow vclocity of 10 i~dli~tion 5 0 ~id~naifnte r setting
a plating bath immersion sheet te~nperaturew liicli is a teniperature when in~niersing
tlie steel in the hot dip galvanizing bath, as a fourteenth temperature range befiveen a
temperature \\~hiclis Ionrert han a liot dip galvanizing bath teniperah~reb y 40°C and a
teniperatorc \\,hich is higher than tlie hot dip galvanizing bath temperature by 50°C;
perforniing an alloying treatnictit to tlie steel at a fiftccntli temperature range of equal
to or lower than 600°C; and cooling the steel to a teniperahirc equal to or lo\trer tlian
40°C.
[0025]
(8) In the oianufacturing method of a hot-dip galvanized stccl slicct
according to (6) or (7): the annealing may be performed at a temperature lo\ver tlian
840°C. ~.
[0026]
(9) In the nianufacturing method of a hot-dip galvanized steel sheet
according to (6)o r (7), the an~lcaliiigm ag perfortiled at a temperature equal to or
higher tlian 840°C.
100271
(1 0) In tl~cn ianufacturing ~iietliotlo f a hot-dip galvatiized steel sheet
according to any one of (6) to (10). tlie n~olteti steel may further contain, by mass%,
one or t\vo or Illore of Cr: 0.05% to 1.0%4h. 4o: 0.01% to 1.0%, Ni: 0.05% to 1.0%: Cu:
0.05% to 1.0%, Nb: 0.005% to 0.3%:fi: 0.005% to 0.3%, V: 0.005% to 0.5%, B:
0.0001% to 0.0l%..Ca: 0.0005% to 0.04%. h.1~0: .0005% to 0.011%. and REhtI:
0.0005% to 0.04%.
[Effects of tlie Inventio~~]
[002S]
According to thc present invention, a hot-dip galvanized stecl sheet \vliich is
suitable for a stroch~raml ember, a reinforcing member, and a suspension nie~l~bfeorr a
vehicle, has a tensile strength of equal to or greater than 980 MPa, and has excellent
plating adhesion and delayed fracture resistance, can be provided at lo\\, cost.
[Brief Description of the Drawiiigs]
[0029]
FIG. 1 is a photograph obtained by observing a cross section of a hot-(lip
galvanized steel sheet according to one enibodiment of tlie present invention \\,hicIi
was processetl using an FIB processing device, with an FE-TEM at a magt~ificationo f
50,000-fold.
FIG. 2 is a tliagram schematically sl~o\vinga calculation inetl~otol f a projected
area ratio of oxitles ill a plated layer of a hot-dip galvanized stecl slieet of the
etnbodio~ent.
FIG. 3A is a flowchart sIio\ving a nlanufacturing method of a hot-dip
galvanized steel sl~ccat ccording to one en~bodin~conft t he present invention.
FIG. 3B is a llo\\,cllart (scquent to FIG. 3A) slio\ving a ~i~anofacturinng~ ethod
of a hot-clip gal\~a~iizesdte el sheet according to one embodi~nenot f tlie present
invention.
[Enibodinients of the Invention]
[0030]
The present inventors have studied to solve tlie aforetiientioned proble~ns.
i\s a result. tlic invcritors liavc fu~~nthdat . afier performins colt1 rolling of stccl \\'it11
cumolative rolli~lgre duction of equal to or greater than 40% using a cold rolling mill
includi~~a g\\ ,ark mll having a roll diameter of equal to or smaller than 1400 111111, by
retaining the See1 at a temperaturerange of 550°C to 750°C for 20 seconds or longer
during heating tlie steel at the time of annealing, oxides containing one or nlorc of Si,
Mn, and Al independently or in coliibination with each other, cm be fornied on a steel
sheet surface layer. In addition, the present inventors have found that, after forn~ing
the oxides on tlie steel sheet surface layel; by immersing tlie steel sheet in a hot clip
galvanizing bath whicli flows at a flow velocity of 10 nl/min to 50 t~~lniiann,d
perfor~ninga hot dip galvanizing treatment, or hot dip galvanizing treatment and
alloying treatment, tlie oxitles can be dispersed in a plated layer so that a pro.jccted area
ratio of the oxides is equal to or niore than 10% and excellent plating adhesion is also
obtained. Fortbet; tlie present inventors have foi~ntlth at by appropriately dispersing
the oxides in the plated layer, the oxides can be usetl as a trap site and tlelayed fracture
resistance is improved.
[003 I]
Hcreinafrer, the enibodime~iwt ill be described in detail.
A hot-dip galvanized steel sheet according to the cmbodimcnt includes a steel
sheet, a t ~al p lated layer on a surface of the stecl sheet. The plated steel sheet ma)^
ft~rtheirn clude various coveririg layers such as an organic layer or an inorganic layer
on a surface of the plated layer. Wl~eress ucll a covering layer is not fornied on the
platetl stecl sheet, tlie plated stecl slieet includes tlie steel slieet, and tlie platetl layet.on
the surface of tlie steel slieet.
First, tlie plated layer tlisposed on the steel sheet \\,ill be described. This
platetl layer includes a hot-dip galvanized layer and a galvannealed layer.
1.11p~li ~tctll ayer is pro\ritlctl( xi tlic surfacc of (lie stecl sl~ccat nt1 contains
oxides co~iteiningo ne or two or liiore of Si, Mn, and A1 independently or in
conibination with each other In tlie embodiment, it is ~iiositm portant to disperse tlie
oxides containing one or t\vo or Illore of Si, Mn, and A1 in the plated layer, in tlie
platetl layer. Particularlp, tlie effect thereof is sigtiificantly obtained by dispersing tlie
oxides in the plated layer so that a projected area ratio when observing the steel sheet
in a surface direction ofthe steel slieet, that is, an area ratio obtained by dividing the
letlgtli of the oxides projected to an interface betureen the plated layer and the steel
slieet by tlie leugth of an interface bet\\een the plated layer and the stecl sheet when a
cross section iaclutling the steel slieet and the plated layer is seen ill a sheet thickness
direction, is equal to or tiiore than 10%. This projected area ratio can also be rcfcrrcd
to as apparent coverage ofthe oxides \vhich make a sliado\\, on tlie surface ofthe steel
plate, \vl~etl~ie steel sheet is seen fro111a bove tlie surface of the hot-dip galva~iized
steel sl~eet. ~\lthough tlie specific tncchanism is iiot cleat; since the oxides have
various defectts. the oxides in the platctl layer trap Iiydrogea (for example, hydrogen
generated by a corrosion reactio~io r hydrogen in the atmosphere) \vl~iclie nters from
thc stecl sheet surface autl delay hydrogen fro111 ctitcri~lgto the inside of the stecl sheet,
and delayed fractore resistance may thereby be improved. Since an a~~to~iiobstielel
slicet is used in alternating wet and d ~eyn vironnicnt, that is, in a \vet-dry etwiron~i~e~it,
Ilydrogen \vhicli is olicc trapped by the oxides existing on the steel slieet surface layer
in the \vet envitan~nentis discharged to an enviro~i~neinnt tlie dry e~lvironme~it.
Accortli~lgl~d:i spersing tlie oxides in the plated layer as describetl above may liave a
greater effect on Lhe tlelayetl fracture resistance ill an actual use environ~nenot f a
vehicle.
100321
Tlie slinl)c ofthc oxides dcscribcd nboveniny be ally of a fil111, g.;lnulnl; or
string shape, and tlie effect of the embodiment can be obtained as long as the prqjected
area ratio is in the range described above. Howevel; the filnl-shaped oxides tend to
have a greater prqjected area ratio with respect to a volunle fraction, and thos, the
shape of the oxides is desirably fornied in the film shape so that the prqjected area ratio
is in the range of the embodiment by the treatment in a short time.
[0033]
The oxitles to be dispersed in the plated layer are set to oxides of Si, Mn, or A!,
because the oxidcs thereof have a high nielting point coniparcd to that of zinc, such
that the oxides (for example, having a filln shape) are easily dispersed in the plated
layer. Particularly, in the case of using the film-shal~etol xides, it is possible to nlorc
easily achieve tlie pro.jected area ratio of equal to or more than 10%. In addition, if
the oxitles are dispersed in a regioti of the plated layer \vithin 5 pin fro111 an interrace
between tllc steel sheet and the plated layel; a more significant hydroget1 trapping
effect is obtained. After forming the oxides on the steel sheet st~rfacela yer, by
performing the hot dip galvanizing treatment, or the hot dip galvanizing treatment and
tllc alloying treatnlcnt, the oxidcs may be tlispersed inside of the plated layer as slio\~,n
in FIG 1. The oxides are oscd on the steel sllcet surface, because the characteristic of
thc oxides, such as a size or ~u~nibdcern sit): is casily controlled and it is advantageous
for generating oxidcs, corresponding to the projected area ratio of equal to or inorc
than 10%.
Herein, as the oxides containing one or two or more of Sil Mn, and Al
independently or in combination \vith each other, SiOz, MnO, A1203, i\,ln2SiO,, and the
like are used, and Si02 ant1 MnlSiO, are preferable.
In addition thereto, the same effect is obtained even in the case of co~ltaining
oxide-(Cr20;; \\hicll contains CI: . . .~ ~ . .
[0034]
011 the otl~ehr and, it is difficult to plate ~l~oltzein~cl c o~itaitli~oigx ides onto
the steel sheet. For example, although tlie oxides are dispersed in the molten zinc, the
oxides for111 clusters due to Van der Waals' forces, and becotlie large oxides having a
size of 1 p n to several mm. The large oxides niay cause non-plating or defects.
Therefore, it is not preferable to disperse the oxides in molten zinc. In addition,
nor~iiallyi,n order to improve the plating adhesion, it is general to reniove the oxide on
the surface of the steel sheet before plating to obtain a nom~aslu rface, and the oxides
arc not for~licdi ntentionally 011 the surface of the steel sheet before the plating.
