Corrosion St udi es or Magnesium and Its Alloys

HY J. l ), l [ ANA 1\'AI.T, * M A.I.M.E. , c. E. NELSON* AND J. A. P io: LOLTBET*

( Phi ladelphi a Meet ing, October l94 r)
T11 E s ubj ect o[ the salt-water corrosion
resist a nce o[ magnesium a ll oys is some-
what like that of the pitt ing of stainl ess
steels in that it in volves a relat ively small
perce;1tage of the a ppli cati ons but recei_ves
a much great er proporti on of the
Actuall y magnesium a ll oys arc in usc in
many ext eri or a ppli cati ons as well as
interi or with no troubl e fr om corrosion.
Magnc; ium a nd its a ll oys have a striking
stabi lity against atmospheri c a ttack, bci ng
far s uperi or to iron. Specimens exposed
unprotect ed t o a tmo:phcric weat hering for
10
years show onl y a s uperrtcia l surface-
film formati on.
The basic nature of magnesium and of
its important alloys is tha t they a re also
resistant to the attack of salt water even in
an unprotected state, giving subst a nti all y
no loss in weight after one year of alternate
immersion in 3 per cent NaCI solution
(Fig. r). This basic behavior is.
masked because of the extreme scnsttt vtty
of these all oys to certa in impuri t ies a nd
combinati ons of im pu ri ti cs. It is known,
and the subj ect o[ increasing emphasis,
that hi gher purit y leads generall y to
greater stability for many material s, non-
meta lli c as well as metalli c. ll o\\'cver, a
review of the literature 011 the corrosion
factors in magnesium alloys shows that
a lmost a ll researchers worked with base
metal in wh ich metalli c impuriti es va ri ed
in uncontroll ed a mounts. The major factor,
that of metalli c impurities, probabl y
Man usc ript recei ved at t he o fli cc of t he Inst itute
Dec . I .L 11)-.\0: re vised AtJril q, l ssul' d :l S
T . P. in METALS St.: ptl'ml K! . ' '>1'
* T he Dow C' hcnncal M1 uland,
Mi chi gan.
greatl y overshadowed t he effects of minor
ones s uch as flu x inclusions, nonmetalli c
impuriti es, porosity, met allographi c state,
whi ch these resea rchers pres umed t o study.
In the present in ves tigati on the rtrst
observat ion of interest is tha t whereas
magnesium of commercial purity (999 per
cent pure) ha s a corrosion rate in alterna te
immersion in .) per cent NaCI solu tion at
room t empera ture of a nywhere from 5 to
roo mg. pe r sq . em. per day, the corrosion
rate of hi gh-purity magnesium is o. r s
o.os mg. per sq. cm. per day. The principl e
foll owed in the experiments was to add t o
such base magnesium other elements,
singl y and in combina ti on, in con trolled
<tnd known amounts and to observe the
corrosion behavi or of the resu lting a lloy.
These experiments show the exi st ence of
what may be ca ll ed " tolerance limits" o[
magnesium a nd some of it s all oys for
certa in impuriti es. The ext re mely small
percentages of impuriti es in volved and the
sharpness of th e corrosion di scontinuiti es
appear t o be qu ite unpredi ctable.
Jn order to ca rry on thi s work , it was
necessary t o de velop a n a nalysi techni que
suitabl e t o t he problem. In some cases it
was necessary quantitatively to a na lyze
impu ri t ies t o less than o.oo 1 pe r cent. The
experimenta l da ta to be presented arc
based on obscrv<ttion of a bout sooo a lloy
specimens and on more than so,ooo
quantitat ive a na lyses.
273
Whil e the prima ry purpose of this paper
is to present t he experimentall y obtained
data on corrosion rates as a fun cti on of
compositi on, a nd parti cularl y to demon-
274 COHROSION STUDIES OF MAGNESIUM AND ITS ALLOYS
t e t he existe nce of sha rp t ole ra nce
limit s fo r certain impurities, it woul d
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natura Uy be of interest to ascerta in whether
t he results can be explained in terms of any
gcnera.ll y accepted theories of
behavior of metals. To this end, prelimi -
nary result a re included from experiments
on spot s pectrographic ana lysis and metal -
lography , on solution potential and over-
voltage measurements, and also on electron
ditTract ion st udies of the al l-important
rdm formations.
T he g reat majori ty of the a lloy composi-
tions studied have been made on 10o-g ram
melts, whi ch a re just la rge enough for
a na lysis a nd corrosion samples. In a la ter
section of thi s paper, however, a re reported
results on materi al made in full productiotl-
scale melt s and fabri cated into standard
lest ba rs, from which the eiTect on mechan-
ical properties of exposure to salt sol ution
has bee n obtained.
COl{HOSIO. i\S ,\ FUi\CTlON OF ALLOY
COM PO 'ITION
E XPERIMENTAL l\1ETHODS
A
1
! agnesiu.m. Pwification Technique
J\Ietalli c magnesium as available com-
mercially has t he foll owi ng ty pical anal ysis
P ER
P ER
CENT
C ENT
Fe.
O . O,SO AI .
0 . 0 1
i\ i .
< o . ooos M n.
0 .00 2
Cu.
< o . oos l'b ..
<o . oo t

