Surface Technoh;gy. ~,. ( ~e " 7 ,) . .

, I ~-~v,, - I I " ,
E l s e v i e r S e q u o i a S . A . , t ~ a u s a n n e - - Pr]~ ~ed in t h e Nether~;~ n.d~

THE FORMATION AND PERFORMANCE

S I O N C' O A ~"', I N ~~ S~ ( ) N Z I N ( ; *

OF CHROMATE

CONVERo

L. F. G. W I L L I A M S

Australian Defe~.~ce Sci,:ntific Service, Moierials Research Labor~t(:,rie~, P.O. Bo:x 50,
Ascot Vah', Vic. 302::, /~!etbournc ( A u ~ r a ~ )
(Received September

2, 1 9~ 6 )

Summary

This p a p e r dea!,s witb ~he m e c h a n i s m s (,f f o r m a t i o n ( f chror, qate ,:o~v e r s i o n films on zinc a n d t h ei r p e r f o r m a n c e characte~4/i-'.~, The c omp~,,dt~[)~
o f c h r o m a t e c o n v e r s i o n films is r o v i e w e d t o g e t h e r wit h t h e e f f e c t s o f a n i o n s
s u c h as s u l p h a t e .
Initially, aging o f films .esmt,s in t h e w e l t - k n o w n h a r d e n i n g o f t h e coating, b u t s u b ~ q u e n t l y , o t h e r c h a n g e s c a n o c c u r , suci~ as c r a c k i n g o f t h e film
a n d a r e d u c t i o n in t h e d e ~ o r p t i o n r a t e o f tLe c L r o m a t e f r o m t b e film. Tiie
c o r r o s i o n p r o t e c t i o n c o n f e ~ e d b y tlae fi!n:s is (iel~e,.~oe,~t: or~ ~
bar~]e'~
n a t u r e o f t h e p r e c i p i t a t o d c t ~ r o m i u m I I I I ) h y d r o x i d e .a,~'*_.._;on. . .the)
.
inbi}~i~.
:...~oo.,,,~,
p r o p e r t i e s o f t h e a d s o r b e d c h r o m a t e , With i r : ~ e ~ ( ~ ~.~: ~- ~}~0'~,,'-~:~
. . . . ,. ..,. . .
o f t h e c h r o m a t e a n d , t.h,a~,:'efore, tl~e 1)rotec~,~oa give;, by t!=,. f~'-n~ arc afro., t
ed b y t h e aging proceeds.
~.ccelerated test n~e~..hods, s~ch ,~:, ~ n(~ salt s p r a ) *
s h o w n to be unreliah~,, The c h r o ' n a I c conte~)t of th~ fi!m ,.)~,s ~:()t ,~r~...~,,~
t h e c o r r o s i o n r~sistance, p r o b a b l y b,~,cause {a) t h e qual_,ty of t h e u r ~ d e r l y ~ ~
zinc plaice has a s u b s t a n t i a l e f f e c t o n ~he c o r r o s i o n r e a c t i o n a ~ ~b} t h e
leacI~ ing rate o r d e s o r p t i o n ~f t h e c h r o m a t e is d e p e n d v n ~ on aai~,,,, ~ }~
films.

Int]~c,ductmn
Chromat

..

~~!

~.~v~

~ ! ~

~ ~

h u m i d s t o r a g e c o n d i t i o n s a n d ~t ~ i'te,a . : ~ r o n ~ a t e d
~vh(w. ti ~,s i,o be sto~cd for
e x t e n d ~ p e r i o d s , In recen~ y e a r s h~,~e t~a~ been a~ i~o~vas~g !r~d t~.)v~.~r~i
l~he use o f zinc e ! e c t r o p i a t e b e c a u ~ o f ~he t o x i c i t y oi cadres, urn a~~d ~s
~'P~w~;r p r e p a r e d Zo~~ ~..... . ~. .L.~ , ~| ~k ~ t ~ ' : ' ~ " ~
F i n i s h i n g , , O ~ o b e r .~ 9 ~ ~.