Oxides of 2.11 or A1 exist in the ~tioltez~iln c as i~tlavoidablco xides. It is
desirable to reniove the oxides as much as possible, or to control a reaction with the
steel sheet, but the oxides may i~ievitably( for example, equal to or less t11a1i 5%) exist
ill tlic plated la)'el: Ho\vever, since tlic plated layer is easily oxidized, there is a case
that oxide ofZn exists on tlie surface of the plated lapel: but this is not counted as tlie
osidcs in the plated layer. -
[0035]
The oxides to be dispersed in tlie plated layer in tlie embodiment are oxides
containing Si, Mn, or Alindependently or in co~ubinationw ith each other. The
oxides call be co~itrolledb y addition of Si, Mn, orN to the stccl sllcet and by
controlling the atmospllere at the ti~iieo f annealing. Meanwllile, wit11 the addition of
elements socli as Ni, Co, and the like mhic11 are l~artllyo sitlized, since, not only the
oxidation of the additive elements, but oxidation of Fe is causetl, it is tiifticult to secure
the prqjected area ratio of the oxides and plating properties. Accordingl~: in the
embodiment, by adding Si, Mn, or A1 as eie~~~e\\nrltlsic l~a re inore easily oxidized that1
Fc to tllc stccl SIICCi~l~. lds ctti~isth e a1111eali1c1o~n tiitions a~ldth e fi~roncc.attnos~~l~erc -
to predetelltiiiied conditions, oxides co~itaini~tthge ele~nentsin del~endentlyo r in
contbii~ationw ith each other, are foniied on the steel slieet surface.
[0036]
It is necessary that the oxides is present so that the projccted arcaratio is
equal to or liiore than 10% as described above \vitlt respect to tlie steel sheet surface.
In the embodiment, since tlie oxides are used to trap hydrogen entering ftoioat the steel
sheet surface, the oxides desirably exist in the plated layer and widely cover the
interface bet\\reen the steel slieet and tlie plated layer. The effect thereof is obtained
by setting the projected area ratio to be equal to or tnorc than 10%. The prqjected
area ratio is tlesirably cqual to or more than 15% and ~iiorcd esirably equal to or more
than 20%. 011 the other hand, if tlie proiected area ratio exceeds 9O%, the alloyi~tg
reaction becomes extretnely slow, and hi@i-temperat~~arlel oyi~tgis necessary to set
Fe% it1 the platcd layer to be in a predctcr~ninedr ange. In this case, since auste~titc
tra~tsforms illto pearlite, a predeler~iiined material property cannot be obtained. The
projected area ratio by tlie oxides cat1 be easily measored by observing tlie cross
section of tl~cho t-(lip galva~lizcds teel sheet. In (letail: as slio\\~nit1 FIG 2, tlie
projected arca ratio can be evaluated based on a ratio of an oxide length in a parallel
direction, wit11 respcct to tlie interface between the platcd layer and the steel slieet.
For esautplc, as shown in FIG 2, in a case \vhcre the osidcs are vertically projected
wit11 respect to the interface (interface approxintated as a straight line) between the
plated layer and the steel slieet, a projected area ratio A (%) can be evaluated based 011
a ratio of tlie projectio~il e~igtli( for esa~itplel,e ngths (L-11-12-13)i ll FIG. 1) of tlie
projected oxides (sliado\\.) \\,it11 respect to the length (for example, le~igtlLi in FIG. 2)
of the interface betwee11 the plated layer and the steel sheet. In tlie enibodiment.
~~icnsurunis~ p~ctrfto riiied at 5 .\risual ficlds at a mag~iificatiu~ofi 10.000-ti~nesa, nt1 tlic - ~ ...
average value thereof is tlefined as the prqjected area ratio. Since the ob.iect of the
oxide dispersion of the embodiment is to trap the liyclrogen entering thereto, with the
oxides in tlie plated layer, the oxides may be overlapped wit11 each other.
[0037]
The con~positioi~die lltificatiot~a nd evaluation of the oxides can be perfomled
by perforn~ingo bservation of the ~liicrostr~~cwti~th~ trhee cross section of the hot-dip
galvanized steel sheet. For example, there is a niethod of processing the cross section
of the steel sheet into thin flakes so as to contai~til ic plated layer, using a focus ion
beam (FIB) processing device, atid then perfonlling observatiol~\\ ,it11 field e~nission
transn~issione lectron n~icroscopy(F E-TEM) and composition analysis \\it11 energy
dispersive X-ray spectrometry (EDX). 111 the embodinient, after manufacturing
san~plesfo r observation with the FIR processing device, the oxides \\,ere observetl with
the FE-'I'EM at a magnification of 50.000-fold. In addition, by analyzing the oxides
\vitll the EDX, the oxides were identified.
[003S]
The plated layer is a hot-dip galvanized layer or a galvannealed layer
containing equal to or less than 15 mass% of Fe. If the amount of Fe exceeds 15
mass%, adhesiol~o fthe plated layer itself is deteriorated and tlie plated layer
fractures, is removcd, and is attached fo a die during processing, and this causcs
defects at the time of the formation. In a case \vllere spot \veldability or a coating
property is desired, it is desirable to improve the properties of the plated layer it1 the
alloying treatment. In detail, after i~nmersingth e plated layer in the hot dip
galvanizing batli, by performing the alloyitig treatment, Fe is introtluced into the plated
layet\ ant1 it is possible to obtain a l~igli-strength hot-dip galvanized steel sheet
inclutling the ~al\~ant~calIac!.icIr having an cxccllcnt coating property or spot
weltlabilitp. However, in a case of perfoin~i~th~eg a lloyii~gtr eatment, if the alliouilt
of Fe after the allopi~igt reatti~eti~s tl ess than 7 inass%, the spot weldability is not
sufticiei~t. Therefore, wvheu performing the alloyi~igtr eatment, that is, when tlie
plated layer is the galvannealed layer, the range of tlie amoutit of Fe in the plated layer
is desirably 7 mass% to 15 inass%.
The cbei~iicalc oiiiposition of the plated layer desirably contains, by mass%,
equal to or less tlian 15% of Fe, and a re~iiaindero f 80% to 100% of Zn, equal to or
less tlian 2% ofAl, and ut~avoidablei mpurities. As the o~~avoidabilmc1 )orities in tlie
plated layer, there are tlilavoidable impurities ~liixcdth erein \\~henm anufacturiug (for
example, l~~iavoidabilme purities in tlie plating bath or cl~emicaell e111cnts coming fro111
the clie~iiicalc otilpositiori of the steel sheet (esclutling Fe, Al, and ZII), or clie~nical
ele~lle~iftrso m pre-plating pcrfomied if necessary (Ni, Cu, and Co)). The plated layer
may co~itaic~li~ emicacl lc~iict~stusc h as Fc, Al, Mg, MI),S i, Cr, Ni, Cn, and the likc, in
addition Lo Zn.
[0039j
A plating weight (amount of plated layer attached per unit area) is not
particularly limited, but is desirably equal to or grcater than 5 g/111~b y one side surface
weight fro111 a vicwpoint of corrosion resistance. In addition, the plating \\,eight is
desirably equal to or smaller than 100 g/m2 by oilc side surface \vcig,ht froiii a
viewpoint of securing the 1)lati1ig adhesion.
In addition, in order to furlher improve tlie plating adhesion. plating mith Ni,
Cn, Co, and Fe. independently or in combination \\:itti each other map be pc~foomied on
the steel sheet before an~ieali~ig.
[OOlrO]
M!licn the plated layer is rlic galvan~~caleltaly er. the cffcctivc A1 concentration
in tlie plating bath is desirably co~itrolledto be in a range of 0.05 mass% to 0.500
mass% in order to co~ltrotlh e properties of tlie plated layer. llerein, the effective N
co~lcentratiolin the plating bath is a value obtained by subtracting tlie Fe
concentration in the plating bath f~0111th e A1 conce~itratioi~nl the plating bath.
In a case where the effective Al concentration is lo\ver than 0.05 mass%,
exceile~a~ptp earance may not be obtained due to significant dross generation. On the
other hand, in a case where tlie effective AI concentration is higher tliau 0.500 mass%,
the alloyi~ipis slo\\. and prodoctivity is degratled. Therefore, the effective Al
co~lce~itratiion~ tih e bath is desirably front 0.05 inass% to 0.500 mass%.
[0041]
In ortler to measure Fe and Al co~itellitn the plated layec, a method of
perfoniiing chemical analysis oTa solution after dissol\ling the plated layer \\it11 acid
atid rcmovi~lgt~ on-dissolvedo sitles, may be used. For esample, a method of
tlissolvi~lgo nly the platetl layer of the gnlvannealcd steel sheet obtained by cutting to
lia\.e a size of 30 mm x 40 mm. \\,it11 a 5% HCI aqueous solution to \\fl~icahn inhibitor
is adtled, while supprcssing elution of a stccl sheet base inaterial, and determining the
Fe ant1 Al co~itcnftr o111s ignal strength obtained by perfortiling inducti\tely coupled
plasma (ICP) e~liissioa~nl alysis of tlie solution and a calibratio~ci urve created fro111
solutions having hiown concel~trationsm. ay be used. By considering variation ia
measurement bet\veen samples with at least three samples c ~o~ut ftro 111t he same
galvannealetl steel sheet, the average of ~t~easurevda lt~eso f tlie samples may be
calculated.
[0042]
In order to improve the coating property and \veldability. upper layer plating
may bc ntlditionall! pcrforcnetl, or \.arious treatnients, for csnmple. chromate trcat~nc~~t.
pliospliating, lubricity i~llprovenie~tlrte atment, wveldability itilproveti~ent reatment, and
the like may be perfortlied on the hot-dip galvanized steel sheet according to the
e~libodi~necaltn,d this does not negatively affect the effect of the embodil~lent.
100431
Next, a steel sheet which is a ~i~ateritaol b e plated will be described.
The steel sheet contaitis chemical components which will be described later, a
microstruch~reo f tlie steel sheet contains, by volunie fraction, equal to or more than
20% ant1 equal to or less than 99% in total of one or two of martensite and bainite, and
a residual structure of the stecl sheet co~ltaitisf errite, and one or two of less tl1an8% by
volume fraction of residual austcnite, and equal to or less than 10% by volutiie fraction
of pearlite.