0 . 0 0 .1 Nn.
<o. oos
and is therefore unsuitable for t he study of
corrosio n behavior of magnesium because
of t he presence of several elements in
amount surt'l cient greatl y to influence the
corro io n rate. ] ligh-purity magnesium was
produced by a special vaporization tech-
nique, since it was found that ma gnesium
nonuniform in iron content was obtained
by simple vaporization. Good purity
magnesium could be produced at a satis-
factory rate by distilling the metal from a
magnesium-lead aUoy and passing the
vapors t hrough a fll ter. After p uri ftcation
the magnesium is stri pped fro m the con-
denser a nd r epresentative samples are
taken for routine analyses a nd control
corro ion tests. Crystals of t hi s purified
J. D. H ANAWALT, C. E . NELSON AND J. A. PELOUBE T
2
75
magnesium are only superficially corroded
even after exposure of a year or more to
3 ; per cent NaCL soluti on. T he original
technical magnesium would be entirely
corroded away in severa l clays if exposed
to 3 per cent l'\a Cl soluti on. A typical
a na lysis of the purifted magnesium product
follows :
Fe.
Ni .
AI. .
Ca.
Cu.
PER
CENT
< 0.001
< 0 .000 1
< o . OOI
< 0 . 00 1
< o . OOO l
Na.
Mn ..
l'b.
Si ...
PER
CENT
0.002
< o. ooos
< 0.0 1
< o . oo r
Pure Attoy Produc! ion 'f"ecllll iquc
The melting a nd all oying of the super-
purity magnesium also required th e devel-
opment of a. specia l techni que a nd a careful
selecti on of ;tlloying materi a ls, so tha t the
desired compositions coul d be made with-
out contamina ti on by oth er undesirable
eleme nts.
It was discovered tha t superpurity
magnesium could not be melted in a n iron
or steel crucible a nd the molte n met al
could not be contact ed with tongs or ot her
apparat us made of these ma t erial s because
of the t endency of the a lloy t o pick up iron.
Recourse was necessary, therefore, t o
materi als of a refractory t y pe, of whi ch
solid graphi te, plumbago, carbon-lined
silicon carbide (Tercod) and sillimanite
were most sati sfactory . T he great bulk of
the a ll oys for the present ex perime nts were
made in sillima nite or plumbago and
spectroscopicall y pure graphite was used
for st irring rods, sampling devices a nd
thermocouple well s. JVfa.gnesium may not
be melted in the plumbago or sillima nite
crucibl es without the use of a nu x because
the metal will a ttack the crucibl e and
contamina tion of the melt wit h a luminum,
iron a nd silicon will result. T he usc of t he
common magnesium melting fluxes, how-
ever , la rgely prevents thi s attack a nd at the
same time prot ect s the all oy from oxida-
ti on. Specially puri fied nu x was used in the
a mount of ro to 30 per cent of t he weight
of the metal. The bulk of the flux was
melted in the crucibl e a nd when hot the
sli ghtly preheated pieces of the weighed
magnesium a nd necessary all oying con-
stituents were added to the crucible with
a careful sprinkling of powdered flux to
inhi bit burning. When t he e ntire charge
was in a nd thoroughl y molten, the a lloy
was stirred carefull y wit h a graphi te rod
several t imes at intervals of a few minutes.
Quiet standing for 5 to I 5 min. was then
a ll owed, a nd fi nally the crucible was
removed from the furn ace, after whi ch the
charge fr oze and was the n cracked out of
the crucibl e, and the frozen flux washed
from the metal. Thi s simpl e technique
avoided pouring of the metal and the
conseq uen t diff1culti es due t o very sma ll
bat ches a nd danger of conta mina.tion. The
ftni shed a lloys we re then cut into sampl es
for a nalysis and corrosion, as will be dis-
cussed la ter.
It has bee n stated in the literat ure that
such s ubstances as :MgO, mag-
nesium oxychl oride or chlorine are a ppre-
ciable factors in the corrosion of magnesium
a nd its a ll oys. In order t o check the present
experimenta l proced ure, a nd because of t he
possibilit y of the occurrence of these com-
pounds in t he product ion or fabr ication of
magnesium, it was considered advisabl e t o
in vest igate the behavior of such substances.
rt was found , providing harmful meta lli c
impuriti es were not simultaneously intro-
duced , that the foll owing ma t eri als have no
signi ft cant effect on t he corrosion of high-
purity magnesium a nd it s all oys: CaC2 ,
N l-r. CI , N I f 4HF. , S, iVI g,. N,, MgO, MgOCI,,
C, li e, N,, CS,, C2ll ,, CO, C02, II 2, II 2S,
li Cl, Cl2, C l-1 .,, SO,, 0 2, natural gas and
a ir. It was a lso found that flu x incl usions
d id not accelera t e the corrosion ra t e of
s uperpure a ll oys in 3 per cent NaCl
solution.
The process and equipment for ma king
the pure a ll oys having now been bri eny
outlined , some further considerat ion will
be given to the sel ect ion a nd prepa ration
of the a ll oying ma teri als used .
COilHOSION STUDIES OF Mi\GNESI UM AND ITS ALLOYS
If lnminnm.- Commercial alumintllll con-
tains far t oo much iron, ni ckel a nd sili con
for use in these ex periments, so a special
grade of aluminum, whi ch contained onl y
about o.oos per cen t iron and other im-
puriti es in ve ry small a mounts, was u eel.
Zinc.- Fortuna. t ely, in thi s case the
regular co mmercial grade of ll orsehead
zinc is of sati sfactory purity.
JIJ! nnga il ese.- Co mmercial met a lli c ma n-
ganese or ha rdener :1ll oys of aluminum and
manga nese have until ve ry rece ntl y con-
tained fa r t oo much iron and ni ckel to be
of usc in the production of pure a lloys. J t
had , however, been previously kno wn tha t
ma ngan ese c;tn be added t o magnesium
all oys by the redu ct io n of M nC1
2
,
1
a nd
since the la tter salt is a vail a bl e in a ve ry
pure st a t e thi s a ffords a good source of
pure manganese. For the mos t r a rt. ,
ha rdeners of pure magnesium with 2 .0 per
cent ma nganese were made in la rge bat ches,
and t hen pa rts of thi s pre-alloy we re added
in t he correct proportio ns to s mall e r melts
as required .
h on.- Normall y iron was added to t he
pure a ll oys, when desired, through the use
of a pre-all oy made by reducing pure
l:'eCI:. with pure magnesium or a pure
ma.gnesi um- base a ll oy. It was ncccssa ry t o
mix the FeCI:l t o be reduced \\' ith a. propor-
ti o n of the regular melting nu x before
adding it t o t he molten a ll oy, in o rder to
prevent the loss of the FeCI:. by excessive
vapori zatio n. I ron conte nts of o.o3 per cent
or slightly over may be obta i ned in t he
binary magnesium-iron a ll oy by the fore-
going tec hni que. Iron can be added by
direct contac t wi t h molten magnesium ;t t
el eva t ed t e mpera tures, but such a. pro-
cedure is not dependa bl e for uniform or
predicta ble compositions.
Nickel , Copper and Lead.-Since ni ckel,
copper a nd lead are avail abl e in a hi gh
degree of purity , a nd alloy readil y with
magnesium, they may be added directl y
t o the ma gnesium aLl oy. Owing t o the
1
References are at the e nd of t he paper.
extremely s mall a mount required a nd the
f'tn e control of uniformit y ;wd qua ntit y
desired, the general practice was to ma ke
pure pre-alloys of magnesium or mag-
nesium-base containing o.o r or 1.0 per cent
of the met als a nd then add a li q uo t po rti ons
of these t o t he intermedi a te a lloys.
Silicon.- Sili con was pe rhaps the most
troubl esome of a ll the elements t o add
because of the lack of a. source of high-
purity sili con and the consequen t te ndency
to introduce simultaneously int o the alloy
cxcessi ve amounts of other impuriti es.
After man y more or less successful a t tempts
to reduce va ri ous pure sili con compounds,
it was ftn a ll y found that the best t echnique
was t o form a pre-all oy by using com-
merci;d 97 per cent ili con (fe rrosili con or
1\o per cent aluminum, 2 0 per cent sili con
