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The Process Metallurgy of Zinc-Coated Steel Wire and Galfan Bath Management

Frank ! Good"in
#nternational $ead Zinc %esearch &rgani'ation( #nc!( %esearch Triangle Park( )C *++,- ./S01
%oger )! Wright
%ensselaer Polytechnic #nstitute( Troy( )2 3*34, ./S01
05stract
The 6hysical metallurgy and related 6rocess and 6roduct 6erformance conce6ts for the
'inc and 'inc alloy hot di6 coating of steel "ire are 5riefly re7ie"ed( and are illustrated "ith a
detailed model of aluminum 5eha7ior in Galfan 6rocess technology! 066lications to hot di6
5ath management 6ractices are set forth!
Background
The coating of iron and steel "ith 'inc to im6ro7e corrosion resistance has 5een 6racticed
in 7arious forms for *8, years( and a thorough descri6tion of the numerous "ire-related
technologies has 5een com6iled in the hand5ook Ferrous Wire!
3
#n general( the 5asic unalloyed
'inc technologies may 5e grou6ed under the headings 9hot di6 gal7ani'ing: and
9electrogal7ani'ing:! ;ot di6 6ractice in7ol7es the 6assage of "ire through a molten 'inc 5ath(
"hereas electrogal7ani'ing in7ol7es electro6lating! The gal7ani'ed steel coating may in7ol7e no
further 6rocessing! 0lternati7ely( it may 5e redra"n( or other"ise re"orked( chromated or oiled!
#t is im6ortant to note that the success of these technologies and the ser7icea5ility of the
final 6roduct de6end su5stantially on 6rior conditioning of the "ire! Critical annealing( cleaning
and flu<ing .in the case of hot di61 6rocesses 6recede the coating ste6! Moreo7er( hot di6
coatings are o6timi'ed 5y the maintenance of small additions of aluminum in the 'inc 5ath and
5y 9"i6ing: and =uenching 6ractices u6on emergence from the 5ath! Modern( in de6th
6resentations on 'inc-5ased steel coating systems may 5e found in Zinc-Based Steel Coating
Systems> Production and Performance!
*
The 6hysical metallurgical 5asis of 'inc-coated steel
has 5een recently re7ie"ed in detail 5y Marder!
?
#t is 6ractical and economical to a66ly a 'inc alloy coating! 0lthough traditional
gal7ani'ed coatings "ith small .,!3@1 aluminum com6ositions are the most 6o6ular( the most
ra6idly gro"ing hot di6 coating is made "ith the Galfan 6rocess( "herein a Zn-A@ 0l coating
is a66lied 5y hot di66ing .all com6osition data in this 6a6er are in @ 5y "eight1! This 6a6er
re7ie"s this 6rocess and 6resents a model for management of the aluminum content in the hot
di6 Galfan 5ath!
Galfan Coating and #ts 0d7antages
#n 3-4,( researchers at Centre de %echerches MBtallurgi=ues( $iCge( Belgium( under
s6onsorshi6 of #nternational $ead Zinc %esearch &rgani'ation #nc!( de7elo6ed the Galfan
coating system( in7ol7ing a Zn-A@0l coating! Most commonly this coating in7ol7es a
mischmetal addition( containing lanthanum and cerium additions u6 to a5out ,!A@! The
Galfan coating system has 5een "idely licensed( and an e<tensi7e set of 0STM Standard
S6ecifications 6ertain! Galfan ingot for 6re6aration of the hot di6 5ath is addressed 5y 0STM
Designation B +A,---( and 5asic Galfan coated car5on steel "ire is addressed 5y 0STM
Designation 0 4A8E0 4A8M--4! The "ire may 5e dra"n after coating( and 0STM Designation 0
+8F .Ty6e C1 6ertains to Galfan coated and dra"n mechanical s6ring "ire! 0dditional
s6ecifications e<ist for strand .0STM 0 4AAE0 4AAM--4 and 0STM 0 -*A--41( for chain link
fence .0STM 0 43+--F and 0STM 0 4*F--A1( for ga5ions .0STM 0 -+F--+1( and for steel-
reinforced aluminum conductors .0STM B *?*EB *?*M--- and 0STM B F,3---1!
The Zn-0l 6hase diagram is sho"n in Figure 3( and an eutectic 6oint e<ists at a
com6osition of A@ 0l and at a tem6erature of ?43GC!
F
Thus( the Galfan microstructure is
largely that of a fine inters6ersion of the 'inc terminal solid solution( H( "ith u6 to 3!* @
aluminum( and the I 6hase( "ith at least 38!-@ aluminum! The eutectic microstructure can 5e
either lamellar or of a rod ty6e( and a mi<ture of the t"o structures is sho"n in Figure *!