In order to securc a tensile strength of equal Lo or greater than 980 h4Pa, a
total of 20% or more of martensite and bairiite is contait~cd. It is not ticccssaly to
particularly limit tlie total \~olotnef raction of nial.te11site and bainite, but \\,lien
considering actual manufacturing, since it is not easy to set the total volume fraction to
loo%, the total volume fraction may be equal to or less tllaa 99%. Since bainite has a
strength lower thao that of martensite, the volume fraction of bainite is desirably equal
to or less than 70%, iii a case of the tensile strcngtl~o f equal to or greater thati 980 MPa.
The residual austcnite transfor~nsin to martcnsite during betiding or tensile proccssing.
Since the inartensite for~iiedin this process is Ilard, the delayed fracture resistance is
degratlctl. Therelhre, tlic volume fraction of tlie residual auste~iitei s set to be less
t1ii111 8%. 111 additio~l,i f tlie volume fraction oftl~epe irlite strachlre exceeds lo%, it
is difficult to secure a strerigtl~o f equal to or greater than 980 Ml'a, and an upper litnit
of tlie pearlite is therefore set to lo%, The volume fraction of the residual austenite
s~ittll iz pcarlitc niay be 0%. . . ~ ~ .~ .
[0044]
However, in a case where elongation is fi~rtlierr equired to be improved, it is
desirable that ferrite be contained at the volume fraction of 40% to 80%. Ductility
(elongation) is itliproved by setting the volunie fraction of tlie ferrite to equal to or
greater than 40%. When tlie volume fraction of the ferrite is less than 40%, the effect
tliereof is slight. On the otlier hand, when the volunie fraction thereof exceeds SO%,
tlie total volume fraction of martensite and bainite beconles less than 20%, and it is
difficult to secure a high strength with the tcnsile strength of 980 MPa. The
nlartensitc nlay be any of tetnpered martensite containing carbides, and quenched
martensite not contauiing carbides. The bainite structure may also be any of lo\vcr
bainite containing carbides in bainite laths, and upper bainite containing carbides
between the laths.
[0045]
Ailean\vl~ilei,n a case of li~rtherim pro\,ing Ilole expandability, it is desirable
that one or two of martensite and bainite at greater than 60% in total is contained.
The reason lip the martensite and bainite are contained at volume fraction of greater
than 60% in total, is to secure a strength of cqaal to or greater than 980 IvPa whilc
inipro\Gng the hole expandabilit); and when the total volutiie fraction tliereof is cqaal
to or smaller than 60%. the effect thereof is slight.
[0046]
In identification, obsen'ation of esisting positions, and measttrement of the
area ratio ofeach pl~aseo f the microstructure \vhicIi are ferrite, niartensite, bainite,
austenite, pearlite, and the residual structure, a cmss section of tlie steel sheet in a
rolling directiotl or a cross section thereof in a direction orthogonal to the rolling
direction is etcl~cdb y a nital rcnzent ant1 a rcagcnt tliscloscd in Japnocsc ilncsaminetl
Patent Application, First Publication No. ,559-219473, and quantitation can be
performed with optical microscope observation with a n~agnificationo f 1,000-fold and
a scanning transmission electron n~icros~opweit h a ~nag~lificatioonf 1,000-fold to
100,000-fold. The observation at 20 or tnore visual fields is pcrfonned, and the area
ratio of each structure can be acquired by a point counting method or image analysis.
Although the measurement n~ethotli s two-dimensional observation, in the steel sheet
according to the e~nbodimentt,h e same area ratio is obtained over all the cross sectioos.
Therefore, the area ratio is equal to the volu~nefr action.
[0047]
Next, reasons for liniitation of the chemical components of the steel sheet
whicl~is a material to be plated \\,ill be described. %of the che~nicacl oniponent
hereinafter represents mass%.
C: C is at1 cletl~ent ~scdto increase the strc~igtho f the steel sheet. No\\~cvcr,
if the C content is less than 0.05%, it is diflicult to achieve both a terisile strengtll of
equal to or greater than 980 MPa and tlie \vorkability On tlie other hand, if the C .- -
contcnt is equal to or more tkan 0.40%; it is diffjcolt to secorc spot weldability. In
addition, the residual ailstenitc is cxcessivelp generated and thc dclayed fsacture
resistance is decreased. Therefore, the range thereof is limited to equal to or more
than 0.05% at~dle ss than 0.40%.
[0048]
Si: Si can be dispersed in the plated layer as the oxide. Tllus, Si is a most
iniporta~a~dtd itive element used to improve hydrogen embrittlemetlt resistance
(delayed fracture resistance). However, \\!hen the added alnount thereof is less than
0.5%. tlie amount of tlie oxitles is not sufficient, and the delayed fracture resistance is
1101 suflicicntly im1)mvetl. Therefore. it is necessary to atld 0.5% or Inorc of Si. 011
the other hand, when tlte added amount thereof exceeds 3.0%, the workability is
degraded, the steel slteet is e~nbrittled,a nd the occurreltce of the delayed fracture is
promoted. 111 addition, the pickling property is degraded. Accordingly, the Si
content is limited to a range of 0.5% to 3.0%. fit addition, Si is a reinforcing element
and is effective at ilicreasi~igth e strength of the steel sheet. Tlie Si content is liiore
preferably fro111 0.5% to 2.5% ant1 eve11 ltiore preferably from 0.5% to 2.0%.
[0049]
Ma: bit1 is a rcitlforcing element and is effective at increasing tlte strength of
the steel sheet. In addition, Mn can be dispersed it1 tlie plated layer as the oxide.
Ho\\,evel; urlien tlie Mn colitertt is less that1 1.5%, it is difficult to obtain a tensile
stretigtlt of equal to or greater than 980 MPa. On the other haud, \\,hen the Mn
contelit exceeds 3.0%, co-segregation of P and S is promoted and \vorkability is
signilicantlp dcgratled. In addition, the residual auste~iiteis exccssivcly gcncrated
and the delayed fracture resistance is decreased. Therefore, 3.0% is set to the upper
limit. A more preferably range ttliereof is from 2.0% to 2.8%.
[0050]
0: O in the steel sheet fomis the oxides in the steel sheet (except surface part).
The oxides contained in the steel sheet degrade elongation and hole expandabilitp.
Accordingl~: it is necessary to suppress the addcd aotount of O in the steel sheet.
Particularly, the oxitles exist as inclusions ill inany cases, and if tlie oxides exist on a
punclietl end surface or on a cut-out cross section, a cut-out-shaped defect or a coarse
tlimple is for~netol n tlie elid surface. .fhis results in stress concentration at the time
of Itole espantli~tga nd higli-strengthening ~)rocessm, id this becomes the origin of crack
formation to cause sig~iifica~dietg radatio~in the hole expandability, bendabilitp, acid
delayctl frilcturc rcsislance. If the 0 contc~lct sccetls 0.006%, this te~~dencbycc olncs
significant, and accordingly the upper limit ofthe 0 cotlte~iwt as set to be equal to or
less than 0.006%. On the other hlu~d,i t is preferable that a s~lialal rllot~llot f 0 be
contained in the steel sheet, but ifthe 0 content is less thaa 0.0001%, it is not
economicallp preferable due to excessively high cost, and aecordi~lglyth is is
substantially the lower limit. IIo~vever, in the hot-dip galvanized steel sheet
accordi~~tog t he e~llbodiments, ince the oxides are dispersed in tlie plated layer, the 0
content ill the plated layer or in the vicinity of tlie interface bet\veen the plated layer
and the steel sheet is higher than inside the steel sheet. Since the oxides existing on
the surface of the steel slieet exist on the surface of the steel shcct or it1 the plated layer,
tlie oxides existing on tlie surface of the steel sheet are not deil~leda s the oxides
containetl in the stcel sheet or oxygen co~lte~oift thc steel sheet. In detail, in a case of
~ileas~~rthie~ l0g c ontent of the steel sheet, the measureme~iti s performed after
removing thc plated layer and perfomling mechanical polishing of the steel sheet
surface by I0 pin.
[OOj 11
P: P tends to be segregated at a sheet thickness ccllter part of the stcel sheet
and embdttles a \veld. If tlic P contetit exceeds 0.04%, the cmbrittlcment of thc weld
bcconles siglliiicant, al~dth creforc the P content is limited to be eqoal to or lcss than
0.04%. If the P content cxcccds 0.04%, the steel sheet is crnbrittlcd and the
occurrence of the delayed fracture is promoted. A lo\ver limit valoe of P is not
particularly specified. but if the lo\ver lilnit value thereof is less than 0.0001%, it is not
ccono~nicala, nd therefore this value is preferably set as the lower liniit valoe.
[0052]
S: S negatively affects the meldability. ant1 ma~~ufacturabilitayt the time of
caheng erfoni~ingth e cold rolling and aiinealing process, and tlie ductility or tlie
bctidabilit): is ilc~l-atletl. In additio~ii.l l tlic cmbodimctit. in ortler to secure a
ntaximont tensile strength of equal to or greater than 980 MPa after the annealing, an
amount of alloy element is great compared to that of soft steel or the like, and the
strength at the tirt~eo f finish rolling tend to bc increased. Accordingly, if the slab
lieating temperature is lower than 110O0C, it is difficult to perfor111 the rolling due to an
increase in a rolling force accontpaoied with the decrease of the finish rolling
temperature, ant1 this may cause a defect of a shape of the steel sheet after the rolling.
The eKects of the embodiment are exhibited without particularly specifying an upper
liltlit of tltc slab heating temperature, but if the heating temperature is excessively high,
it is not economically preferable. Titereforc, tlte upper liniit of tlte slab heating
temperature is lower than 1300°C.
[0070]
In tlte embodiment, theAr3 transforntation point is calculated with the
t'ollo\\~ing equation.
Ar3 transfbm~atiotip oint rC) = 90 1 - 325 x C + 33 x Si -92 x (kin + Ni / 2
+Cr/2+Cu12+Mo/2)
(C, Si, Mn, Ni, Cr, Cu, and Mo in the equation arc cacb component contcnt [mass%] in
the steel.)