harde ners), a dding these to very pure mag-
nesium or magnesium all oys in a proporti on
suf1'1 cient to produce a fin al sili con content
of 1 .o t o t o.o per cent, and then removing
a ny iron thus added by a precipita ti on
treatment, so that the end product would
be a pure magnesium-base all oy cont aining
appreciabl e sili con but ve ry littl e iron. This
pre-all oy could then be a na.lyzed and used
in making o ther sili con-containing alloys.
More ComjJlinllcd If /loy !l ddit ions .- The
usc of ha rde ncrs or pre-alloys, a s has been
prev iously mentioned , made the producti on
of the more compli cated combina ti ons of
elements possibl e. In practi ce, la rge ba t ches
of the vari ous classes of pure base alloys
we re made up with no impurity additi ons
and a lso with indi vidual and varying
amount s of the different elements t o be
studi ed. In t hi s way, through the use of
some so to t oo base alloys, almost a ny
desired alloy could be made by mixing the
proper g roup of base alloys in calculated
proportions, without fea r of a ltering the
ge neral a lloy compositions by such mixing.
M et!t ods of Analysis (Sec If ppendix A)
i\l[ost of: the a nalyses were made by a
spectrochemi cal method. Occasional check
J. D. HANAWALT, C. E. NELSON AND J. A. PELOUBET
277
were mafi c by dependable
chemical procedures.
In order to compare the composition of
small corroded areas on a particular speci-
men with the composition of the non-
corroded areas, it was neces ary to use a
procedure somewhat different from that
described in Appendix A.
Samples of the areas to be studied,
weighing ro t o 20 mg. each, were taken
by use of a small drill, the di a meter of
which was less t ha n the diitmeter of the
area to be sampled. Thi s material was
dissolved in dilut e sulphuric acid and t he
solutions were brought to a concentration
of 5 per cent ba.-cd on the magnesium.
On each one of a. pair of spectroscopi cally
pure graphite support i11 g electrodes, o.o.;
mi. of thi s solution was phtcccl a nd. then
dried. The resulting salt was excited by
means of a 22oo-volt a.c. a rc. From this
point on the analytical proced ure was
identical to that described in Appendix A.
Specimens selected for thi s type of
analysis were treated in several different
ways prior to sampling. '.!.'he first group of
specimen was subjected to the regula r
corrosion test and then samples were taken
from the corroded and noncorroded a reas.
1\trany of t he corroded areas showed an iron
content as high as o.o5 rcr cent whil e the
noncorrodcd areas contained less than
o.oo2 per cent. I fowcvcr, t here were cases
where there was no difTercnce in the iron
content of t he two areas after corrosion.
Later tests indi cated that the rca on for t hi s
probably was that most of the iron had
already left the corroded area either by dis-
solving in the corroding medium or by being
mecha nically removed as the magnesium
a round t he iron particles di ssol ved.
The next group of specimens was sub-
ject ed to the corroding medium only until
the bad areas began to appea r. i\ll samples
taken from t hese specimens showed greater
iron concentrations in t he corroded areas.
Eleven different specimens analyzed in this
ma nner showed iron concentrations in the
corroded areas varying from s to so times
greater than the iron concentration of the
noncorroded areas of the same specimen. A
specimen treated in this same manner was
analyzed by microchemical methods using
t he aa' dipyridyl reagent. This analysis
showed o.oor 5 per cent iron in the good
areas and o.oi 5 per cent iron in the cor-
roded or bad areas.
A t hird series of samples was taken in
the following manner. A specimen was
cleaned and polished on one surface. This
surface was carefull y mapped and approxi-
mately roo samples were taken from areas
over the entire surf ace. The specimen was
then immersed in the corroding medium
u nlil corrosion spots appeared. The small
samples previously taken were then divided
into two groups, one group being taken
from t he areas that corroded when placed
in the corroding medium and t he other
group from a reas that did not show attack .
T he iron content of the ftrst group of sam-
ples was o.ooS per cent. The iron content
of the second group was o.o014 per cent.
In a fourth method a specimen was
mounted under the mi croscope a nd a drop
of 3 per cent NaCl solution was pl aced on
it. The action of this solution was observed
just long enough to locate deftnitely the
source of allack, indicated by the evoluti on
of bubbles of hydrogen. Thi area was then
marked and "'ashed with di stilled water.
The sample taken at this area conta ined
o.os per cent iron. The iron content of a
sample taken from the unaltacked area
contained o.ooi per cent iron.
In addition to analysis for iron, all of
the <tbove- mcntioned samples were ana-
lyzed for ni ckel and chromium, two other
metals that could cause increased corro-
sion. ln no case was nickel or chromium
detectable by either the spectrochemi cal
or mi crochemical techni ques.
Corrosion Testing
The specimens produced by the alloying
technique described were subjected to a
CORROSION STUDIES Ol' MAGNESI UM AND ITS ALLOYS
st a nda rdized corrosion testing procedure.
r\ t the same time an accura t e spectroscopic
ana lysis of the impurity content was
obtained. The actual specimens for cot-ro-
sion t esting <tnd a nalysis were carefully cut
from sections of t he a lloy that were known
to be uniform a nd free from inclusions of
nux. 'J.'he corrosion sample was cut t o a
uniform size of ;)1 by I by 1 ) > ~ in. along
with the two a nalysis electrodes 78 by
7.Z by % in. each.
For testing purposes, the specimens were
ftrst drilled near one end t o accommodate
a 78"-in. glass hook. Subsequentl y the
sam pies were ground all over on ~ L cl ean
Ko. so grit rot a ting a brasive cloth. T hi s
abrasive was of a n aluminum oxide t ype,
whi ch did not harmfully contamina t e the
met al being ground. Finer ftni shes were of
no :t dditiomt l value. The grinding was
carried deep enough t o eliminate all saw
ma rks and original surfaces. Careful
ha ndling permitted the omission of a
degreasing operation before t he corrosion
test.
Hef ore the corrosion test, the samples
were weighed t o the nearest milligra m and
measured t o the nearest miLlimeter. From
t he la tter ftgures t he original a reas were
calculated.
The standard corrosion t est is essentially
an alternate immersion-emersion in 3 per
cen t NaCl soluti on. The cycle consist s of
7 ~ min. in the solut ion followed by 2 min.
in air. During the la t ter time interval the
specimens do not completely dry.
The specimens were di pped into indi-
vidual glass containe rs as a means of
avoiding the contamination of one speci-
men with corrosion product f rom another.
At frequent intervals, distilled wa t er was
added t o the containers t o ma ke up for
loss by evapora tion. T his not only provides
a more uniform concentra tion of NaCl but
ensures a compl et e wetting of the samples
on each cycle. Every t wo or three weeks
(or oft ener if necessary) the t est solutions
were renewed in order to prevent undue
accumula tion of corrosion p roduct.
The tempera ture of the a.tr and salt
solution was that of the surrounding room,
a nd was within the range of 6o
0
to JOoF.
lt should be pointed out here that impure
specimens corrode more rapidl y than pure
alloys with increase in t empera ture, while
the corrosion ra t e of the latter is independ-
ent o( the room-t empera ture cha nges.
T hus, while working wi t h specimens o( low
cot-ro ion ra te in det ermining impurity
tolera nce limi ts, t he normal temperature
vari a tion is not an essential factor.
The corrosion t est was continued for a