~ ~i;

~}~,~'

106
TABLE 1
Classification of c h r o m a t e eoaversion coatings
Coal3ng tyoe

Typica~ a p p e a r a n c e

Typical
coating
weight
( g m 2)

Typical
CrtVt)
content
(rag m 2)

A-(~iear

"l~ansparent, clear s o m e t b n e s ~.~ith

at bluish tinge

u p to 0.5

B-Bleached

T r a n s p a r e n t w i t h slight
iridescence

u p to 1,0

5 - ~0

C-Iridescent

Yellow iridescent

1.0 - 1.5

50 - IO0

D-Opaque

O![ive green shading to b r o w n or

bronze

=, 1.5

I 0 0 - 200

. - ~ - , ~

greater cost. ~ munitions are often stored for lengthy period=, under
conditions of normal atmospheric cycling o f t e m p e r a t u r e and humidity,
haterest at Ma~fial~ R e , arch J'.~boratories (MRL) has been cent,red on the
pro~,ective properties of the~,e films. To understand the corrosion

mechanisms, basic knowledge was required of the formation a',d aging

properties of ~he films.
This paper outlines the d,~eloprnertt of c h r o m a t e conversb n coating,,~
on zinc and dmcusses their m e c a a n i s m of format.ion and bash: st ~cture. The
mode of corrosion of chroma:;ed zinc electroplate is presented as we~l a:; a
discussion of accelerated corrosion test m,:thods.

Deve~.opment of t h e chromating process

After the early discovery by Wilhelm [ 1 ] , Anderson [2 ] made a comprehensive study of the formation of chromate co~wersicn coatings on zinc.
He d e v e l o p ~ t h e well-known Crcnak solution [200 g Na2Cr..~OT-2H20,
6 - 9 mi H2SO4 (s.g. 1 . 8 4 ) a n d 1 I of H20)~ which operated at ~oom temperature with immersion times of 5 - ! 5 s . These cnr,.,
" mate e o n w r s i o n coatings
were an iridescent-yellow cotour. Other ch_romatmg solutions were developed
later but these continued to rely on an ac,di~'
~ e dichromate solutio~ with
added at.iotas [3 ] such as sulphate, c~loiide, fo!,mate, phosp?ate ~n,d fluoride. As ',hown below, these anions h,~e a s~ectacu!ar effe~;t o.~ the rate of
formatAo~ of films on~ zinc [4 ]. T h e advaniager~ o f v ~ i o u s prepri,etary seiutions are ~ot cle~xly r e ~ r t e d b u t , in those results publish,.~i [ 5, 6] e~d in
unoublished work by Esmore ~ d Lindemayer, t h e C~onak pruce~s was equivalent in c.mos~on
"~-~ '
preventio,~. ~o 1;he proprietary ~ l u t i o n s testc~O.. ~ m e of
these res,,lts are s how~ inF g.. ! in whwn t h e t i m e ~ failur~ in a salt spray
test of r , r o p r i e t ~ y and Cronak proce~e~ i~ co~pmed. Adva~ces in

TABI, E 2
P e r c e n t a g e c : , m p ~sitio~i <)f a n u m b e r
c o a t i n ~ / s ,n z i n c

o i ( ' h r ( ) n , : ~ : ( ' c,:~)~,,~ , ,~,.>~

C',roo.ak

,..r~,Y3, ;~a.*. '.

Chromiam(V['
C h r o m l ~ u m ( l l )"
,,~
~u p h a,, ("
C h t)ride
Lilac
Waler

~';.7
28

19

15

Re%rent("

l'-~ 1

l ~'71

T ! '2
2:, - 3t)

3
2~',

"
:2 ~.

3.3

21 -

'2. I

3,!,

'2 .~ 1 2 . 5
- ~.)

'

,!

Ii

":
:':qilh~&!

i
,

, :z

A!t,i.).o~.~gh t h i s a l k a } d ~ , ,

..........

108

d
~2

O*

02

03

Concentration, Na:~RQ~,mol/l
Fig. , . The effect o f s o d i u m sulphate a d d i t i o n s on the weiglht of film f o r m e d and v zinc
d issolved ot~ a 120 a immersion in 0.12 m~l I I Cr
, o~
~a soluttons at 20 'C,

Tire m e c h ~ m

of formaation of chromate conversion coa$ings

This is one area which h ~ received very li~le attention. Since the early
work of A n d e ~ n [~] ahd .Clarke m~d Andrew [7] there have been few
publications on the rate of formation of films [8] or on the effect of added
anions on the chmmating reaction [ 4, 9]. Chemical analyses of the fihas
formed on zinc (Table 2) are consistent with the following reactions:
Cr~O~- + 14H" + 6e -, 2Cr a" + 7H,,O

(1)

Zn-* Zn ~' + 2e

(2)