1007 11
The finish rolling tenlpcratilre of the liot rolling (hot rolling finish
temperatore) is set to be equal to or higher lltan the Ar3 transfor~t~atiopno int. Tile
effects of tlte entbodilncnt are esliibited \vithout particularly specifying the upper limit.
Iftlle rolling temperatt~re is lo\\.er than theAr3 transformation point, it is difiicult to e
ntanufactore as the rolling force becontes excessively high, ant1 the hot rolling is
performed with the dual phase of the ferrite and the austenite, and accordingly the
, nlicrostructut.e of tI~cst ccl sltsct afcr the hot rolling bccomes inllnniogcneous. That
is, the ferrite ge~ieratedi n the finish rolling is stretched it1 the rolling, is coarsened, atid
the ferrite transfor~nedf i o ~tili~e austenite has a film shape after the rolling. Even if
the cold rollillg and the a~ll~ealinarge perfonlied to perfonii the microstruch~rec ontrol,
the steel sheet having tlie illhomogeneous microstructnre is not preferable as thc
materials valy \\it11 respect to each other and tlie delayed frdcture resistance is
degratled. On tlie otller hatid, it is not preferable to set tlie finish rolli~igte mperature
of the hot rolli~lgto au excessive higl~te mperature, as it is necessary to set the heating
ternperato~.eo f tlie slab to an excessive high temperature for securing the tclliperature.
Therefore, an upper limit temperature of the fitlish rolli~lgtc niperature of thc hot
rolling is desirably equal to or lower than 1000°C.
[0072]
The conditions of the cooling after tlie hot rolling are not particularly
specified: and tlie effects of tlie embodiment are obtait~cdb y using a cooling pattern for
perk>rming the microstructure control for the respective requirements.
[0073]
Coiling is performed after the hot rolling. It is necessary to set a coililig
temperature to be froni 300°C to 700°C. If the coiling tempcrat~tree xceeds 700°C,
coarse ferrite or pearlite structc~reis generated in thc hot-rolled structure, strllcturc
i~~liomogerleiatyft cr tlie annealing becomes sigaificaot, and inaterial anisotropy of a
final protluct beco~iless ignificant. 111 adtlitio~li, t is not preferable to perforn~t he
coiling at a temperature exceeding 700°C, a thickness of the asides formed on the steel
sheet surface is excessively increased, ant1 accordingly the pickling property is
degraded. 011 the other lia~~idf ,t he coiling temperature is equal to or lo\ver than
300°C1 the strength of the hot-rolled sheet becomes great, and accorditigly the cold
.rolling l'orcc bcco~iicsli igll. This res~~litlls diflicctlt!. ofthc cold rollin: or tl~c
manufactoring ditficulty such as slieet breakage.
In addition, the roughly-rolled sheets may be joined to each other at the time
of the hot rolling to continoousiy perforni tlie finish rolliag. The ro:oughly-rolled
sheets may bc coiled once.
[0074]
The pickling is perfor~lled on the hot-rolled steel sheet \\~11icl1is coiled as
described above. The pickling is important for ilnproving the plating properties as tlie
oxides 011 the steel slieet surface cai be removed. As the pickling method, a wellh1o\\~
11li lethod may be used. In addition, the pickling rilay bc perfor~liedo nce or lliay
be perfor~llctls eparately multiple times.
100751
The pickled hot-rolled steel slieet is sub,jccted to the cold rollirig \\it11 the
cu~nolativero llitig redaction of 40% to SO% and the sheet passes through a continuous
galvanizing line. Since Si, Al, or Mn \~liichf ornls the oxides described above is
supplied by tlle diffi~sionf io~nth e inside of the steel slieet (in particular, on the grain
boundary), the oxides are easily fonucd in the vicinity of the grain boondary of the
steel sliect surface. As a result, if tlic grain size of the ferrite is great, the ratio of the
grain boundary on tlie steel sheet st~rfaccis small, and it is diffic~~tolt s ct the prqiected
area ratio of the oxides to be equal to or more than 10%. In geacral, fcrrite as coldrolled
is stretclled in a rolling tlirection and the ratio of the grain bot~ndarpis small.
As a result, in a case \vIierc the structure as cold-rolletl is annealed, it is difficult to set
the pro.jected area ratio of the oxitles to be equal to or more than 10%. Accordingl~: it
is necessary to promote the formation of tlie oxides by recrystallizing the ferrite and
decreasing tlie grain size, before forming tlie osides. W11en the cuniulative rolling
. - . . rctluction oftlic colt1 rollins is less than 401!/u. strain necessary for rccrystallization isnot
sofficiently introduced. In addition, tlie ductility of the final product is degraded,
and therefore this is set to tile lower limit. Further, when tlie ccuniulative rolling
reduction is less than 40%, it is difficult to niaintain a flat shape. On the other hand,
in the cold rolling with the cunlulative rolli~igr eduction exceeding SO%, it is difficult
to perfomi tlie cold rolling due to the excessive cold rolling force, and therefore this is
set to as upper limit. A more prelerable range thereof is 45% to 75%. As long as
tlie cumulative rolling reduction is in tlie range described above, the effects of the
enibotlinlent are cshibited withoot particularly speci@ing tlie tiuniber of rolling passes
and the rolling reduction of each pass.
I00761
In the embotliment, the diameter of a work roll \\!hen perforn~ingth e cold
rolling (roll tliameter) is set to be equal to or smaller than 1400 mm. The dianieter
tlicrcof is desirably equal to or smaller tl~an1 200 nim and more desirably equal to or
snialler than 1000 inm. The reasons thereof are because the kinds of strain introduced
uaqr depending on tlie roll tlian~etersa nd shear strain is easily introduced \\,lien using a
roll \\;it11 a small diameter. Since tlie recrystallizatio~e~a sily occurs froin a shear band,
the recrystallization rapidly occurs when wing a steel sheet \vliicli is subjected to the
rolling \writ11 tlie roll \\,it11 a small diameter wvhich fornis many sliear bands. That is, by
perfofoniiing thc rolling using the work roll \\,it11 the snlall roll diametel; it is possible to
start tlie recrystallization bcfore the oxides are formed.
Herein, nhen setting an entering slleet thickness before an initial pass in each
rolling process (for esample, cold rolling process) as a reference, the cumulatiw~e
rolling reduction is a percentage of ctttnolative rolling reduction \\it11 respect to the
reference (difference behveen tlie entering sheet thickness before tlie initial pass in the
. . . . . .rolling and an csisting sl~ectl ~ick~tcaslsi cr a final pass it1 the rolling). ~ ..
[0077]
The effects of the e~iibodi~iieanrte exhibited \vithout pa~ticalarlys pecifying a
heating rate in a case where the sheet passes through the plating line. However, the
heating rate which is less than 0.5 "Clsec is not preferable as tlie productivity is
significantly degraded. 111 addition, the Iieating rate exceeding 100°C is not
econotuically preferable, since it causes excessive equipme~iitn vestmeat.
[0078]
I11 the embotlimcnt, tlie stcel sheet is retai~icdin a telilpcrature range of 550°C
to 750°C wlicn heating to the aancaling temperature in a case \\here the sheet passes
through the plating line, for 20 seconds or longer. This is because the
recrystallization sofftciently proceeds in this temperature range, \\hereas oxide
foniiation is delayetl compared to tlie recrystallization. The oxitles containing Si, Mn,
or Al indcpendently or in cotnbinatio~\i\ !it11 eacll other, tcnd to bc fornlcd on tlie grain
boundary oftlle ferrite on the steel sheet surl5ce firstly, and use the grain bo~nldaryo f
fine ferrite fornietl by the rec~ystallizatio~asl a generation site. Tliat is, atier
perforniing the cold rolling, by perforniing tlie retaining in this teniperature range. it is
possible to start the rec~ystallizationb eforc forming the oxides. It is not desirable to
set the temperature ill the retaining to be lo\\rer than 550°C, as a long time is necessary
for the rec~ystallization. It is not desirable to set tllc temperatt~rc in the retaining to bc
Iiigl~erth an 750°C, as tlie oxitles are rapidly fornied and the oxides on the grain are
formed on tlie grain bounda~yi n the midtlle of the recrystallizatio~io r grain gro\\.th.
Ho\\lever, once after tlie oxides are fornied, the retaining for a long time inay be
perfornied in the temperahlre range of higlier than 750°C for the niicrostr~~chc~ornet rol.
Tlie same effect is obtained nit11 the structure having the ferrite as a priliia~yp hase or
\\.it11 the structure I~~vint:l x bainite or martensite as a primary phase. It is not
desirable when the retaining tinle at 550°C to 750°C is shorter than 20 seconds, as the
recrystallization does not sufficiently proceed. On the other hand, retaining for lotlger
than 2000 seconds is not preferable as not o11l~r is the productivity degraded, but also
tile fornlcd oxides are thick, causing the non-plating. Tlie retaining is preferably
perfornied for 40 seconds to 500 seconds. Tlie retaining does not only represent
isothermal maintaining, and may include change in tlie temperature such as heating or
maintaining in this temperature range.
Since tlie oxides are forn~edo n the ferritc grain boondary in priority, the
osidcs have a network structure, in many cases.