peri od of 16 weeks. Specime n that did not
survive the entire time were not ed as
destroyed. At the end of t he t est period,
the sample were prepa red for the final
weighing by a complete removal o[ all
corrosion products. This was accomplished
by means o[ a r -min. immersion in boiling
20 per cent CrO, solut ion t o which has
been added I per cent AgN03.
3
A Cr03
solution alone does not appreciably attack
magnesium or its alloys, but a considerable
a mount of sodium chloride is carried over
t o the cleaning ba th within the corrosion
product. If thi s were allowed t o remain in
t he cleaning solut ion, the resultant hydro-
chloric acid would a ttack the specimens
a nd produce er roneous weight losses.
T herefore, a concentra t ed AgN0 3 solution
is added to t he 2o per cent Cr03, yielding
a fine precipita t e o[ Ag
2
Cr0 4 This Ag2CrO.
reacts in turn t o precipitate any chlorides
that may be brought into the cleaning
solut ion.
After the cleaning opera tion, washing in
water a nd dryi ng, the specimens were
reweighed. From the determined weight
loss, original areas a nd time of test , the
corrosion rate was calculated as milligrams
loss per squa re centimet er per clay.
All specimens were examined visually
not only t o obtain informa tion on the t ype
of attack but t o locate a ny extraordina ry
defect s that might cause the quantitative
results t o be unreliable.
Fig. 2 is included to aid readers in
obtaining a visual picture of the corrosion
J. D. HANAWALT, C. E . NELSON AND J. A. PELOUBET
279
corresponding to a certain numerical
rate in milli gra ms per square cent imet er
per day.
.I .5
corrosion rate. T his phenomenon is de-
scribed by saying tha t t he tolera nce limi t
of magnesium fo r iron is o.oq per cent.
I.
DISINTEGRATED
IN
35 DAYS
10.
COI<J<OS ION J{i\TE, MC: . I" F. H SQ. CM. PER Oi\V.
F IG. 2 .- 1\l' l' l: i\H i\ NC' I: I IF S I"ECIM'" NS ll i\V I NC: D I FF I: HE NT COilHOS IO N l( i\ TI:S i\FT I: I( 4 MONT II S
J\ LT I:HN ATE I M!\f i: RSI ON JN 3 I'I: R SODI UM
R I:S U I.TS
Graphi cal presenta ti on of the resul ts
obtai ned in thi s work is used as an aid t o
an easy visualization of the corrosion da t a.
As has been menti oned, commercial purity
magnesium has widely varying corrosion
ra tes within t he ra nge from 5 t o roo mg.
per sq. em. per day whil e high-purit y
magnesium has a ra te of o.I5 o .os mg.
per sq. em. per day.
Fig. 3 gives a broad view of the corrosion
of magnesium binary alloys wi th va ri ous
common element s. Whil e some clements
a re not ha rmful in la rge proporti on, oth e rs
a re detrimenta l even when present in
minute amounts. T he present importa nt
all oy compositi ons co me fr om combina tions
of the eleme nts tha t arc not ha rmful t o
corrosiOn. T he common impuriti es in
commercial magnesi um all oys a re iron,
ni ckel, copper , lead a nd silicon. More
detailed considerat ion of these impuriti es
in the imrort a nt magnesium alloys con-
taining aluminum, ma nga ne c and zinc is
then necessary. One begins with the st udy
of iron, ni ckel and copper in magnesium.
The results are shown in Figs. 4, 5 a nd 6
for iron, ni ckel a nd copper, respect ively.
In a moun ts up to o.oq per cent , iron
has no effect on the corrosion ra te of
magnesium. Any excess of thi s qua ntity,
however, causes a ma rked increase in
ln Fi gs. 5 a nd 6, simil a rly, there is a sharp
t olerance limit for ni ckel at less tha n o.ooo5
per cent a nd for copper ncar o. T per cent.
T he effect of the alloy elements ma n-
ga nese a nd zinc on the impurities iron,
ni ckel a nd copper is seen in Figs. 4, 5 a nd
6, respect ively, whi ch show th:tt in the
cases of copper and iron the t olerance limi t
is uncha nged though the in crease in cor-
rosion rate due t o copper or iron above
t hci r respecti ve t oleran ce limi ts is consid-
erabl y red uced by the presence vf about
J. O per cent of ma nganese or zin c.
Fi g. 5 shows that the t olcra nce of mag-
nesium for nickel is greatl y changed by
manganese and is raised wit h in creasing
manga nese conte nt , being a bou t o.ooJ per
cent ni ckel for 0. 2 per cent manga nese a nd
abo ut o.or 5 per ce nt ni ckel for 2 .0 per cent
manganese. It also shows t ha t zinc serves to
raise the tolerance li mit of magnesium for
ni ckel.
Whil e the usc of 0 . 2 to 2 .0 per cent man
ganese and of r.o t o r. 5 per ccn t zinc
appears a rbi tra ry, these choices arc i ncli -
catccl bcca.usc t hese amounts correspond t o
t hose in common mngnesium all oys.
A logical continuat ion of the ex per i-
ments would be t o show the effect of the
presence of aluminum in magnesium on t he
t olerance limi ts for iron, nickel and coppe r.
When one a ttempts t o do thi s for iron he
280
CORROSION STUDIES OF i'v!J\GNESIUM i\ D ITS ALLOYS
gets results as shown in Fig. 7, in " hich it
is shown that with even a very small
content of a luminum the tolerance li mit
for iron has d roppecl from o.oq r er cent t o
FE
cu
15
NI , Co
10 1-!------1--
5 Hl-------1
2
which gives a cornpa ri on of the results
wit h o.o per cent ma nganese a nd 0. 2 per
cent ma nganese. vVith 0. 2 per cent manga-
nese the tolerance limit for iron does not
3 4 5
I PERCENT OF ADDED CONSTITUENT I
F1 c . 3 O F MACNESI UM ,,J.LOvs.
a few thousandths per cent a nd that wit h
7.0 per cent aluminum it is about o.ooos
per cent. With Jo. o per cent a lu mi num, the
limi t is too low t o be determined even
t hough producti on a nd a nalysis ca n wit h
s ufT1cient care be carried to about o.ooo2
per cent iron. Therefore, study o[ the t oler-
ance limits of other impurities, s uch as
copper and nickel, in the system magne-
sium-aluminum would be very dillicult ,
since it would require p ractically nil iron.
I t is only possible t o proceed in a satis-
factory ma nner by working wit h t he system
magnesium-aluminum plus a small amount
of ma nganese. T he action of this small
amount of ma nganese is shown in F ig. 8,
drop below o.oo 2 per cent, but instead holds
very consL1nt over a wide ra nge of alumi-
num content. A few hundredth per cent
manganese is s uffi cient to give this effect.
Next comes the st udy of the impurities
iron, ni ckel, copper in the magnesiu m-
alumin um-o.2 per cent ma nganese system
instead of in t he magnesium-aluminum
system.
The enect of aluminum wit h o. 2 per cent
manganese on the impurities iron, nickel
and copper in magnesium is shown in Figs.
9, 10 and u, respectively . T he aluminum
content in the specimens indi cated in these
graphs varied in the range 2 to 12 per cent,
with t he great majority of the specimens
J. D. HANAWALT, C. E . NELSON AND J. A. PELOUBET
lying bet ween 4 and 8 per cent. Whi le the that of the ni ckel probably not a t all , since
aluminum changes greatly, a nd in fact , is the o. z per cent manganese would account
_,._
" I CORROSION RATE
/
MG/ CM
2
/DAY
"
90
I
X MG
"
80
0
MG 1.0 MN
I
"
.c. MG 1.0 ZN
I
70
"t!
60
I
50
X
I
40
30
X I
I
20
I
10
"
0
I
I
"
1.0
0 .5
I
..
0 Q .... v
""J'
... x ;:"
"'
0
0 .004 .008
.012 .016 .020 .024 .028 .032 .036
I PERCENT FE I
ftC . 0!' ON MAC: ;\ ESI UM- Mi\ NGAI\ IcS I:
the ma in determining factor of the position
of the iron tolera nce li mit , it changes the
positio n of the copper limit very little a nd
fo r the s mal l shift from < o.oo 1 per cent t o
o.oo 1 per cent ni ckel , whi ch docs t:1ke place.
Since these large amounts of aluminum
COHROSION STUDIES O.F MAGNESIUM AND iTS ALLOYS
have a. negli gibl e cfTecl on t he copper a nd
ni ckel lulerance li mits, it is unnecessary to
I CORROSION RATE I
MG/CM
1
/ DAY
90
80
X
X
70
Since magnesium containing a luminum
in the order uf several per cen t docs not
--
1.----
v
MG
/MG0.2 MN
60
I
50
1/
X MG
0
MG 0.2 MN
40
0
MG 1.0 MN
X
.Cl.
MG 1.0 ZN
30
20
X
10
X
I
I ,.j
1.0
lj
Vfo"
0.5 X
v.