Tl'e reduced Cr a" is precipitated on the surfa..e of the zinc probably

as a hydrated oxide. Zinc is only found in ~:ne film in trace quantities and
normally accumulates in the chromating solution. These reactions, however,
are dependent on anions which do not appear in the above ~quations. For
eample, in pure CrOa solutions it is well known that zinc does n o t dissolw:,
to ~r,y a[ preclable extent. On the addition of sulphate (Fig. 2), the zinc
dissolves and a visibM coating is formed on the zinc surface.
All recent evidence f4] supports the proposal oy McLaren et al. | 1 0 ] ,
that chromate conversion coatings are hydrated cbromium(iYt) oxide films
with adsorbed anions such as chromate and sulphate. Nevertheless, the early
suggestion of Anderson [ 2 ] , t h a t the film consists of a basic chromium
chromate, has appeared in s o m e recent publications [11 - 1 3 ] . The
chromium(Ill) hydroxide should precipitate if the pH in the vicinity of the
zinc surface is approximately 2. Although ~he pH of most chromating solutions is lower than this vatu~ tha hyd~oger~ i~,,~ i~ ,.~.o..,~...~ ~.......... ,:~-and the pH change at the surface permits the preeipi~Ltion of CrIOA)a.
This surface pH value is reported to have been measured for a 0.07 mol
1 ~ (~(VI! solution containing a d d ~ sulphutic aci'd [14]. At low H2804
concentrations, a p H o f ! , 7 5 ~
m e ~ u r e d ~ m ~ i i a t e t y on immersion and
this was n,~in~ined for ~ m e min~t~,,i~At-hi~er.H~SO:~
,
. .......
tone-at;rations
the
pH d e c r e ~ e d linearly
v ~ u e . For
example~ ~dth 0.02 mo
t o stabilize at
the zinc surface.. This :~otk a l s o ~iaowed t h a t t h e pH was : i n d e ~ n d e n t o f

TABLE

E f f e c t o f h e a l i n g ()n chromat-,~' e,)ating, s [ ~ r, ]

T e m p e r a ~ urn'
~t" d r y i n g

Room
50
75
1 O0
150

A p p e : ' r a n e ' af!~'r 9f~ h

,salt s p r a y *
Zn

Cd

NC
TC
SC
C
C

NC
NC
S(:
,;
C

* N C , n o c o r r o s i o n ; ' F C", t r a c e c o r r o s i o n

, , e a c h a l ) l e ('r( V | ~
~ ~ fi ~m
,,pg c m
,
Zn

20
2()
13
0.3

b'(? , s l i g h t c ( ~ r r o s i o n ; C ,

general c o r r o s i o n .

whether cast or plated zinc was used. It is unfortunate that Aub()4 addition.
were used during these experiments beeause, as already indicated ~ Fig. 2,
t h e s u l p h a t e ion as well as; i.he h y d r o g e n ion d i r e c t l y a f f e c t s t h e ch:'c ma~in~

reaction.
T h e role o f a d d e d a n i o n s d u r i n l i c h r o m a t i n g , ~s b~triguin~. Tl~ey at(,
u n l i k e l y to affect, d i r v c t l y e i t h e r o f th..e red~>x r~,a,:tions a~d pr~bat,,iy :~,c~ t~v
e i t h e r c o m p l e x i n g w i t h c h r o m i u m ( t l ! ) in the, film or a l t e r i ~ th:, i;~"-~:i:"r~ i<,-.
o f t h e p r e c i p i t a t e d c h r o m i u m ~ l l l ) t~vdroxul~ b y a<l~<~r~
~ ,
~-.:i.-.,
Fig. 2 d o e s n o t (~ccur w i t h th(:. c h l o r i d e ion 14]. :ks t h e stai:,iiit) ('(~:~sla~,:<
for c h r o m i u m ( I : ~ l ) c(:)ml~i(:,x.~,"~ o f (:1 a n d S(,~i" at' ~, si~nitar ~h,t,~~ i"~ ',;~,
, ' o m p l e x i n g r e a ( t i o n was t h e mai.u reas~:;n f()r t h e ~ha;~(, ,:)f ~.h,, , . ~ r v , , , . :~
m a x i m u m w o u l d also h e e x p e c t e d for Ci a d d i t i o n s . 'i'hie~ skaggosls ~.ha;i. t i~( ~
s u l p h a t e o r . h l o n d e is i n ( o r p o r a t e d in t h e film b v a d s o r p t i o n si,~,;lar ~) vh(,
m o d e o f i n c o r p o r a t i o n o f c h r o m i u m ( V i i . The welt~ka(1)w~ dif[eren(:(' i~:
a d s o r p t i o n p r o p e r t i e s be',.we~,n qr~
,,,.,.~ a n d C1 t",m ~. .a. .c.c. ,. ~. .u. .n t f:)r ~'::~-:, d ~ f f ~ ~ ~ . 0 .
in film w e i g h t v e r s u s con~:en : r a t i o n o f a d d e d a n i o n cur-ecs ',-~i. ~Fl~is e:, !~tar.a
t i o n is f u r t h e r r e i n f o r c e d b y t h e c h e m i c a i analys,.~s in Tagi(, 2 wr~('h s h o w
t h a t a h i g h e r p r o p o r t i o n ()f SO~ t h a n Ci is retain(~d in ~:.hc f:.;.
~.~.