[0079]
After the retaining, the annealing is performed. In order to cause tlie oxides
containing one or niore of the oxides containing Si, Mn, or t\l independently or in
co~nbinationw ith eacli other to be contained in tlie plated layet; in the annealing
process of a continuous galvanizing line (CGL), after forniing the oxides of oxidizable
elements on tlie steel slieet surface, it is necessary to perform the plating and to
introtlucc the oxides into tlie plated layer. For forniitig'thc osides of Si, MI, or Al on
the stccl sheet surface, tlie atmosphere of the a~uicalingp rocess in the continilo~~s
galvanizing line is controlled to bc in a suitable range. That is, it is particularly
important to manage the Hz concentration and tlie dcw point in the anncaling
atnlospliere with the annealing tenlperature. Herein, in tlie embotliment, tlie
annealing is pcrformetl ill conditions of an N2 atmosphere in wliicli tlic H2
concentration is cqoal to or less than 20 volume%, tlie dew point \~l~icils ie qual to or
higlier than -2OoC, and the maxinl~um heating temperature of 750°C to 900°C. If tlie
n~;~siniuhmea ting temperature is lower than 750°C, escessive time is necessary to
rck>rni a solitl solution of carbidcs formed at tllc tinlc of tlie ilot rollin?. the carbides or
a part thereof remain, or tlie nlaltensite or the bainite is not sufficiently obtained after
the coiling, and accordingly it is difficult to secure tlie strength of equal to or greater
than 980 MPa. On the other hand, heating at an excessively high temperature is not
only not economically preferable as it causes increase in costs, but also causes
difficulties in which the sheet shape at the time of passing the sheet at the 11igl1
temperature is degraded or the lifetime of tlie roll is reduced, and therefore the upper
limit of the maximum heating teniperature is set to 900°C. Tlie heat treatment time in
this temperature rangc is desirable 10 scconds or longer to dissolve the carbides. In
contrast, a heat trcatnlent time which is longer than 1000 seconds is not econo~~iically
prcScrable as it causes an increase ill cost. The heat treatment time is Illore desirably
eqaal to or shorter than 600 seconds. Also, for tlic heat treatment, retailling at tlie
n~asimttm teml)erature may be pcrrormed isothcr~~~aollry t,h e cooling may be started
directly aftcr 1)erforniing gradient heating to cause tlic te~nperaturet o reach tlic
~nasinia~l~ne atingte niperatore, for esllibiting the erect of the embodinlent. It is not
desirable to set thc dew point to be lower that1 -20°C as the prqiected area ratio
dcscrihetl above esceccls 90%. The 1-12 concentration exceeding 20 volume% is not
desirable as it causes costs to sig~ificantlyin crease.
Tl~eio \\cr liniit of the H2 concentration is desirably 0.05 volunle% to set the
filmace atmospherc to a reduction atmosphere for Fe. The den~poinits desirably set
to be equal to or lower tl~a5~0i° C for suppressing tlie oxidation of Fe in the furnace.
The dew point is niore desirably set to be equal to or lo\ver than 40°C and even more
desirably set to be equal to or lo\ver than 30°C.
[OOSO]
Tlie ferrite is formed during tlie annealing at 750°C to 900°C or during tlie
coolin$.fi.o~nt hc masinic~mI ieati~l:tc~iipcrat~6~50~3~C~. t~A~c cortlin$ly, for f~~rthcr
improving the elongation, in a case where tlie ferrite area ratio of tlie microstructure is
set to equal to or liiore tliati 40%, tlie a~uiealingte mperature is desirably set to be less
tlian 840°C. By setting tlie annealing temperature to be less than 84OoC, a ferrite
fraction at tlie titiie of the ruiticaling can become great, and accordingly tlie structure
containing much ferrite can be obtained even after cooling. I11 addition, the structure
n,liicIi was the austenite at the titiie of the aluiealing is transfor~ned into anp of
martensite, bainite, residual austeaite, ant1 pearlite, after tlie cooling.
On the other Iiantl, to fi~rtherit liprove tlic hole expandability, in a case where
thc area ratio of the tiiarte~isitea tid bainite of the niicrostructure is set to be more than
GO%, tlie annealing temperatore is desirably set to be equal to or higher than 840°C.
By setting the annealing temperature to be equal to or liiglier tlia~Si 40°C, tlie austenite
fraction at tlie time of the annealing can be increased. The aostenite is transforn~etl
into the baiaite or tlie martensite in the cooling after tlie annealing, and accordingly thc
fraction of tl~cb ainite and tlie inartensite can beconie l~igli.
[OOS I]
Regarding tlie annealing before plating, n Scndzimir nictliod of "lieatitig the
stccl slieet in a aon-oxidation atmosphere after degrcasing and pickling, atuiealing in a
reduction atniospl~crec ontainillg Hz and N2, tl~enc ooling to the vicinit)~o f a plating
batli temperatarc, and immersing the stccl slieet in the plating bath", an all reducing
ft~rnacem ethotl of "adjusting an atmospliere at the time of annealing, lirst oxidizing a
steel sheet surface, tl~enp erforming cleaning before plating by tlie reduction, tliell
inlinersing tlie steel slieet in a plating batli", or a flus nietliod of "after perfornli~ig
tlegrcasing ant1 pickling of a steel slieet, perfomling flux treatment using amnionium
cliloride or the like and then immersing tlie steel sheet in a plating bath" may be
apl~liedn ftcr cliati~i~tiligc mctl~odi f ncccssary inaccortlancc \vitli processes of the
embodiment.
[eon]
After finishing tlie annealing, the steel sheet is cooled to a te~iiperaturer ange
of 500°C to 750°C (first cooling or third cooling). An average cooli~igra te frotii tlie
maxi~iiuml ~eati~tiegli iperature oftlie a~ltiealitigis set to 1.0 'Clsec to 200 'Clsec. It
is not desirable to set the cooling rate to be lo\ver than 1 "Clsec, as tlie productivity is
sig~iifica~itdlyeg raded. On the other hand, sitice an excessive increase io tlie cooling
rate causes an increase in manufacturing costs, the upper li~iiiits preferably 200 "Clscc.
[0083]
After that, tlie cooling is performed at a cooling rate which is eqttal to or
higher tlian I "Clsec and is faster tlia~tih e first cooli~igra te, to a temperature range
bet\veen a telnperattlre which is lower tlian a hot dip galvanizing bath temperatare by
40°C a~ida temperatare \rl~icRi s higher tliali tlie hot dip galvanizitig bath te~iipcratnre
by 50°C (second cooling). The cooling rate is set to be equal to or liiglier than
1 'Clscc because, if tlie cooling rate is lo\\; tlie ferrite or pearlite is escessively
gc~icratedi n tlic cooling process and accordit~glyit is difficult to securc tlic strength of
equal to or greatcr tlta~9i x0 MPa. Mean\\~liiles,i nce an excessive increase in the
cooling rate increases manc~facturingc osts, the oppcr li~iiiits preferably set to
200 "Clsec. In the cmbodimcnt, the hot dip galva~iizi~btgat h temperature is set to be
440°C to 460°C.
[OOS4]
Insteatl of second cooling, bcfore tlie i~n~iiersinthge steel slieet ill the platitig
bath: tlie cooling (foorth cooling) may be performed once to a temperature of 25°C to
500°C, and the11 in a case where a cooling stop teniperattlre \\,as lo\ver tlian tlie
. tenipcrat~~rc\\-hicisl il oner tlinn a liot dip galva~iizingb at11 tcnipcrature by.40°C. tlie
steel sheet may be heated again to the heating range of 350°C to 500°C and retained.
When the cooling is perfornied in the temperature range described above, a hard phase
such as ~ilartensiteo r bainite is fornicd fro111 non-transformed austenite during the
cooling. After that, by perfornling the heating again, the hard phase is tempered.
The ten~peringi ndicates precipitation of carbides, or recovery and rearxangenlent of
dislocation, in tlie hard phase, and by performing the tempering, the hole expandability,
the bendability, or tlie delayed fracture resistance is improved. The lo\ver limit of the
cooling stop temperature is set to 2S°C because excessive cooling requires significant
equip~nenitn vestment. In addition, even if cooling is perfornled excessively, effect
thereof is also saturated. I11 addition, after tlic re-heating and before the plating bath
inlmersion, the steel sheet is retained in (he temperature mnge of 350°C to 500°C.
The retaining in this temperature range not only contributes to the te~nperingo f
~nartctisite,b ut also elinlinates tempcrattlre irregolarity of the slieet in the \vidth
direction and improves the appearance after plating. In a case where tl~eco oling stop
temperattlre of the fourth cooling was 350°C to SOO°C, the retaining may be perfornied
\\,ithotit perfomling the re-heating. The tinlc for perfomling thc retaining is desirably
set to be eqt~atlo or longer than 10 seconds and equal to or shorter than 1000 seconds
to obtain the effccts tliereof. Ln order to generate the bainite tmnsfom~ationa nd to
stabilize the rcsidoal aostenitc, the retaining time is desirably set to 20 seconds to 750
seconds and inore desirably set to 30 seconds to 500 seconds.
[OOSS]
After tile second cooling or retaining in the telnperature range of 350°C to
500°C. the steel sheet is ini~ilersedin the plating bath and liot dip galvanizing is
perforn~etl. A range of a plating bath immersion slleet temperature (teniperatore of
,, . . tlie steel shccl \\hen inmicrsing tlie stccl sheet iti.tlic liot tlip gal\,nnizin~I) ath) is set to
a temperatore range between a temperature lower than a liot dip galvrmizing bath
te~nperatoreb y 40°C and a temperature higher than the liot dip galvanizing batli
temperature by 50°C. It is not desirable to set tlie hot dip galvanizing bath illutlersioli
slicct tetilperature to be lo\ver than tlie temperature lower than the hot dip galvanizi~tg
bath temperature by 40°C, as heat release at the tittte of hot dip galvauiziog bath
imntersion is great, a part of the nlolten zinc is solidified, and the plated appearance
may be degraded. I11 a case \\'liere the sheet temperature before ii~nmersioni s lo~\ler
tlta~tlh e telnperatore lo\\~ctrh an the hot dip galvaniziltg bath temperature by 4OoC,
heating tnay be adtlitionally perfornied by an arbitrary methotl before the hot dip
galvanizi~lgb ath iiii~nersionto control the sheet temperature to be equal to or higher
than tlie temperature lower than the hot dip galvanizing bath tetnperah~reb y 40nC, and
then the steel sheet niay be i~nmersedin tlie plating bath. 111 addition, if tlie plating
bath imniersion sheet tcmperature escccds thc tcmperature higher than tlic liot dip
. . galva~i~zb~a~thi gte mperature by 5OoC, it causes an operational problen~a cconlpanying
the hot dip galvanizing bath telnperature increase. Tlie plating batli inay contain Fc,
Al, Mg, Mn, Si, Cr, or the likc in atldition to pure zinc.