A
#t is
6ossi5le for the Galfan microstructure to contain H dendrites( and such dendrites may a66ear in
conJunction "ith the rod ty6e eutectic structure!
A
The Galfan microstructure is sensiti7e to
cooling rate( "ith ra6id cooling refining the eutectic structure and tending to eliminate H
dendrites!
The additional of mischmetal to the Galfan com6osition im6ro7es the fluidity and
"etting characteristics of the molten alloy!
The Galfan coating 6ro7ides im6ro7ed corrosion resistance in com6arison to a
con7entional gal7ani'ed coating( com5ining( in effect( the 6assi7e corrosion inhi5ition of
aluminum o<idation "ith the acti7e and 6assi7e effects of 'inc! %e6resentati7e data are sho"n in
Figure ?!
8
Beyond this( the eutectic structure is =uite ductile( and Galfan 6rocessing a7oids the
more 5rittle intermetallic 6hases that can e<ist in con7entional gal7ani'ed coatings!
+
;ence(
Galfan coated steel "ire can 5e e<tensi7ely redra"n and su5Jected to relati7ely se7ere "ire
forming o6erations! 0driaensen has discussed the ad7antages of Galfan coated "ire( 7is-a-7is
con7entional gal7ani'ed "ire( for steel s6rings and s6ring manufacturing( including consistency
of s6ring length .associated "ith a decreased frictional interaction "ith coiling tools1( and the
good adherence of the Galfan coating to organic coatings!
4
T"o Galfan Processing #ssues
Molten Galfan alloy is not com6ati5le "ith the flu< systems normally used "ith
con7entional gal7ani'ing! While alternate flu<ing arrangements are 6ossi5le( this 6rocess
limitation has led to "ide usage of :dou5le di66ing: 6rocesses "herein the Galfan hot di6
sim6ly follo"s a con7entional gal7ani'ing hot di6( as schematically illustrated in Figure F!
#n the dou5le di6 6rocessing( the 6ro6erly annealed( cleaned and flu<ed steel ac=uires a
gal7ani'ed coating in the first 5ath! This coating "ill generally include a series of iron-'inc
intermetallic com6ounds at the iron-'inc interface( together "ith an o7erlay that is nearly 6ure
'inc! The series of intermetallic com6ounds can 5e a source of coating 5rittleness! When the
gal7ani'ed "ire enters the second 5ath( containing molten Galfan( the 5ath tem6erature "ill
generally 5e high enough to melt or dissol7e the essentially 'inc gal7ani'ed o7erlay( and(
furthermore( to transform the iron-'inc intermetallic layer into an aluminum-iron-'inc
intermetallic! /6on emergence from the Galfan 5ath a layer of essentially Galfan alloy
solidifies on to6 of the transformed aluminum-iron-'inc intermetallic layer!
The a5o7e scenario is not one of steady-state( ho"e7er( and the aluminum that enters into
the aluminum-iron-'inc intermetallic layer inherently lo"ers the aluminum concentration in the
Galfan 5ath! Thus( Galfan 5ath management re=uires the monitoring and management of the
aluminum concentration! This 6a6er sets forth( 5elo"( a 6rocess model that can 5e used 5y
Galfan 6rocessors to understand and undertake such 5ath management!
0 Model of Galfan Bath 0luminum Concentration
$et us start "ith the assum6tion that the 6rocess line is a5le to add Galfan alloy to kee6
the 5ath mass constant in the face of "ithdra"al of alloy from the 6assage of "ire! #n such a
case( the incremental de6letion of aluminum in the 5ath( associated "ith an increment of "ire
coating( can 5e e<6ressed as follo"s>
.M1 dC K - # d0 L .,!,A1 G d0 - C W d0( .31
"here C is the aluminum concentration in the 5ath( dC is the incremental change in 5ath
aluminum concentration( d0 is the increment of "ire surface coated( M is the mass of the 5ath( #
is the mass of aluminum 6er unit of "ire surface area in the transformed intermetallic layer( G is
the net mass of Galfan melt remo7ed 6er unit of "ire surface area( and W is the mass of the
Galfan o7erlay that solidifies 6er unit of "ire surface area!
The e<6ression at the left in =uation .31 is sim6ly the incremental mass of aluminum
lost "hen an increment of "ire surface area( d0( is coated in the Galfan 5ath! The first
e<6ression on the right of e=uation .31 is the mass of aluminum that is lost to the transformed
intermetallic layer "hen an increment of "ire surface area is coated! The second e<6ression on
the right of =uation .31 is the amount of aluminum that is added to the 5ath 6er increment of
"ire surface area( assuming simultaneous 5ath re6lenishment "ith Galfan alloy! The third
e<6ression on the right of =uation .31 is the aluminum lost 6er increment of "ire surface area
coated sim6ly due to the solidification of the 5ath alloy on the emerging "ire!