z v


0
0
.002 .004 .006 .008 .010 .0 12 .014 .016 018
I PERCENT N I I
FI G. s.- EFFECT OF - I CKEL ON" M.\ La\ES LUM, AND M.AGNES l UM- llKC.
sludy the eiTccts over a wide range of
aluminum, as was necessa ry in connect ion
with iron.
di ssolve more t han a few tenths per cen t
manganese at t he freez ing point, one need
not study the eiTects of more t han this
] . D. HANAWALT, C. E. KE LSON AND J. A. PEJ"OUBET
percent age of manga nese on magnesium-
alumi num a lloys.
Next , since zinc was effecti ve in red ucing
I CORROSION RATE
MG/CM
2
/ DAY
90
X MG
80
0 MG 1.0 MN
L:;.
MG 1.0 ZN
70
60
)(
/
50
/
X
40
/
30
20
MG MN
10
v--
-
I
)(
1.0
0.5
/

X l(
x MG MN
0
I
0 .I .2 .3
copper in the magnesium-alumi num-o. 2 per
cent ma nganese system must be studied.
Fi gs. Q, 10, and r 1 show the results of
X
/
//
v
/
/
X
/-G
-
MG ZN
.4 .5 .6 .7 .8 .9
I PERCENT cu I
F 1c . 6. - l : FF J:cT OF cOPPER ON ,\ ND
t he ha rmful effects of iron, nickel a nd copper adding o.s and 3 per cent zinc to the mag-
in magnesium, its act ion on iron, ni ckel and nesium-a lumin um-0. 2 per cent ma nganese
CORROSIO
1
STUDIES OF J\f AG J:SI UM AND ITS ALLOYS
all oy:;. l' ig. o s hows that o.s per cent zinc
docs not shift the positi on o[ the iron toler-
ance li mit at 0.002 pe r cenl. but somewhat
red uces t he magnit ude ol t he corrosion rates
I CORROSION RATE I
MG/ CM
2
/ DAY
15
/10 AL
mag nesium- a luminum- m:Lngancsc- ni ckel
a ll oy , 3 per cent zinc has shifted the tol-
era nce li mit from o.oo 1 to o.oo 2 per cent
ni ckel :wd greatly reduced the corrosion

-
- -
I
/ /
/
/ /
I
10
I
- / -
.5 - 4 AL
----"
---
- -;J""
/
/
C AL
/
/
I
/
/
/

L.
/
/

---

/
/
/
...-
/
/
-----
----- 0
0 002 004 006 ooe 0 10 01 2 0 14 0 16 ore 020
I PERCENT
FE I
1' 1< :.
7.
(IF
for hi gher percentages of irun. ll owevcr,
additio n o( 3 per cent zinc gi ves a n inter-
esting result in t hat t he t olerance limit is
raised to o.oo3 per cent iron and t he cor-
rosion rate grea. Li y red uced fo r hi gher per-

rat e at hi gher percentages of ni ckel. Fi g. 11
s ho ws t hat o. s per cent zinc rai ses the cop-
per tolera nce li mit onl y sli ghtly whereas
3 per cent zinc raises it to at least o. s per
cent copper.
t:_;C1
9
- '--
8

0 .0 PERCENT MN 0.2 PERCENT M N
Sf>'\OEO AREA -t . 2 MG/CM'IOAY ' SHADED AREA . 2 MG/CM
2
/0AY
7

6 - 1- - -
,_
:I
-
f--

5 - - 1-

4
-
3

f--

2
I






0
0 004 008 .012 016 0 004 .OOB .012 .016
!PERCENT FE I I PERCENT FE I
FIG. 8 .- El'FECT OF MANGAl\'ES I: 0 TilE IRON TO LE RANCE OF M'AGNESlUM-ALUMl NL:M.
centages of iron up to o.or z, at whi ch poin t
a increase of corrosion rate begins.
Fig. 10 shows that while o.s per cent zinc
has little efTect on t he corrosion behavior o[
T hese data ser ve to show that t he
magnesium all oys st udied are characterized
by tolera nce limits fo r iron, nickel and
copper when present singly in the alloys.
J. D. HANAWALT, C. E. NELSON AND J. A. PELOUBET
I t remains to show t he results when the on the contra ry, there exist s a n interaction
impuriti es are simult a neously present. of some or all of them, whi ch would result
'
CORROSION RATE I
MG/CM
2
/DAY
.'ALMN

x MG AL MN
o MG AL MN .5ZN
D. MG AL MN 3ZN
'/

/ MG AL MN .5ZN

'
I '
1.0
I
I
_;

.
, 5
'
/.
rwr.r. .

0 002 004 006 008 0 10 012 014 .016 .018
I PERCENT FE I
FI G. 9.- I: FrECT OF Ot\' .\ N D
i\t i \ N" GAN ESE- Z l NC.
I CORROSION RATE
I MG/CM
2
/DAY
X


1,0 A
I
X MG AL MN
.5
0 MG AL MN .5ZN
I
D.
MG AL MN 3ZN
A
I

0
0 .002 .004 006 .008 .010 012 .014 .016 .018
I PERCENT Nl I
f-'l t:. I O.- f<:FFECT OF N I C "EI. ON t\ N IJ l t\CN ES! Ui\1- AI.UMI NU.\l -
Mi\ NL:i\NI::SE- ZI NC.
Without experimental work it could not be
known whether some of t he elements
counteract the effects of others or whethe r,
in a lowering of the tolerance amounts as
determined for the individual elements.
As evidence of these possibiliti es, it is
ROSTON STUDIES OF M1\ GNESI UM 1\ N D lTS A LLOYS
poi nted out t hat 0.01 per cent aluminum
grea ll y increa::;ed the sensiti vity to iron
whil e o.o 2 per cent ma ng;tne::;c, on the other
ha nd , was very efTeclive in counteracting
l CORROSION RATE
MG/CMz/ DAY
20
I
10
VMG l MN
I
a I loy:; in whi ch the i mpu ri li es ::;omewha t
excccdccl their tolerance a mounts.
!\ ::;t udy of thi s second group of alloys
::; howed tha t there were no cases having
X
MG AL MN
0
MG AL MN .5ZN
A MG AL MN 3ZN
1.0
; t MN .!,.
"
. 5
I

"
()')<,
MG AL MN 3ZN

X
""
X
X
0
0 .05 10 15 20 .25 .30 35 .40 .45
I PERCENT cu I
l'rG. 11 .- EFI' I':CT OF COPPI: I{ ON /\ i\" 1)
Mi\ NGAN I:St>Z I :--.rc.
t he corrosi vc cfiecl of iron. Th u::; even ex-
tremely small amounts of certain clement s
may result in sl ri king changes in t he cor-
rosive effects of ot her clements.
Further, in order lo make t he result s of
practica l importance, one must st udy not
only the combina ti ons of the known ha rm-
ful impurit ies, iron, n ickcl and copper,
but must include as well Lhe common im-
purities silicon a nd lead, even though
separately silicon and lead ca u e no corro-
sion, though present in a mounts 10 l imes
as great as t heir normal a mou nt s in com-
mercia l a lloys.
I n order to answer t hese questions, t he
corrosion rates were studied for a group of
magnesium-aluminum-manganese all oys in
whi ch t wo or more of the element s iron,
nickel, copper, silicon a nd lead were present
- none, however, being present in excess of
its tolerance limit as deter mined indi -
vidua lly- and also for a second group of
obse rvable coun teracting effect on the
corrosive action of a ny of the impurities.
From the study of t he f1rst group, how-
ever , it was found that dcf1n it e interaction
exist ed for combinations of iron with
copper, lead or silico n. These combinations
were t hen studied in detail, wit h t he results
as shown in Figs. 12, tJ a nd 14.
The signiftca nce of t he boundary lines
d rawn on Fi gs. 12, 13 a nd 14 is that wit hin
these lines corrosion rate does not exceed
o. 2 mg. per sq. em. per clay whi le outside
of these lines t he rate is greater than o. 2
a nd the ref ore greater than the rate for
high-purity magnesium. T his means t hat
t he compositions outside the lines have a
detrimenta l efTect o n the cor rosion resist -
a nce. DifTtcult ies due to a nalysis a nd
uniformity of composition of these speci-
mens were great er than when only one
impurity was being studied, and this
accoun ts probably for the failure of the
J. D. HA C. E . NELSON AND J. A. PELOUBET
points to determine a more precise location
o( the bounda ry line. Nevertheless the
points give strong evidence of the exist ence
of t he a reas subst a ntia lly as shown.