LO0861
If the osides cover the steel sheet surface, a problcm such as non-plating or
delay of alloying easily occors. Partict~larlpt, he osidc of zinc esists on the surface of
tlie liot dip galvanizing bat11 or in thc bath. Since tlie ositlc of zinc and the oxides
fosriied on tlie steel sheet surface havc high affinity ant1 tlie oxide of zinc is easily
attaclicd tl~ereto. a problem of non-plating or an appearance defect easily occurs. 111
tlie embodiment, since tbe oxides of Si, Pvln. or Al are dispersed in tlie steel sheet
st~rfacen, on-plating or delay of alloying easily occurs. I n a case of dispersing the
oxides to llavc the prqiccted ;[sen ratio of cquztl to or inore than 10% so as to supprcss
hydrogen embrittlement, tlie tendency thereof becomes sigciificat~t. Accordi~lgl>:i n a
case of for~iii~linthg e oxides of tlie embodiment on the steel sheet surface, molten zinc in
the plating bath flows at ajet rate with a flow rate of 10 m1111in to 50 md~nina, nd
accordingly the attachme~ito f the steel sheet and tlie oxide of zinc is prevented, and
prevention of tion-plating and protiiotio~lo f alloyi~lga re perfor~lled. As a result, the
oxides call be dispersed in tlie plated layer. Norlilall); an oxide film ofZn or N,
which is called scum, floats in tlie hot dip galvanizing bath, and this causes non-plating
or delay of alloying. Tlic present i~lvcntorsh ave fol~tidth at, in a case \\(heret he
oxides exist on the steel sheet surface, the scu~nis easily attached at tlie time of
immersion of the steel sheet into the bath, and thos non-plating (defect affecting the
steel sheet in the plated layer) is easily generated. The scum attached to the steel
sheet does not only cause the non-plati~igb ut also delays the alloying. This trend
beconies partic~~larsliyg nificant ill the steel shcct containing a large amount of Si or
M I A delailetl meclianisnl is not cleal; but it is considered that the non-plating or the
delay of alloying is promoted by reaction of the oxitles of Si or E\?n formed on the steel
sheet surface and tlie scorn which is the oxides as well. If the flow rate is lower tllaci
10 mlmin, the cffect of suppressing the tion-plating by tlie jet flow is not obtained, and
the oxides are attached to the steel sheet surface, and this causes tlie appcaratice defect.
On the other hand, if the flow rate excccds 50 ild~ili~tlii,e effect thereof is saturated and
a pattertl caused by tlie flow ofzinc is generated, and tlie appearance defect easily
occu~.s. In addition, escessi\~ee quipment investment increases cost. Therefore, tlie
flow rate of the molten zi~icin tlie plating bath is set to 10 i ~ l / ~ t~o i5i0~ iln l~nin.
Herein, a dircctio~ol f flux of the molten zinc is not particularly li~~liteadn,d it is only
preferable to control a flax magnitutle.
[OOSZl . .
After i~iimersio~tlii,e steel sheet immersed in tlie plating bath is taken fro111 the
plating bath and wiping is perfornled as necessaly. When wiping is performed \vith
respect to tlie steel sheet, it is possible to co~itrotlh e aniount of plate to be attached to
the steel sheet surface (plate attachnient amount). The plate attachment amount is not
particularly limited, but is desirably set to be equal to or niore than 5 g/m2 per one
surface fi.0111 a viewpoint of fitrther increasing tlie corrosion resistance. In addition,
tlie plate attachment amount is desirably set to be equal to or less than 100 g/mZ per
one surface fro111 a viewpoint of fi~rtheri~ lcrcasingp lating adlicsion.
[OOSS]
In a case of fnrther perforn~ingtl ie allopi~igtr eattiient of the plated layer, it is
perfos~ned at a temperature equal to or lower than 600°C. Mean\\4iile, if tlie
ten~peratureis higlier than 600°C, carbides are fomled to decrease tlie residual
aostenitc volume f'raction, excellent tloctility is difficult to secure, tlie hartl phase s~lch
as n~a~-tcnsiitse s oftened, or a larse alnoont of pearlite is generated, and accordingly it
is difficult to secure a maximum tensile strength of equal to or greater tlian 980 MPa.
On the other hand, it is not preferable to set the alloying treatment tetiiperatllre to be
lo\ver than 460°C, as the alloying is delayed and the protluctivity is degraded. lo
addition, if the alloying treatment temperature exceeds 600°C, the Fc content in the
plated layer niay escecd 15 mass%, and accordingly~a dhesion of thc plated layer is
lost. 111 a case of not performing the alloying treatmcnl, the Fe content in the plated
layer docs not exceed I5 niass% as long as tlie eontlitions of the e~nbodinicnat re
satisfied.
[0089]
FIG. 3A and f:IG. 3R show flowcharts of the manufacturing niethod according
to onc cn~bodinlcnot i'thc present i n ~ n t i o ntlc scribetl ''1 bo vc.
[0090]
In addition, skin pass rolling may be performed to correct tlie steel sheet shape
and to realize an improvenient of ductility by moving dislocation introduction.
Rolling reduction of the skin pass rolling after thc heat treatnient is preferably in a
range of 0.1% to 1.5%. If the rolling reduction is less tlian 0.1%, the effect thereof is
slight and tlie co~itrolis dificult as \\sell, and therefore this is set as tlie lower limit. If
tlie rolling reduction exceeds 1.5%, the productivity significantly decreases and
therefore this is set as tlic tipper limit. The skin pass may be perfomled in-line or offline.
In addition, the skin pass \\it11 tlic target rolling retluction may be perfomled at
onc time or rimy be perfor~ncdb y being divided into several times.
[0091]
Tlie material or the hot-dip galvanized steel sheet of the prcsent invention is,
in principle, ma~iufacturcdb y perfol-~ningre fining, steelnial;ing, casting, hot rolling,
and cold rolling processes ivhicli are typical steel manafacturing processes, but the
effect of tlie present invention can be obtained even \vith tlie product manufactured by
on~ittinga part or all of the proccsses as long as tlic conditions according to tlic present
invention are satisfied.
[Examples]
~00921
Next, the present invention \\;ill be described in more detail with examples.
Slabs including coniponents s11o\\'n in Table I \\.ere heated to 1200°C, the hot
rolling was performed u~itlerh ot rolling contlitions disclosetl ill Table 2-1 to Table 2-4,
and afler performing water cooling \\:it11 a \Jrater cooling zone, coiling treatnlent \\!as
perfornied at temperatures slio\\~ni n Table 2-1 to'l'able 2-4. Tlie tliickness of tlie hotrollcd
sliccts \\,as sctin a range of 2 nl~nto4. 5 nim. After pickling tlic hot-rolled
sheets, the cold rolli~tgw as perfor~~teadt a predeter~ttinedc old rolli~tgre duction so as
to set the sheet thickness after tlte cold rolli~tgto 1.2 mm, and the cold-rolled sheets
were obtained. After that, the cold-rolled sheets \\,ere retained under tlte co~tditio~otfs
Table 2-1 to Table 2-4 in a temperature range of 550°C to 750°C in continuous
galvannealing equipnient under the conditions shown in Table 2-1 to Table 2-4, the11
perfonti annealiag, cooling, and if necessary, re-lteatiitg and \\,ere itnlttersed in the hot
dip galvaniziltg bath \\4iicl1 was controlled to have predetermined conditions, and then
were cooled to a room temperature (25°C). An effective A1 co~tce~ttratiion~ tth e
plating bath was set to a range of 0.09 mass% to 0.17 mass%. Apart ofthe steel
sheet \\,as immersetl in the hot dip galvanizing bath, then \\,as subjected to the alloying
treatment ultder tlle various conditions. and \\.as cooled to roo111 temperature. A
coating weight at that tintc was set to approxi~uately3 5 ~/III'f or both surfaces. Lastly,
tile skin pass rolli~tg\\ ,as performed for the obtained steel sheets \\,it11 a rolli~~g
reductio~lo f 0.4%.
'fhe properties of the steel sheet rnatt~~factured.undtehre co~lditio~dise scribed
above arc sho\vn ill Table 3-1 to Table 3-4.
In the tensile test, a JlS No. 5 test piece was collected as a sample fio111 tlie
shect having a thickness of 1.2 mm ia a dircctio~oi rthogonal to the rolling direction,
and thc tensile property was evaloated based on JIS 22241: 201 1.
[0093]
Tlle obse~vationo f tlie oxitles ill the plated layer \\,as pcrfomicd by
perfomting struchlre observation \\.it11 the cross section of the hot-dip galvanized steel
sheet. After processing the cross section of the hot-dip galvanized steel sheet surface
layer into thin flakes so as to coataiil tlte plated layer \\,it11 tlie focus ion beam
proccssi~lgd cvicc. the obscrvation by.FE-TE%In ~ld1 112 composition analysis by crlcrsy
dispersive X-ray spectrometry (EDX) were perforn~ed. The observatio~\i\ ,as
perfor~ileda t 5 visual fields at a magnificatio~oi f 10,000-fold to 50,000-fold, and the
co~tipositioo~ri tlte area ratio was deter~iiined.
[0094]
The Fe attd an A1 coliterit in the plated layer was measored by dissolvi~tgtl ie
plated layer in a 5% HCI aqueous solution to which an inhibitor \\,as added, re~tloving
non-dissolved oxides, and then performing ICP emission analysis of a solution.
Three sattlples were measured and the average value \\,as set to Fe% of tlie plated layer
[0095]
The evaluation of tlte co~iipositioo~ri tlte area ratio of the oxides can be
perfor~iiedb y perfor~ili~tlhge structure observatio~wi itli the cross section of the hot-(lip
galvanized steel sheet. For exa~nplet,h ere is a method of processing the cross sectio~l
of the steel sheet into thin flakes so as to contain the platcd layer with the lbcos ion
beam (FIB) processillg device, and then perfomling the observation witli field emission
trallsmission electron n~icroscopy( FE-TEbl) and composition analysis with energy
dispcrsive X-ray spectrometry (EDX). Aftcr manufactt~ring samples for observatio~l
\\,it11 tlie FIB processing device, the oxides \wre observed with FE-TEM at a
magnification 01'50,000-fold. 111 addition. by a~lalyzi~tihge oxitles \\,it11 ED);, the
oxides co~~bled identified.