=uation .31 can 5e usefully reorgani'ed as follo"s>
"here
dC K - . M L 2C1 d0( .*1
M K N # - .,!,A1 GO E M .?1
and
2 K W E M! .F1
Further reorgani'ation leads to the e<6ression>
dC E . M L 2C1 K - d0! .A1
&ne can no" sim6ly integrate 5oth sides of =uation .A1! &n the right side( one can integrate
5et"een the limits of 'ero and the total surface area coated( namely 0! &n the left side one
integrates 5et"een the limits of the starting 5ath com6osition( C
,
( and the final 5ath
com6osition( C
3
( arri7ed at after the coating of "ire of surface area 0! The resulting e=uation is>
.3E21 Nln .M L 2C
3
1 - ln .M L 2C
,
1O K -0! .81
Multi6lying through 5y .21 and raising 5oth sides of the e=uation to an e<6onential( one o5tains>
.M L 2C
3
1 E .M L 2C
,
1 K e<6 .-201! .+1
Finally( if one su5stitutes Z for ME2( one o5tains the relati7ely con7enient e<6ression>
C
3
K .Z L C
,
1 e<6 .-201 - Z! .41
&f course( Z is N# - .,!,A1 GO E W "ith 2 5eing WEM! &ne can see( 5y ins6ection( the tri7ial case
of C
3
sim6ly 5eing C
,
"hen no area of "ire has 5een coated! 0 6ractical illustrati7e calculation
is undertaken 5elo"!
0 Practical <am6le
Consider the Galfan coating of *(,,, kg of 3 mm diameter steel "ire! The length of
this "ire is ?*?(,,, m and the surface area( 0( of this amount of "ire can 5e calculated to 5e
roughly 3(,,, m
*
! /seful formulae and ta5les for such calculations may 5e found in the
hand5ook Ferrous Wire!
-
)o"( let the 5ath mass( M( 5e maintained at 3,(,,, kg! #n such
6rocessing( the gal7ani'ed and Galfan coating "eights can 5e relati7ely insensiti7e to line
s6eed( and a 6ractical 6rocess might in7ol7e a gal7ani'ed coating of *A, gEm
*
and a o7erall
coating "eight after the Galfan 5ath of ?*, gEm
*
! Thus( the 7alue of G "ould 5e +, gEm
*
!
Careful measurements of the intermetallic layer after 6assage through the Galfan 5ath in such
cases "ill re7eal an intermetallic layer "eight of a5out *, gEm
*
( "ith an aluminum le7el( #( in the
intermetallic layer of a5out 4 gEm
*
! The 7alue of W is therefore .?*, - *,1 or ?,, gEm
*
! &n this
5asis( Z is ,!,3A( 2 is ,!,,,,? m
-*
and 02 is ,!,?! Thus( C
3
can 5e calculated as a5out ,!,F4(
do"n only F@ from the C
,
7alue of ,!,A!
0t a line s6eed of *, mEmin( and "ith si< lines in 6arallel( this "ire could 5e 6rocessed in
FA hours or 7ery roughly si< eight-hour shifts! During this time( the Galfan alloy to 5e
re6lenished "ould 5e a5out +, kg .+, gEm
*
< 3(,,, m
*
P 3(,,, gEkg1( and an aluminum
su66lement of *, kg "ould maintain the aluminum le7el! The su66lemental aluminum addition
is sim6ly F@ of the 6roduct of ,!,A and the 5ath mass of 3,(,,, kg! ;andled on a 6er shift 5asis(
careful 5ath management can( in 6rinci6le( 5e achie7ed!
More refined modeling can 5e done( as necessary! 0mong other considerations( one can
adJust for the 5ath 9o7erfill: constituted 5y the aluminum that is added on to6 of the Galfan
re6lenishment! ;o"e7er( this sim6le model offers a good start for so6histicated 5ath
management analysis!
General Procedure
/sing the =uation .41 and reasona5le 7alues of the se7eral 6rocess descri6tors and
6arameters in7ol7ed( one can certainly 6lan tentati7e 5ath maintenance 6ractices for a "ide
7ariety of Galfan 6rocessing lines! The general a66roach "ould in7ol7e a rate of 5ath
re6lenishment "ith Galfan alloy together "ith a rate of addition of su66lemental aluminum! #t
should 5e noted that the addition of aluminum re=uires care( lest e<cessi7e 5ath surface dross
result and foul the coating 6rocess! The addition of molten aluminum is ad7ocated( "here
6ractical( although useful techni=ues e<ist for su5mersion en route to dissolution!