w h e n n e w l y f o r m e d . Thi~ can be (~verc,.;me by air d r y i n g for 24 i~ or ~y

f o r c e d d r y i n g . I h e t e m p e r a t u r e at whic! ~, t h e ' r ...... ~
' :fi~.a~-~;iv
affects the pro~ective t~roperties of these coatings degwnds on ~h,:, t~a~ ~ ,,!
h e a t i n g a n d t h e m e t h o d u s e d t o evaluat,e t h e c o ~ ' o s i o a rvsis~ance. ~~,r
s h o w n in Table 3 and t h i s b,as

be~:,~,

r"--~'~.m'~"~ L , ~.............. ' .....

110

panels were subjected to excessive hea~, the chromate was not leached from
the film during salt spray testiag and there was an accompanying loss in
cgrrosion resistance. However, when the samt pmaels were subjected to an
outdoor.2xposure test, the corrosion resistance of panels heated to even
80 C for 2 h gave similar p~rfotmances to air dried panels [ 16]. The weli=
established procedure [ 3] of restricting the drying temperature has some
h, undation but, in many instances, and particularly with type A m~d B films,
higher temperatures may be used without any detrimental effect on the
protective value of the film.
Heatint4 to 150 C results in the formation of ~ 2 0 3 , as determined
by X-ray analysis.., and, if the film is still in contact with the zinc metal, zinc
chromate is also detected [2]. This effect was noted for free Cr(OH)3 as
early as 1901 [ 17 ]. If heating of the article after chromating is unavoidable,
e.g. for relief of hydrogen e m b r i t t l e m e ~ t post-treatments with sodium silicate, barium nitrate or glycerine are., reported to be partially successful in
preserving the corrosion resi~t~n,ce i[18]. However, it is usual to form the
chromate coating after her. ~ing, when it is customary to reactivate the zinc
surface with a short dip i~:: an acidic solution [ 3 ].
Once the films are formed, they '.an be cracked by heating, storing in
dehumidified air at room temperature, placing them m a vacuum or placi~:g
them out in dry' sunny conditior,s for ,>ne day [ 16]. The cracking of the film
is shown in Fig. 3 where an air dried film (no cracks evident) was ulaced ~n
the scanning eiectton microscope. D,.spite the appearance, there is n~,
degradation in corrosion protection associated with simple cracking of ~he
films either in the salt spryly or c u t d o o r exposure test [ i 6].

Corrosion protection of chromate conversion coatir,:gs

As already mentioned abo~e, the comparative corrosion protectioa of
these films depends to a large extent on the t y p e of environr~ent in which
they are exposed. For example, heating of the coating affects the response to
a salt spray test but not to a~l o u t d o o r exposure test. An understanding of
these apparent anomalies re<luires a reasonable knowledge of the mechanism
of the protection of the zinc by chromate coatings.
In protecting the underlying zinc all chromate conversion coatings act
C coatings, is typically 0.1 - 0.6 pm thick. For coatings which contain only
minor amounts of Cr(Vi), i.e. type A and B in Table 1, this i,~ the main mode
of protection of the zinc. A typical time to failure in the salt: spray test for
such coatings is 24 - 48 h.
Type C and D coatings also contain c h r o m a t e which is adsorbed on the
Cr{OH):~. in aqueous medium this can be leached from the coating am.l can
lead to a repassivaLion of damaged areas on t h e surface. This ~ate of desorpt~oa of chromate aopears t o be dependen~ on the history o:~tlhe coating. In
an accelerated test like ~he ~ t t spray., the deso~ption occurs readily wi~h air

11

(a)

(c)

tb)

(d}

Fig. 3, Scanning e!ectron mierographs of c!~romated zinc pane|s: (a) air dried ::~1 ~~::~~
(850 x ) , ( b ) a n d (e) dal:ksp~,tson the surface after ~.7 b ~a~t spra?' ie:;tit:~: ~:r~d ~d}l.i~ :,,.~.~
spot as (b) with the eorrosio products relnoved {,: 150).