r
0 0 0
.14
.12
0
0
.10
0
0
0
.08
1\ 0
\ 0
.0 6
<
0
.0 4
0
\.
0
.
.
.02
0
oA\
0
)( 0)( )(.
0
techni que. i\ lloys of magnesium, mag-
ne ium plus 3 per cent aluminum and mag-
nesium plus 3 per cent aluminum plus o.o5
per cent ma nganese were made with vary-
X .Z .20 MG/CM
2
/DAY
0
) .20 MG/CM
2
/ DAY
---- - -
0
0 .002 .004 .0 06 .008
I PERCENT FE I
.010 .012 .014
1-"I G. 1 2 .- C O RROS IOI\" OF l:SE COKT AI N I NC: IRO N AND CO Pl' io:R .
When 3 per cent zinc is a.dded t o mag-
nesium-aluminum-ma nganese alloys, no
evidence for interactions of t he type shown
in Figs. 1 2 , 13 a nd 14 can be det ect ed .
1\l i:T i\I.LO<: Ri\ PI ll C 1: \: A i\ 11 N ,\TI ON
MI:T II OD
The a ll oys for met allogra phic study were
prepared from high-puri ty magnesium a nd
pure a lloying materials in a uniform
ma nner as rega rds alloying and pouring
ing a mounts of the single impuriti es iron,
nickel and copper in such proporti ons as to
cover a ra nge from s ubsta ntiall y zero to well
a bove the tole rance limi t for t hat pecili c
impurity in each of t he basic compositions
mentioned. T wo t ypes of castings we re
made, one sand-cast in a standard tensile
mold, the other chill -cast in a graphite mold
of }:l by cross secti on. Samples for
study were cut from the sa me place on each
casting in such a way as to present a n
average cross section. Most of the com-
CORROSION STUDIES OF "MAG NESiliM AN D I TS AU, OYS
p<t rati ve da t a were taken from observati ons
on the chill-cast samples. ll owever, cxil mi -
nati ons were also made of the
I PERPC:NT I
1.00
0
.90
0
0
.80
0 " 000
00 0
.70
.60
\
_\
.50
" x_\
0
0
.40
X \
0
X
"

1\
.30
X
\
X
xx
X
0
.20
0\
0
<
0
oox
XX
xx
.10
,..)( )( )()( )(

\
X
X

2:)( )(
ot,
0
0
XX
X
0
0
0
lx
lo
0
0
.) . Final wet poli shing on a simil a r
II' heel covered wi th velvet , using a di sti ll ed-
water of relev igated a lumina .
.20 MG/ CM
2
/DAY I
> .20 MG/CM
2
/DAY I
0
0
0
0
0
0 .001 .002 .003 .004 .005 .006 .007 .008 .009
I PERCENT FE I
Jo'r G. 13.- CORROSION OF M.AG NESI UM ALUMrNUM" MM\ C:A NE Sic CONTAI NI NG l R0:-1 AND LEAD.
sa mples, in order t o check t he effect of t he
ra te of chi ll.
The specimens for met ali ographic exam-
inati on were prepared by the foll owi ng
st eps:
1. Rough grinding up t hrough ooo
French e mery paper.
2 . Wet poli shing on a horizontal rotati ng
wheel covered wit h Vel-Cha rn ee cl oth ,
using a di sti lled- water suspension of No.
6oo alundum.
4 Etching t o bring out the vari ous
constituents, as will be di scussed in more
detail later.
RESULTS
Whi le examination of t he samples in the
as-poli shed st a te indi cat ed the presence of
some of t he impurities, it was found neces-
sary to evolve a n etching tech nique for
each element in order to obtain positi ve
identiftcation. In samples containi ng iron,
J. D. HANAWALT, C. E. NELSON AND J. /\. l'ELOUBET
particles of the iron phase ca n be seen in the
as-polished conditi on, but more positi ve
ide n ti ft cati on depends on t he fact t hat
exposure to ordina ry t ap water for a few
I I
.9
"
>(
0
.8

. 7

0
0
.6
0
0
.5
0

" X 0 0
0
0
.4
0
.3 f----
0
X X
X
0
.2
..
X
0
X
00
0
0
X 0 O
0 0
. I I" "
0
x Ox
)(
0
0
0 X
0