[0096]
111 order to cause the oxides contaillil~go ne or more of the oxides containing
Si, bln, or A1 indepc~ldentlyo r in combi~lationw ith each other to be contai~~eildl the
plated layer, after forming tlte oxides of oxidizable elements on tile steel slteet surface
in the annealing process of the CGI,, it is necessary to perfomt the plating and to
i~~trotluctlclc osidcs into thc plntctl layer.
[0097]
Next, in order to evaluate tlie tlelayed fracture resistaace, test piece
manufactoring by a U bending test and a delayed fracture resistance test by electrolytic
charge were pcrforn~cd. Tltc delayed fracture resistance of the hot-dip galvanized
steel sheet manufactured based on the method of the present inventio~\i\ ,as evaluated
based oa the method disclosed in Non-Patent DOCLIIII3~.I I~
In detail, afier perfomling mechanical cutting of the steel sheet, the c~.oss
section \\,as subjected to n~echanicagl rinding, and the U bending test was performed at
10R. A strain gauge was attacl~edto tlie center of the obtained test picce, and botlt
ends of the test piece \\,ere contpressed \\lit11 the bolt to apply stress. The applied
stress urns calc~rlatedb y the strain ofthe monitored strain gauge. For load stress. tlie
stress correspontling to 0.7 of TS \\,as applietl, that is, a strcss of 700 MPa in a case of
the steel sheet Ila\'i~lgth e TS of 980 MPa class, a stress of 840 Ml'a in a case of tlie
steel slleet having tlte TS of I 180 MPa class, and a stress of 925 MPa in a case oftlie
.. steel sltcet having the 7's of 1320 MPa class. 'fliis is because it is considered that tlie
residual stress introdt~ceda t the tinie of forniation has a relatioi~sliil)w ith the TS of tlie
stcel sheet.
F~rrthcr,t he hole expandability \\,as evaluated based on JFS T1001.
[0098]
The obtained LJ bending test piece was immersed in an ammonium
tliiocyariate solution, tlie steel sheet was set as a cathode ant1 a platinti111 elcctrotle \\'as
set to all anode, an electric current \\:as llo\vetl at a current density of 0.1 r i i ~ / c na~n~d ,
an clectrol~.ticc harge test \\,as perforlnetl for 2 hours. Hydrogen generated in the
electrolytic charge test niay enter tbe steel sheet to cause tlelayed frachlre. After tlie
clectrol\,tic cli:u'~c tcst. thc test picce was takcri i.orn tlic solution and tbc center part of
the U bentling test piece was visually observed to inspect for presence and absence of
cracks. However, the plated layer may be cracked at the tinie of the U bellding test,
and \v11eo observing the surface after the electrolytic charge test, tlie cracks thereof
may be incorrectly deterinined as the cracks generated by the delayed fracture.
Herein, after the delayed fracture test, tlie plated layer was dissolved in the 5% HCI
aqueous solution to \\,hich an inhibitor was added, and presence and absence of the
cracks on the steel sheet surface were observed. Since great stress is applied to a
bending processed part, if cracking is generatetl, proceeding thereof is rapid.
Accordingly, in the cxamplcs, in a case \vlicre the cracks were present, all the cracks
becanlc large opening crack, and presence and absence of the cracks could be easily
visually determined. In the examples, by using a niagnifying glass or a
stereomicroscope, the test pieces \\{erec arefi~llyo bserved, tlie presence ancl absence of
tlic cracks \\'ere confir~iieda gain, and it was confirmed that tliere \\?eren o fine cracks if
there were no opening cracks.
[0099]
In res~~lotfs dclayed fsactt~rcte st sIio\\,n inTable 3-1 to Table 3-4, "GOOD"
indicates that no cracks \irere generated on the end portion and "BAD indicates cracks
generated on tlic end portion.
The plating properties \Irere evaloated as follo\vs.
GOOD: no non-plated part
BAD: non-plated pait observed
I'o\vdering resistance was evaluatctl by detertnining Whether or not po\vdering
occurretl, when performing pressing.
GOOD: no po\vdering occl~rred
BAD: poivderin~o ccurred
I11 an exatnple includi~tgth e II~II-platedp art, suficiettt adl~esiono f the plated
layer was not obtained.
[01 001
The tneasured tensile strength, delayed fracture rcsistance, plating properties,
and Fe% in tlle plated layer are slio\\rn in Table 3-1 to Table 3-4. It is found that all of
the steel sheets of the present i~ive~ttihoa~vle high stre~igtlot f equal to or greater than
980 MPa and have the escellellt delayed frach~rere sistance ant1 the plating properties
(non-plating and powdering resistance).
On the other Iiacltl, in the examples ia \vliich any of conditio~~iss o ut of the
range of the present invention, at least one of the tellsile strengtli, the delayed fracture
resistance, and the plating properties (noa-plating and po\vdering resista~lce)is
degratled.
111 all example in \vhic11 tile coltl rolling reduction was set to cqaal to or more
than 90%. the sheel was brokcn it1 the ~~titldolef the process ant1 the sheet could not
passed. 111 adtlition, in all example in \vliicli t11e cold rollitlg reduction \\$as set to less
than 30%, the sheet shape was not stable, rlifliculties occurrctl at the time of passing
the sheet, ant1 therefore the sheet passing \\'as stopped. Since both steel sl~cctsc ould
not be evaluated, tlte results thereof are itat s11o\~cti n 'rabies.
The reniaintier of the components of Table 1 i~ldicatcsF e and unavoidable
itnpurities, and "-'' indicates "not detected". Underlitled valaes in Tables indicate
values out of the range of the present invention. ;'*I", "*2" "*3", and "*4" in Tables
2 and 3 are as the description in the lo\ver ])ortion of Tr~ble3 -1. In addition, GI in
Tables indicates the hot-dip galvanized steel sheet including the hot-clip galvanized
layer, and GA indicates the hot-dip galvanized steel sheet including the galratlnealed
layer. that is, tltc gal\.annc~~lcsttlc cl sllcel.
[O 1021
[Table 2-11
[0103]
[Table 2-21
[0 1041
[Table 2-31
[0 1051
[Table 2-41
[0106]
LTable 3-11
[0107]
['fable 3-21
[O I081
[Table 3-31
[O 1091
[Table 3-41
[Industrial Applicability]
[0110]
The present inventiotl proviclcs a high-stretigth hot-clip galvanized steel slieet
\\4iich is suitable for a ~(ructuraml ember, a reinforcing member, and a suspension
member for a vehicle. has the tensile strength of equal to or greater than 980 MPa. and
has escellent delayed fracture resistatice. at lo\\, cost. Accordingl>: great contribution
to automobile lightening can be espected atid the it~dr~strieatYl ect is estremely l~igli.
Table 1(1/2)
Table 1(2/2)
Table 2-1 ( 1 2 )
UNDERUNED VALUES INDICATE VALUES OUT OF THE RANGE OF THE PRESENT INVENTION.
5.T
Table 2- 1(2!2)
UNDERUNED VALUES INDICATE VALUES OUT OF THE RANGE OF THE PRESENT INVENTION.
Table 2-2(1!2)
UNDERUNED VALUES INDICATE VALUES OUT OF THE RANGE OF THE PRESENT INVENTION.
Table 2-2(212)
JNDERLINED VALUES INDICATE VALUES OUT OF THE RANGE OF THE PRESENT INVENTION.
Table 3-1(1/2)
*I: IN A CASE WHERE THE STRUCTURE CONTAINS FERRITE AND CARBIDES,
THE CARBIDES WERE COUNTED AS FERRITE.
*2 IEIDICATES THAT RE-HEATING WAS NOT PERFORMED SINCE A SHEET TEMPERATURE
IS HIGHER THAN 350°C.
*3 INDICATES THAT ALLOYlNG TREATMENT IS NOT PERFORMED.
*4 INDICATES THAT COLD ROLLING COULD NOT BE PERFORMED SlNCE A COILING TEMPERATURE
IS LOW AND STRENGTH OF A HOT-ROLLED SHEET IS EXCESSIVELY GREAT.
Table 3-1 (212)
UNDERIINED '!ALLIS IADICATF. VALUES OUT OF THE RANGE OF THE PRESENT INVEhTlOh
F FERRITE. E+ RAIIIITE YR RESIDIJAI. AJSTENITE t-I MARIkNSITE. P: PEARIITk.
*1: IN A CASE WHERE THE STRUCTURE CONTAINS FERRITE AND CARBIDES,
THE CARBIDES WERE COUNTED AS FERElTE.
*2 INDICATES THAT RE-HEATING WAS NOT PERFORMED SINCE A SHEET TEMPERATURE
IS HIGHER THAN 35OoC.
*3 INDICATES THAT ALLOYING TREATMENT IS NOT PERFORMED.
*4 INDICATES THAT COLD ROLLING COULD NOT BE PERFORMED SINCE A COILING TEMPERATURE
IS LOW AND STRENGTH OF A HOT-ROLLED SHEET IS EXCESSIVELY GREAT.
Table 3-2(1/2)
Table 3-2(2/2)
Table 3-3(112)
Table 3-3(213)
NOTE I
Table 3-4(liL?)