d r i e d c o a t i n g s d u r i n ~ t h e f o r e d a y s o f t h e t.est~ 1~~ ~'ompa~isox~, ~he ,..:~(.~v~,~,~

d o e s n o t d e s o r b froa~ c o a t i n ~ s w h i c h have b e e n ~;.~te~i to SO (~ f~~ 2 }~ i !~i}
In o u t d o o r e x p o s u r e w h e r e t h e l e a c h i n g is m. t~ch s l o w~'~,
.:. ,~ ~i:~
..............
~ ,~l.~(~r:c~~::
, ;,~"~.
.... ~~f
w e r e h e a t e d [ ~ao'j o
It is easy t o u n d e r s t a n d t h e p r o b i e m s <,f accei~:rat~d <:~::,r~~s~.:~-,. i c - ~ ~
c f ? y p e G a n d D c o a t i n g s {air d r i e d ) as r~p~d i e a c h i e g o f t,he cb:ron:~a~.e ir~)~~
t h e film i~ r e q u i r e d , This is n o t a n o r m a l circ~':~si:ar~ce, as corrosi':~v~ ~:i~t}-~~
c h r o m a t e ~ zinc e l e c t r o d e p o s i t m a y t a k e ~o:~t~;.s o r eve;~ year.:.~. 3:h~s. ~:orr~,[at i o n s b e t w e e n a c c e l e r a t e d test m e t h o d s anP, :0~,~ua! o~.~tdoor ~",v~:,s.~..~r,~::a'~
misleading ]
un,~.ess"t h e r e is a c~o~.
: ' a,~ ' e ' ~ ,
. . . . . . . . . . . . ~..-v~,~. ,~,~
in t h e a c c e l e r a t e d ; e s t a n d 'l:he a c ~ . a ; :::;-:sur~ .;i~,e~ 1-:k?r i ~ a t a n c e , Kat~z e t a t .
f20] re~rg~
a g o o d c o r r e l a t i o n b e t w e e n p a n e i s e x N ) s ~ in t h e salt. s p r a y
te,,~t a n d d u p l i c a t e s e x p o s e d c l o s e t~:~ b e a ~ : : : :

112

....

!Ill
II

Fig. 4. The ~ver~qI~t:i~ to mpl~'~van~ of white ~me~. ,a produc~ it, the ~alt ~pray u~stmg
of six different batehes (A - F} of ~mmercial zinc ~tectroplate, ~howia[ the var~tio~ in
:re~ult~ f~om four diffe~nt o ~ ~ a l
a i r ~pr~y cabin~t~ [ 221,

The first s i ~ o f c o r r o s i o n o f chromated zinc ~n the mlt spray te~t [ 21 ],

'~he humidity test a:~,d outdoor exposure [ 161 is tt~e apl~2arance ot black
spots. Th~ is due to corrosion under the chromate conversion film~ ~ shown
in Fig. 3 fear spots produced in the salt spray test. 'l'he chromate coating
usually covers the corrosion product, as shown in Figs. 3(b} and (c}. The
corrosion product can be seen in Fig. :;(c ). 'When tI',.~ corr)sion products are
removed, F~g. 3(d) shows that corrosion of the 13 ut]~ l~hick 7h~c electro, plate
has occtu~red through to the steel surfa~.'*:.

Salt spray t ~ t s
Most :;alt spray tests conform generally with th<- ASTM B117 standard
test method, except ~hat the volumes of the cabinets are often less than t~e
0.43 m 3 (15 ft "~) specified, t6~ho:~gh the grading of panels is comparable
from one cabinet to apother, the absolute time to failure cannot be
c o m p ~ e d accurately from one cabinet to ~ g t h e r . The resuits of two series
~f comparative trials ef salt spray cabmets have been published [ 22 ] and
~hc w variations in time to failu~ of up to i000%. The histogra~a (Fig. 4)
:shows figures for electroplate prepar~i by ~x different ptate~ and tested by
focr different laboratories, Similar in~x~nsislencies have been re~<)rted wher~
cor~parat;v,~ s~lt spray test trials have been conducted [23].
The ~easons for the lack of correL~.~on have n o t ~ e n resolved. 1~ was
~eaerally f~tt [ 16 ~3] t~h~t the inco~sistencies were caused by impurity
:te~'els in the s~t, the w a ~ r or t a'~e a m
~ ~n an effo~ to el~im~nate ~wo of these
va::iabla:, a third comme~'cial e x ~ c i ~ ~
c o n d u c t ~ by Materials R ~ a r ~ h

2
O

~, tO0

o
v

.~:

Fig, 5. The a w . r a g e t i m e t o , q ~ p e a r a n c e o f wh~tc curc~sion / p ~ d a.:ts o n ~;etb ,~I-s~ pa~+'~.~

tZinc p l a t e d a r d c h r o m a t e d ,n ~,ne bat.oh) t')~ d u l ) l i , ' ~ e 0',~I,e~" men~.~ ~n ~'ivc ,~if;er~'n~ ~.;~!'