X X
0
0
X c31\
X
XxX.X i X
X X
)()()( *,px 0 0
1:\x
0
0
0 .001 .002 .003
0
0
be allowed t o take place while the speci-
men is under observa ti on wit h the mi cro-
scope. Gas can be seen to be evolved
slowly from the part icles, accompa ni ed by
X
.z . 20 MG / CM
2
/ DAY
0
>
. 20 MG /CM'I DAY
0
oP
0
0
0 0
0
0
0
0
j
.004 .005 .006 .007
I PERCENT FE I
FI G. O F ('UNTA I :-.J i i': ( : IRON 1\ N D SI I. I CON.
seco nds causes a di ssoluti on of the mag-
nesium-ri ch matri x a round the iron parti -
cl es, as is indicated by the appearance of
broad circl es around the inclusions. Longe r
attack by tap wat er or salt soluti on may
grad ua l broadening of the anod ic areas
surroundin g t hem. ;\ ctual counts of the
numbe r of iron particles in a st a ndard a rea
of t he va ri ous specimens ind icat e the num-
ber of part icles to be approximately
CORROSION STUDIES OF MAGNESI UM AND ITS ALLOYS
proportional t o t he iron content. Some of
these fact s have also been noted by
\' osski.ihl cr. '
1
In comparing the number of
particles in a magnesium-iron all oy with
that fo r a magnesium-.) per cent aluminum-
iron, one fi nels that at o.oo r per cent iron
no pa rticles can be seen in the magnesium-
iron whereas a number ca n be seen in the
magncsium-3 per cent aluminum-iron. At
their respecti ve iron tolerance limits, 0 . 0 1 7
and o.oo 2 per cent iron, the two all oys ap-
pea r to contain approximately the same
number of pa rticl es, but the in the
magnesium-iron a rc somewhat small er. One
f u rthcr observati on of in tcrcst is tha t the
particles have a random di stributi on and
lend to segregate in varying degree through
I he samples. Although a determinat ion
wit h any degree of acc uracy is diflicu lt , it is
roughl y es timated tha t the particle diame-
ter of the iron constituen t at the tolera nce
li mit is of the order of o.oooo 1. in. , whi le the
ave rage di sta nce between particles is about
o.ooo t to o.ooos inch.
In copper-containing magnesium, the
compound lVfg2Cu can be detected by
etching in a soluti on of 74 per cent di -
et hylene glycol, 2 s per cent water a nd r
per cent 1-11'\0,.. In a specimen containing
o.os per cent copper the Mg2Cu compound
is almost entirely in the grain boundari es,
whereas if o.t o per cent copper or over is
present the Mg2Cu compound is not on ly
in the grain boundaries but also a great
number of particles appea r throughout the
mat ri x.
For magnesium and its alloys containing
ni ckel, it is possibl e to use the glycol et ch
to reveal the ni ckel phase. Although onl y
a li ttle work has been clone t hus far , it is
worthy of note that a magnesi um- ni ckel
compound ca n be seen in the grain bound-
ari es at ni ckel contents as low as o.ooos per
cent.
SOLUTION POTENTIAL AND HYDRO-
CE:'\ OVERVOLTACE MEASURE.YIENTS
In order to aid in the test of the appli ca-
bility to the corrosion results of any
accepted electrochemi cal theories, some
measurement s of soluti on potential and
hydrogen ove rvoltagc are included. The
measurements we re made in 3 per cent
NaCI under the conditi ons used for the
corrosion tests, with the hope that some
correlati on of results would be possible.
Unfortunately, the electrochemical meas-
urements a re not complete enough at the
moment to cover the behavior of mag-
nesium-base all oys as a fun ction of varying
impurity content , and therefore do not aid
in an explanation of the existence of the
sharp di scontinuiti es or tolerance limits.
ll owcvcr, da ta arc presented to show why
certain clements a rc detrimental to the
corrosion resistan ce of magnesium.
M I:TIIOD
f P1epmntion of Samples
Magnesium-alloy el ect rodes were ground
to a size of o. s by o. s by 5 em. on aluminum
oxide abrasive paper, the ftnal cut being
made with No. 3 2 0 grit. The samples were
not handled after grind ing, since grease
delayed the attainment of a steady poten-
tial. The shape of ot her metal electrodes
used in the test s depended somewhat on
the samples avail abl e. The surface prepara-
ti on was t he same as for magnesium alloys.
M easn1'C11l ent of li.lcc/rode Potentials
The electrode potentials were measured
with a Leeds a nd Northru p special wide-
range type K potentiometer, using a
Weston unsat urated cell as standard. T he
potentials were measured in the cell
metal : 3 per cent NaCI; sat urated calomel
electrode at 25 .oC. Precautions were
taken to prevent diffusion at the liquid
boundary, and frequent checks of the
working calomel electrode against a refer-
ence gave differences never exceeding
o.ooo2 volt. Each elect rode was observed
for a period of at least 24 hr. In all cases a
steady potent ial was achieved af ter 1 2 hr.
Once a steady potential had been achieved,
it remained constant in most cases to
J. D. HA AWALT, C. E. NELSON AND J. A. PELOUIIET
within o.oos volts as long as observed
(maximum 48 hr.). A few elect rodes varied
by o.or volt in 48 hours.
M ea.surement of 1/ ydrogen Overvoltages
Hydrogen overvoltage, defined as the
negative potential t hat must be applied to
an electrode to liberate hydrogen at a
specified current density, was measured by
passing a current through the electrolytic
cell: metal cathode: 3 per cent NaCl
platinum anode and measuring the in-
crea e in potenti al of the metal electrode
above t he zero current value, with respect
to the saturated calomel elect rode. The
ovcrvoltages used in the calculations were
measu reel a t a cu rrcn t dcnsi t y of 5 ma. per
sq. em. Since t he relati ve values arc
essentially independent of current density,
t his choice i somewhat a rbitrary.
R ESULTS
Some results that seem to be of particular
interest are given in T able 1.
EI.I: CTRON DTFFR1\ CTIO'J P,\'I."''I: RNS
OF SU RFACES
'.l.' hc na ture of the protective Ji.lm fo rma-
tion on the surf;tces of metals is recognized
to be an important factor in metallic
corrosion. The possibility exists of obtain-
ing some information about t he structure
of such li lms directl y by mea ns of electron
diffraction if the ft lms happen to be in a
su fli cienll y crystalline st a le.
The compositions studied included Ig,
.Mg-6AI, Mg-1Mn, Mg-6AI-o. 2Mn, Mg-
4AI-.3Zn-o.2Mn. The specimens had pre-
viously been exposed to dry air, disti lled
water, 3 per cent NaCI solu tion, a nd other
treatment. J\ specia lly high dispersion and
resolution was obtained in these patterns
by using a distance from specimen to
photographi c plate of 72.3 o.r em. and
by controlling the high potential supply
of minus 40 kv. to within 3 volts. The
electron-beam pinhole diaphragm was 0. 25
mm. a nd t he pinhole to lens distance was
7 5 em. The surface of the specimen covered
by the convergent electron beam was 0.7
by I.o centimeter.
TABLE I.- Values of Solu.t-ion Potential and
Hydrogen Overvoltage Determined in 3 Per
Cent Sodium C!tloride
Composition"
Mg ... .
Mg-o.oz Fc . .
. . ...
Mg-4sAI ( Mg.,i\ L,)
Mg-6JAI ( Mg, A!,) .
AI. .......... .
1n .
Mn ...
Mg - 1. 2 Zn . ..
MK-7J Zn ( M gZn) .
( MgZn,).
Zn .. ... ... . .
Mo<- s7Cu ( Mg,Cu) ..
'' tl-84Cu ( MgCu,).
Fe .... ... . . , ... .
Fc- soAI ( FcAb) .
Co .. . .
Mg-ss Ki ( Mg, t\i) .
Ni ..... . . . ..... .... . . . .
...... . ... .
( MgAg).
Solution
Potential
I . 70
1.57
I . 7 (1
l . 24
I . 2 J
. a(>
. 70
.27
. 7J
I . 27
I .09
I . 06
I . 0 1
0.91
0 . 73
0.72
o . so
0.92
0. I 5
I . 64
0 . 25
Hydrogen
Over-
voltage
0
0 . 0 2
0 . 66
o. s z
0 . 7 0
0
79
o. J S
0 . 39
0 . 2.)
o . 34
o . SJ
o . 39
0 . I J
0 . . ) 4
o . s6
o . J s
o. 7 1
0 . 0 5
I . 02
0 . 17
I . 19
" Magnesium it nd a lloys lis lcd
arc of puri ly.
RESULTS
T he results of the electron clifTracliun
study were negative in that they failed to
show a ny substantial difference in the
patte rns as a functi on of t he composition
of the aLl oy. I n dry air at room temperature
the result was a difTu e :MgO pattern. In
aqueous media at room temperature the
result was t he pattern of Mg(OHh,
though with relati ve intensities of t he lines
differing from those of bulk Mg(Oll )z, and
with indi cations of slight varia tions in li ne
positions. These intensity variations are
probably related to orientation effects, bul
wi ll require further study, as will also t he
ot her differences observed. The published
literature on electron diffraction studies of
magnesium structures also gives evidence
for anomalous