Table 3-4(212)
[Document Type] CLAIMS
[Claim 11
A hot-dip galvanized steel sheet comprising:
a steel sheet; and
a plated layer 011 a surface of the steel sheet,
\\$herein the steel sheet contains, by mass%,
C: equal to or more than 0.05% and less than 0.40%,
Si: 0.5% to 3.0%,
Mn: 1.5% to 3.0%,
0: limited to 0.006% or less,
P: litiiited to 0.01% or less,
S: linlited to 0.01% or less,
Al: litilitcd to 2.0% or less,
N: limited to 0.01% or less, and
the reniainder including Fe and unavoidable impurities,
\vlierein a microstrocture of the steel slicct contains,
by volu~nefr action, cqual to or more than 20% and equal to or less
than 99% in total of one or two of a martcnsitc and a bainitc, and
a residual structure including a fcrrite, and one or two of a residual
at~steniteo f less tlia~i8 % by volunie fraction, and a pearlite of equal to or less than
10% by \.olnme fraction,
\vlierein a tensile strengtl~o fthe steel sheet is equal to or greater than 980
MPa.
wherein the plated layer is a hot-dip galvanized layer ~\~hiccIoi ntains oxides
inclutlin~o ne or t\vo or ti~orco f Si. Mn. ant1 hl. contains cqual to or less than 15
mass% of Fe, and the remainder including Zn, Al, and unavoidable impurities, and
\\.herein when a cross section i~icluditigth e steel sheet and the hot-dip
galvanized layer is seen in a shket thickness direction, a projected area ratio which is
an area ratio obtaitlctl by dividing a lengtt~o f the oxides projected to ail interface
between the hot-dip galvanized layer and the steel sheet by a length of the interface
betnreen tlie Iiot-dip galvanized layer a~idth e steel sheet, is equal to or liiore t11,ui 10%
and equal to or less tliati 90%.
[Clai~u2 1
Allot-dip galvanized steel sheet coliiprising:
a stecl sheet; and
a plated layer on a surface of tlie steel sheet,
\\,herein the steel sheet contains, by mass%,
C: equal to or more thali 0.05% atid lcss than 0.40%,
Si: 0.5% to 3.0%,
bln: 1.5% to 3.0%,
0: limited to 0.006% or less,
P: limited to 0.04% or less,
S: limited to 0.01% or less,
Al: limited to 2.0% or less.
N: limited to 0.01% or less, and
the remainder including Fe atid unavoidable implirities,
n,herein a microstructore of tlie steel sheet contains.
b~~volumfrea ction, equal to or more than 20% and equal to or less
than 99% in total ofone or t \ ~ of a martensite and a bainite, atid
a resitlu;~sl tructure iticlttili~ai~ f crritc, ant1 o~icor two of a rcsid~tal
austenite of less than 8% by volume fraction, and a pearlite of equal to or less than
10% by volun~efr action,
~vlierein a tensile strength of tlie steel sheet is equal to or greater than 980
MPa,
wherein tlie plated layer is a galvannealed layer wllich contains oxides
including one or t\vo or more of Si, Mn, and Al, contains equal to or niore than 7
mass% and equal to or less than 15 mass% of Fe, and the remainder including ZII, Al,
and unavoidable impurities, and
\\,herein \\then a cross section including the stcel sheet and the galvannealetl
layer is seen in a sheet thickness direction, a l~rojecteda rea ratio \\~liiclii s an area ratio
obtained by dividing a lenglh orthe oxides projected to an interface bet\wreen the
galvannealed layer and the steel sheet by a length of the interface between the
galvannealed layer and thc steel sheet. is equal to or more than 10% and equal to or
less than 90%.
[Claim 31
The hot-dip galvanized stcel shcet accortling to claini 1 or 2,
\\herein tlie ~nicrostructurcc ontains, by voltunle fraction, 40% to 80% of
ferrite.
[Clai~n4 1
The hot-dip galvanized steel slieet according to claim 1 or 2,
\vllerei~it lie microstructure contains, by volume fraction, more than 60% of
one or t\vo of niartcnsite and b:liriite.
[Claim 51
'l'lie tensile hot-dip galva~lizeds teel sheet according to claim 1 or 2,
\~hcrcit~hle steel shcct fi~rtliecr ontains. by inass?h. one or two 01-n ~orco f
Cr: 0.05% to 1.0%,
Mo: 0.01% to 1.0%,
Ni: 0.05% to 1.0%,
Cu: 0.05% to 1.0%,
Nb: 0.005% to 0.3%,
Ti: 0.005% to 0.3%,
V: 0.005% to 0.5%,
B: 0.0001% to 0.01%,
Ca: 0.0005% to 0.04%,
Mg: 0.0005% to 0.04'36, aiid
REM: 0.0005% to 0.04%.
[Claim 61
A manufacturing inetliod of a hot-dip galvanized steel sllcet, tlie method
comprising:
casting a tnolten steel including a chemical components according to claim 1
to obtain a steel;
heating the steel to a first temperature range of 1100°C to lower than 1300°C,
dircctly or after cooling once;
completillg a hot rolling of tlie steel at a telnperature equal to or l~iglietrl la~i
an As3 trailsformation point;
coili~igth e steel ill a second tetiiperature range of 300°C to 700°C;
pickling tile steel:
perfomling cold rollilig of tlie steel \vith a cumulative rolling reduction of
40% to SO% using a cold rolli~igm ill iilcluding a work roll having a roll diameter of
retaining tlie steel in a third tempereture range of 550°C to 750°C for 20
seconds to 2000 seconds duri~igh eating the steel to an annealing tealperatore, when tlie
steel passes tl~ouglal continuous galvanizing line;
~liailltainingth e steel in a fourth temperature range of 750°C to 900°C for 10
seconds to 1000 seconds, in an N2 atmosphere in \\rliich an 132 concentratio~ils equal to
or less than 20% and a den, point is equal to or fiigher than 20°C, \vIiile perfomling an
a~~nealing;
perfornli~lga first cooling of cooling tlie steel to a fifth temperatore range of
500°C to 750% at an average cooling rate of 1 "C/sec to 200 "C/sec;
l~erfomiinga secontl cooling of cooling the steel to a sixth temycratore range
between a temperature \vliich is lo\ver than a hot dip galvanizing bath temperature by
40 "C and a tclnperature which is higlier than the hot dip galvanizing bath tenlperature
by 50°C1 at an average cooling rate \vhicll is 1 "Clsec to 200 "C/sec and is faster than
the average cooling rate or the first cooling;
gal\i?nizing tlle steel by i~nmersingth e steel in a hot clip galva~iizingb ath
\tr1iich t10\\~sa t a flo\v velocity of 10 mlmin to 50 ~ud~uainft er setting a plating bath
immersion sheet temperature \\~liiclii s a tenlperatc~re\v hen i~liniersiligth e steel in the
Ilot dip galvanizing bath, as tlie sixth temperature range; and
cooli~lgtl ie steel to a temperature equal to or lo\ver than 40°C.
[Claim 71
A manufacturing iiiethotl of a hot-dip galvanized steel sheet, the metltod
comprising:
casting molten steel including a chemical components according to clai~l2i to
obtain a steel;
. . Iloatin? the stccl to a sevcntli tempcrittt~rcr an~eof I 100°C to lo\\.cr thiut . ~~
1300°C, directly or after cooli~igo nce;
completing a hot rolli~lgo f tlie steel at a temperature equal to or higher than
a n k 3 t ralisfor~ilatiop~oi int;
coiling the steel in an eighth temperature range of 300°C to 700°C;
pickling tlie steel;
perforliii~igc old rolling of tlie steel \\it11 a cu~ilulativer olling reduction of
40% to 80% using a cold rolli~igm ill including a \vork roll having a roll diameter of
200 111111 to 1400 mai;
retai~ii~tilgie steel in a nintll temperatore range of 550°C to 750°C for 20
seconds to 2000 seconds during heating the steel to an annealing tempcraturc, when the
steel passes through a co~itinuousg alva~lizillgli ne;
maintaining the steel in a tenth temperah~rera nge of 750°C to 900°C for 10
sccotids to 1000 scconds, in an NZa tniospl~erein \\~liicla~n HZc oncet~tratioti~s equal to
or less than 20% ant1 a dew poilit is equal to or higlier tliati 20°C, wliile performing an
annealing; -.
performing a third cooling of cooling the stecl to an elcvctith tc~npcrature
range of 500°C to 750°C at an average cooli~tgra te of equal to or lilorc than 1 "Clscc
arid 200 "Clsec;
j)erforming a fourth cooling of cooling tlie steel to a twelR11 temperature range
of 500°C to 25'C, at an average cooling rate \\~liicils~ 1 "Clsec to 200 "Clsec and is
faster than the average cooling rate of the third cooling:
heatins the steel again to a thirteenth tempei.ature range of 35OoC to 500°C, in
a case \\,here a cooli~~stgo p temperature of the fourth cooli~~isg l ower than 350°C;
retaining the steel in the thi~teentltiC lnj)erahlI'e range;
~nl\.anizi~tilgie stecl by i~tlmersinstl ie steel in a hot dip galvanizi~igb ath
\\~Iiichfl ows at a flow velocity of 10 ni11iiit1t o 50 nllmin after setting a plating bath
immersion sheet temperatc~re\e Iiich is a temperature when inunersing the steel in the
hot dip galvanizing bath, as a fourteenth tcinpesatuse range between a tenlperature
\vliich is lo\vcr than a hot dip galvanizing bath teniperatt~reb y 40°C ant1 a temperature
which is higher thao the hot dip galvanizing bath temperature by 50°C;
perfon~~ia~ni gal loying treat~nento the steel at a fifteenth tenlperatt~rer ange
of equal to or lo~vetrh an 600°C; and
cooling the steel to a temperature equal to or lower than 40°C.
[Claim 81
The manufactc~ringn iethotl of a hot-dip galvanized steel sheet according to
claim 6 or 7, \\,herein the aiinealing is perfornied at a temperature lo\ver tlian 840°C.
[Claim 91
The manufacturing method of a hot-dip galvanized steel sheet according to
clain~6 or 7. wl~ereint he annealing is performed at a temperature equal to or higher
tlian S40°C.
[Claim 101
The n~anufactoringm ethod of a hot-dip galvanized steel sheet according to
claitu 6 or 7,
\\,lierein tllc niolten steel further contains, by mass%, one or two or n~orco f
Cr: 0.05% to 1.0%,
Mo: 0.010/o to 1.0%,
Ni: O.Oj'% to 1.0%,
Cu: 0.05% to LO%,
Nb: 0.005% to 0.3%,
Ti: 0.005% to 0.3%.
v 0.005% to 0.5%,
B: 0.0001% to 0.01%,
Ca: 0.0005% to 0.04%,
Mg: 0.0005% to 0.04%, atid
REM: 0.0005% to 0.04%.