s~andard steel p;,~ets(,n a 2

p l a t e d a n d c h ~ o m a ,ed in

h ~.imuttant o, t~s+':~:g)~s~arc i: t h ~ c a b i n ~ . I s

one

. . . . . . . . .

w a s d i s s o ! v c < ! in die,tilled ws,.,,,r t o m a ~ e t,:," 5 , ; ~

effort

was mad-

,,:) s t a n f l a r c l i z e ,.he o ~ + r a t o r s

Jwi , ~

ir + h e i r

.~,~,i,,~.~.
.... i

-, ++ ~....

s t e e l p a n e l s w e r e a l s o e x l : ~ ) s e d in t h e s aig s p r a y ~:abi~-~t,~,; ~
w~ i~:?, ~,~;-~
~v+.,re d e t e r m i n e d f o r a 2 4 h p e r i o d .
T h e r e s u l t s o f t h e trial ar~ c o l l a t e d ir~ ~'i~,~+,, 5 ~ , ~ ....~ ~'~ ",~~,~, ',: :~I ,~ : /
achieved previeusly

~see F i g . 4). S i x z i n c ~.,~o~: ~ w~ ~'c c.,,p~,~cd ,~, ,,,~;, c a b m e ~

114

and the results axe given ~s a r~. average time to failure. Duplic~Le tests were
conducted in each cabihet. The differences in time to faiture between the
~two runs in each cabinet ranged between 0 and 40% whilst i.he ave~'~:~e time
for ail experiments was 181 h ~ i t h a sta~dard deviation of 48. The worst
:individual results were 47% high and 39% '~w when compared with the
average. If values o f 96 or 72 h are to be used rigidly as standard values in
the salt test, then even the values obtained under quite well-controlled co.~ditions {more stringent than the A~,TM Bl17 S t a n d a r d ) a r e not sufficiently
reproducible.
The comparison between the time to failure for the zinc plate and the
weLght loss of plain steel panels can be ~een in Fig, 6. When analy~d by
linear regressio~ a value of the coefficient of determination (r ~ ) was 0.12,
confirming that there is no s!gmf cant correlation between the two variables
m Fig. 6,
The ASTM Standard B l 1 7 repox~s that periodic fluctuations in air
pressure of 3.4 kPa (0.5 psi) can result in a two-fold increase in corrosivity
,of the fog as shown by the work o f Damey and Cavanagh [ 25 ]. On close
,examination of their paper, the corrosivity (as measured by weight loss of
one ~eel p a n e l ) o n l y vaned stgmflcan,ly in one of the four experiments
where a 1,63 mm air nozzle was positioned 0.13 mm below the tip of the
fluid nozzle. This one point is n o t repeated in the paper even when better
,control of the pressure was achieved i- a second series of experiments. The
problem of air pressure changes or so called u ritical pressure effects has not
been detected in any of the trials cor~iucted by MRL. Other dot~bts about
l:Le reproducibility of the work of D~:sey and Cavanagh [25] are raised by
l:he fog collection rates. For example under supposedly identical c~nditions
i~ the one cabinet with the one nozz;e, the fog collection rates for f~ve
lifferent runs varied as follow~, 0.9, ~;1, 3.0, 1.0 and 0.8 ml h 1 The critical
pressure effect has no apparent the~.retical explanatic, n and some
confirmatory work should be attempted. In the third ~riat conducted by
,~
[24] the weight floss for the st~4 panels varied from 0.14 - 0.19 g/day
for the nine different experiments. Therefore, the lack of re~)roducibflity
i~ the results for the zinc plated panels cannot be ~)xplained by a .nt~cal
pressure effect.
In summary, the salt spray test accozdmg
- ' ~"
to ASTM Bl17 is n o t a reproducible test for the evaluation of chrcmated zinc el .ctrc p,ate on steel, even
wh(:n the quality of the reagents is st~=tctly controlled. Ti~e variatior~ may be
~utr t,o pu~uuanu~ it~ ~,nu a~mospn('re ~.:r may restll~ trom :~uor~le cll~lerences
in the storage conditions under which the panels are distributed t o the
~arious laboratories and stored p~ior to the test (i.e. the effect of aging of the
films). In any event, the actual times to failure are misleading when trying to
assess a partic~dar item for o u t d o o r exposure.
m