&57iously( 6eriodic 5ath analysis should 5e undertaken to monitor and fine-tune this
a66roach! Certainly direct o5ser7ation of 5ath mass re6lenishment needs "ill 6ro7ide a refined
estimate of the 7alue of G! Similar o5ser7ations of gal7ani'ing 5ath re6lenishing needs should
6ro7ide a reasona5le estimate of the gal7ani'ed coating "eight( "hich "hen added to G "ill gi7e
the o7erall coating "eight! The 7alue of W can 5e estimated 5y su5tracting *, gEm
*
from the
o7erall coating "eight( and so forth!
#n general( =uation .41 and the illustrati7e calculations a5o7e should only ser7e as a
starting 6oint for 5ath management 6olicy de7elo6ment! So6histicated 5ath management
6ractices e7ol7e from an e7er-increasing e7aluation of the 6rocess under scrutiny( not unlike the
de7elo6ment of control methodology in 9smart: systems!
Summary
The 6rocess metallurgy of the 'inc "ire coating technology has 5een re7ie"ed "ith
em6hasis on a dou5le di6 Galfan 6rocess! 0 6rocess model has 5een set forth as a guide for the
de7elo6ment of so6histicated 5ath management techni=ue!
%eferences>
3! Ferrous Wire( Qolume 3 .0!B! Do7e( editor-in-chief1( Wire 0ssociation #nternational
.Guilford( CT1( 3-4-( 66! A*+-A84!
*! Zinc-Based Steel Coating Systems> Production and Performance .F!! Good"in( ed!1(
The Minerals( Metals R Materials Society .Warrendale( P01( 3--4!
?! 0!%! Marder( 9The Metallurgy of Zinc-Coated Steel:( Progress in Materials Science(
*,,, Qol! FA( 66! 3-3-*+3!
F! S !$! Murray( Binary 0lloy Phase Diagrams .T!B! Massalski( ed!1( 0SM .Materials
Park( &;1( 3-48( 6! 34A!
A! F! ;inter5erger( W! Maschek( and S! Faderl( 9#nfluence of Ty6ical Process Parameters
on the Microstructure of Galfan Coatings:( Zinc-Based Steel Coating Systems>
Production and Performance .F!! Good"in( ed!1( The Minerals( Metals R Materials
Society .Warrendale( P01( 3--4( 66! *43-*-*!
8! 2! /chima( M! ;asaka( and ;! Toga( 9ffect of Structure and Mischmetal 0ddition
on the Corrosion Beha7ior of ZnA mass@ 0l 0lloy:( G0$Q0TC; U4-( The #ron
and Steel #nstitute of Sa6an .Tokyo( Sa6an1( 3-4-( 6! AFA!
+! S !%!;! Shah( S!0! Dile"iJns and %!D! Sones( 9The Structure and Deformation
Beha7ior of Zinc-%ich Coatings on Steel Sheet:( G0$Q0TC; U-*( Stahl und isen(
3--*( 6! 3,A!
4! $! 0driaensen( 9Corrosion Pro6erties of Wire Forms Made "ith Pre-Coated S6ring
Wires:( W#% 8E3---( S6ringer Qerlag .Bam5erg( Germany1( 3---!
-! Ferrous Wire( Qolume 3 .0!B! Do7e( editor-in-chief1( Wire 0ssociation #nternational
.Guilford( CT1( 3-4-( 66! 83?-8A4!
3,! S !$! ;ostetler( 6ri7ate communication( 3--4!
Figure Ca6tions
Figure 3! The Zn-0l 6hase diagram!
F
Figure *! %e6resentati7e microstructure of a Galfan coating( sho"ing lamellar and
rod-sha6ed eutectic structure!
A
Figure ?! %e6resentati7e data sho"ing that a reduced rate of corrosion is sustained 5y
Galfan coated "ire in com6arison to gal7ani'ed "ire! Data "ere taken in an industrial
atmos6here .0magasaki( Sa6an1!
8
Figure F! Schematic re6resentation of a dou5le-di6 Galfan 6rocessing line!
Figure 3! The Zn-0l Phase diagram!
F
Figure *! %e6resentati7e microstructure of a Galfan coating( sho"ing lamellar and rod-
sha6ed eutectic structure!
A
Figure ?! %e6resentati7e data sho"ing that a reduced rate of corrosion is sustained 5y
Galfan coated "ire in com6arison to gal7ani'ed "ire! Data "ere taken in an industrial
atmos6here .0magasaki( Sa6an1!
8
Figure F! Schematic re6resentation of a dou5le-di6 Galfan 6rocessing line!

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