Humidity testing
T h i s test c l o s e l y a p p r c . ( i m a t e s t h e t y p e o f corrosioi.~ (~x.t:(~ri,~,,:ed :~ a
l r o p i c M e n v i r o ~ m e ~ ! . It also. t,r~,~bably m o r e r,:~alis~i('a!ly, roI,!~,s~ , - ~,~ ~ ..
o f corrosi(~n in p a c k a g e s w h i c h aro st.r:,red t:,~(~,r ~,'~,~,ii'~i~,~- ~,2 . . , : ; ,
temperature and humidity. Various humidity-temperature
cyctes h~ve b e e n
used i~ t h e general t e s t i n g o f zinc, a l t h o u g h t h e A u s t r a l i a n S~an ~rc~ 17 c 11 9 7 6 d e f i n e s or.ly o n e sot o f c o n d i t i o n s ( 1 6 }: at 55 C a n d a m i n i m u m o f
o/,-, \
5 h at 3 5 ,~,. ')t'he D r a f t I n t e r n a t i o n a l S t a n d a r d I S O / D I S 3 6 1 3 r e s t r i c t s ~he
t i m e o f storage' b e f o r e t e s t i n g o f c h r o m a t e d zinc t o w i t h i n t h e r a n g e 24 . 7?.
h l h - e s u m a b l y , this is t o a l ! o w t i m e f o r t h e c o a t i n g t o d r y o u t u i t h o u t
a l l o w i ~ g a n y s u b s e q u e n t chan~e~ m p r o p e r t i e s s u c h as l e a c h i n g rate.
H o w e v e r , t h e s e c h a n g e s in t h e f lrn d e p e n d o n t e m p e r a t u r e and h u m i d i t y as
well as t i m e . In a series o f tests ~vhere t h e panels t o o k s e v e r a l mon~:hs t o prep a r e a n d ~ e r e t h e n s t o r e d for 3 - 4 m o n t h s at t e n , tarot t e n p e r a t u r e , n o n e o f
t h e p a n e ! s e x h i b i t e d a w h i t e c o n ' o s i o n p r o d u c t aft ?r ~1 dag~ ~,~?o,a~r~ l(~ ~,,,
h u m i d i t y test ['~61. T h e c h r o m a t e was n o t leachec, f r o m t.i.~: i~,m a~ .,sho~n
by differential .~ulse p o l a r o g r a p h i c a n a l y s i s o f t h e .:onde~zsed w a t e r C o l l e c t e d
as r , m o f f f r o m t h e p a n e l s . T h e s e r e s u l t s c o n f i r m t aat aging, of the film ca~
h a v e a d r a s t i c e f f e c t o n t h e s u b s e q u e n t c o r r o s i o n r e s i s t a n c e of c h r o m a t e d
zinc e l e c t r o p l a t e .
plate in t h e h u m i d i t ? ' test b u t , as p a n e l s h a v e to be s~:~.~.~:~,,~i t(~ ~i~, ~,,st
withi~a '~,2ch strin~er-t t i m e limits, this t es~ m ~ , t l , . ( ~ l
~.
~" ~. . ~
' .......
:

( ; h r o m a t e ah~ ty ~is
in an earlier p u b l i c a t i o n [ 3 ], it was s t a t e d tt!~t "'th(, ~'hr~ ~-,~a~.~ a~.~.:.~i\~,
seelos to be m o s t p r o m i s i n g (e~ a q u a l i t y c o n t r o l t~s' t b u t a t ,.~:~i~,vai,i ,~
a m o u n t o f inv.estigator / w o r k m u s t be ux~dertak~'; !~,~.,f(~r a ~:-~ti,f~,'~,,r'.,
s t a n d a r d c a n be establish,~d ''. A f t e : a n u m b e r o f e ~ . p e r i m e ~ t s , ',r a ~ l ~ , , ' a ~ "- ~, ~ o , :
the .chromate content

othe

f i l m a l o p e d o e s ~ o t det("r.min~ tl~.(' ! ,',-)t~.,- : ,

v a l u e o f t h e film, E a r l y results b y Katz e t ,'.~] [20,] a ~ !;~t~ ~r ,~ ,,.., i :~''

s h o w e d t h a t , for zinc pla"~e prepm"ed at t h e ~.)~.~' ~i~,~,. ~i~.,~.r,, ~ ,
:,~ . . . . ~:
b e t w e e n titan, to f a i l u r e in t h e salt s p r a y tes~ a~d ('i~r, .rr, a ~ .," " :;~ ~,~,~,:'
zinc s a m p l e s w e r e p l a t e d b y a ~.t, m b e c ()( cliff, ~ r ~ :~');,~,~~'~ ;~
s p r a y t,est (see Fig. ] ) a n d t h e re.su!Ls m d i , ' a t , , ~.hat Li~., ~.~',~-~ ~;.-,- ,. . . . . . . . .
d e p o s i t m a y well be a rr ajor c o n t . ~ ' i b u t ~ f a ' ~ ) r . M ( ~ r ( , : r , . : e r ,
,,vt~,;~
:~.:;",,~
w e r e e x p o s e d o u t d o o r s , it was ~ o t i',()ssibi( t~~ m a k e :~.~v (,~rr~.~,!:v~b e t w e e n c h r o m a t e c o n t e t ~ t and c o ~ o s i o ~ , r~si ~ta~'e. cwei~ ~ t i ~ i~a~,,~[~ i'i~,',~
u n d e r i.~ent~,ica~ c o n d i t i o ~ [ 1 6 ] . IL is int.er('.~li~u to :~)t(, i~. Fi.. i ti~a~,
a l t n o t i g h sc, m~, p a n e l s f a i e d t,h~ ci~ro~.~at~, a ~ . .
~
,
t h e y d i d n o t ~ e c e s s a r i l y fai! ti;e sa![ s~.~ra>

:tt6

'

~ e t e f o m , although the chromate ~ntent enhances the protective

.valueof chromate ~nversion films, it is not a good me&sure of the corrosion
resistanC,
The~~
for thin ~ e that aging affects the ext~ction of the
*
e
chromate from the fl m a n d the profiles of the zinc plate appear to be a
:~ajor contributing factor in determining the corrosion of chromated zinc

Conclusions
Iridescent chromate conversion coatings are still si:m~Ia~ ~o those,
ori~s~y ~ u ~ :
by:bmd~n,[2] and the major advance in moderns.
pro:prie~ ~ ~ i o m m-~h~ the time o f immersion : ~ . ~ al~red to suit;
i.e,Lty~ A c~tinga)are a more recent

~Ihe ~ ~ :

0f~e,:,~~tmg.pro~

invoh~es the precipitm ion

of Cr(OH)~ with t ~ . ~ l s ~ t ~ n of anions such as chromate in the fihz,.
More ~ o w l ~ g e o n the mechanism of the reaction is need~, particular y
wit!
m~otion.
is on both tt e
~amer !ay~
of the chromate
,,~sorbed in the .~iim,~t~ingofthe film affects the d ~ ~ t i o n of the c.hr<,Im~,
ate and makes ~ difficultto predict the protectivevalue of these films.
Accelerated corrosion testssuch as the saltspray ~st do not produce reli;~ble
,resultsand do not correlate with outdoor exposure tests. In general,
chromate content of the film does not correlatewith corrosion resistanc~of
the chromated zinc electrcplated by a number of firm~. This leaves the
corrosion testingof chroraated zinc in a very unsatisfactorfstate.
References
E.
E.
3 I,.
4 L.

J. Wilhelm, U.S. Paint, 2,035,380 (i936).

A. An der~)n, Proem Arnec Electroplaters' Sot., 31 (1943)6.
F. (3. Wil{iams,
F. G. Wi|~iams,~
~76) 355.
5 T. Biestek, Ft. tnSt, :Mech. Precy~, ',15(t967) 47.
6
E. Halts, M e t ~ ~l~eat., 14 ( t 9 4 7 ) 1 6 4 ,
7

G. Woldt, Werks~.ffe Korros~, 1-2/{:!961 )486.

9 ~, I. L+~vitin~, ~ . Fi: .: :.ram. 34 (~t960) 2075.
10 K. G, McLa~en, ,J!,i
H.,G~
~
-~
M. E. Rope~. Me. i~IF, m s h m ~ J,,
12 H ~ ~ . . . . . .
13
[4

Ele~
t5 A.[

SoL, I (1961) 161, I%).

~'in;~hin~, 4.2 ( t 964) 163.

117

16
17
18
19
20
21
22
23
24
25
26
27

L. F. G. Williams, to be published
M.J. Feree, Bull. Soc, Chim., 25 (1901) ~)20.
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(19"72).
it L. Katz, K. I,. Proctor and F. Nagh~,, P r o c J,m~, ~(~c 1 ~ . ~ , : , ~:~.~i~ ~;
(1957 ) 203.
L. F. G. Williams, Corrosior, Se;.. 13 ' 1 9 7 3 ) ;J~5.
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(1973) 18.
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communication.
L. bI. l~more, Materials Reseaxch La,)oralories, iX'lelbo~lrn,, p~ivate cornrnunica~.~on.
V. M. Darsey and W. R. Cavamgh, Proc. Arner. S(,c. T~,sting Material:~, 48 (1948) 15:;
L. F. G. Williams, paper presented to 6ti~ tnt. Congr. on Metallic Corrosi(~n, Sydney.
1975.
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