Visual observations of the protective
film formed in aqueous media on mag-
nesium alloys with aluminum in the range
CORROSION STUIYI ES 01'' MAGNESIUM AND ITS ALLOYS
up to 10 per cent plainly show t ha t t he
ftlm is thinner t he higher t he aluminum
content of the alloy, and t herefore strongly
indi cate tha t t he chemi cal or physical
na ture of t he ftlm is difierent , depending
on t he percent age of aluminum in t he
alloy.
It has been taled in t he lilerature
7
t hat
the prot ective coat on manganese-con-
tain i ng magnesium alloys is ma nganous
hydroxide at least in su Li al pa rl.
The electron d iffraction results reported
do mean t hat .\ 1g(Oll h or .:\ l g(OII h
modified slightl y, is a major part of the
fil m, independent of the all oy composit ion
wit hin the ra nge of compositi on covered.
T hey should not be in Lcrprclcd to mean
tha t the ftlm acti on is not grca. Ll y det er-
mined by the presence of alu mi nu m or
manga nese compounds, since these may be
a morphous or for other reasons m<LY not be
det ect ed by electron di ffraction.
DISCUSSIO. OF R
Probably t he most extensive discussions
in t he li t erature on t he corrosion behavior
of magnesium a re by W. Schmidt a nd W.
Schultze
8
and by W. Schull7.c.
9
T hese a rc
excellent articles and devote considera ble
space t o the effects of metalli c impurities
in magnesium. T hey do not , however,
ma ke a study in suflicicnl detail t o bring
out the critical relat ionships presented in
the present paper, so no very direct com-
pa ri on of result s is possibl e.
It is commonly accepted
10
-
12
tha t the
corrosion of magnesium in salt solutions is
entirely electrochemical in nature, the sole
cathodic reacti on being t he evoluti on of
hydrogen gas, the anodi c reaction consist-
ing of t he passage of Mg++ ions into
solution wit h subsequent reaction with
OH- ions to form Mg(OH) 2 or perhaps the
direct forma tion of Mg(OHh on t he surface
of the metal by t he discha rge of OH- ions.
Constituents nobler tha n magnesium pres-
ent as a second p hase in the magnesium
should act as cathodes for local corrosion
cells. One might. then logicall y look for a n
explanation for t he t olera nce limits in
terms of the limi ts of solubility in t he
alloy for the constituent concerned. T his
may possibly be the explana tion for t he
t olerance limit of magnesium for copper
al a bout o. r per cent . Mctallographic
exil mina ti on shows t hat copper is soluble
l o a small degree in magnesium.
13
-
16
It is
soluble Lo about o. 2 per cent at 400C. a nd
the solubi lity d rops with tempera ture t o
something less tha n o.os per cent at room
t emperature. In the as-cast metal, which
is the st a t e used for t he corrosion test s,
t here appears a precipit at e of the copper
phase in large quant it ies for copper con-
t ents of o. r per cent or great er.
Examining the case of iron, which in
magnesium has a tole ra nce limi t a t o.o17
per cent, it is found t ha t t he li mit of
solubility in molt en magnesium a t t he
freezing point is sli ght ly under o.o2 per
cen t. ll owever, in the solid state, metal-
lographic examination shows i ron t o be
insoluble down t o a t least a few thou-
sandt hs per cent. T he numbers of iron-
phase particles (which occur within the
grains) that can be cou nlecl in the micro-
scope are proport ional to the iron content
of the magnesium. Tlut s it is certain that tlt e
solid solnhili:!y li111 it alllllltc tolerance l i mi t
rio not corrcs /Jiintl i n lilis case. Furt her
studi es may show whether the liquid mag-
nesium solubil it y limit is of a ny significance
in rela t ion to t he t olerance limi t.
For magnesium-a luminum alloys a nd
magnesi u m-alumi n um-ma. nganese alloys,
the solubili t y of iron in t he li quid state is
a pprccia ble a t high temperatures but is less
than o.oor per cent iron at t he freezing
point. T he iron solubi li ty in solid magne-
iurn-alumin um or magnesium-aluminum-
manganese is also very low. Metallographic
examina tion shows the particles of the iron
phase t o be present a t as low as o.ooos per
cent iron. T!terefore the tolerance li mi t a.t
o.oo2 fNr ceut iron does not correspoud to a.n y
solu bilit y lim i f in these alloys.
J. D. HANAWALT, C. E . NELSON AND J. A. PELOUBET
293
The iron pa rticles appear t o be in ra ndom
distribution, t he concentration of particles
being higher at some places a nd lower at
others. T his agrees wi t h t he results of
chemical and spectrographic spot a nalyses,
whi ch also were a ble t o show segregat ion of
iron in t hese alloys. It is of interest t o note
that on the a verage the number of pa rticles
of iron phase per unit of surface observed
in magnesium a t o.o q per cent iron or in
magnesium-alumin um at o.oo2 per cent
iron is a pproxima t ely the same, while the
number of iron-phase particles in magne-
sium a t o.oo2 per cent iron appears t o be
only a very small fra cti on of t he number in
magnesium-alu minum at o.oo2 per cent
iron. T he pa rticlcs arc very sma II and, at
t he percentage corresponding to the t olcr-
~ l l l C C limit , a rc separated at distances esti -
mat ed t o be of t he order of magnitude of
o.ooo1 in. Presumably the composili on of
the particles in m;tgnesium is iron, whil e in
magnesium-aluminum or m<tgnesiu m-alu-
minum-ma ngancsc t he composition is FeAb
or some more compli cat ed substa nce.
An explanation might be found for t he
great increase in corrosion rcsult i ng from
only a small increase i n the number of
pa rti cles beyond a cert ain critical number
in tha t up to thi s cri t ical number the
corroding spot s arc isolated and do not
contact or expose new particles, but t hat
beyond t hi s number t he particles arc close
e nough t oget her so th:tt the corrosion
ca used by t he pa rti clcs exposes new pa rli-
cles t o t he corroding medium. T his t heory
assumes t ha t each pa rt icle causes a. dcftnite
a mount of di ssolution of magnesium but
does not need t o make a ny assumption
about the mecha ni sm by which t he corro-
sion due t o the particle is slopped after a
defmite a mount of corrosion has taken
place. For specimens with i run below t he
tolera nce limit , t he fact mentioned pre-
viously, t hat there are random segregations
or regions of higher concentration of
pa rticles, accounts for the obser vation tlmt
t here may be localized a reas of visible
corrosion in such specimens. The iron at
such places was found by special analysis
t o be above t he tolera nce limit. The con-
ception of a. specimen with impurit y above
it s t olerance limi t is, t hen, that for such a
specimen t he regions of hi gher concentra-
tion a re so numerous t ha t they t ouch each
ot her and cover t he surface, or perhaps,
said more simpl y, the impurity concentra-
t ion is such t ha t the tolera nce li mit is ex-
ceeded a t every point. Specimens wi t h
average i mpuri ty below the tolerance limi t
may, a nd do, ha ve isolated a reas in whi ch
the average impurity content for t hese
:trcas exceed the t olernnce limi t.
Further hypotheses would be necessary
t o predi ct t he absolu te magni tude of the
t olera nce limi t for a ny parti cula r case.
Since t he particles do not t ouch each ot her
(as do the base a t oms in the "critical
resistance limits" of T a m ma nn) but rather,
for example, in iron inclusions, appear to be
of the order of 10 to 100 times their diam-
et er apart in the ncighborhoou uf the
criti cal concentra t ion, the ab olute magni -
tude of the critical concentration depends
upon the extent of corrosion caused about
each pa rt iclc. l'roba bly corrosion conti nucs
until the particle is removed by under-
mining itself. T hi s is the simplest a nd most
plausible theory and has conftrma ti on in
the experiments on metallography and spot.
a nalysis of corroded a rcas.
J\s has been shown by t he measurements
of solution potenti als and hydrogen over-
voltage, the particles of impuri t y serve as
cathodi c points, wh ich permit the evolu-
t ion of hydrogen gas. lt is possible that
t here exists a criti cal anodic current density
below whi ch protecti ve f-i.l m forma t ion
t a kes place but a bove whi ch corrosion can
continue. T he na ture of the fdm t hat forms,
and the criti ca I value of the a nodic current
density that will pe rmit the ftlm lo form,
should both be functions of t he composit ion
of t he alloy. T he magnitude of t he anodic
current densit y is governed by the amount
of hydrogen gas tha t can be evolved a t
2
94
CORROSION STUDIES OF MAGNESI UM AND ITS ALLOYS
cathodic areas. The la rger the rati o of
ca lhodi c area to anodic area, the smaller
the di stance between these a reas and t he
hi gher t he conduct ivity of the elect rolyte
a nd of t he surface ftlm, the greater will be
the amount of hydrogen evolved. i\s dis-
cussed later, it should be a functi on o[
the "dri ving force" measured by t he excess
of the difTerence in soluti on potenti als
between anodic and cathodi c a reas over the
hydrogen overvoltage of the cathodic area.
If corrosion is stopped by fum formation,
it may be necessary not only for the film to
form over t he a nodic area but to be able
to grow over and shu t ofT or " st rangle "
the cathodi c areas. It is on ly when polar iza-
tion a t the cathodi c a rea i: accompli shed
at negligibl e current that corrosion can be
said to ha ve ceased. Thus one may be con-
cerned not only with a critical anodi c
current density that allow ftlm [ormation
but with a cri tical size of cat hode areas,
whi ch t he anod ic ftlm is capable o[ shutting
off.
The following experiment can be inter-
preted as evidence [or the existence of a
critical value o[ current density as discussed
above. If a magnesium-alloy specimen with
all impuriti es below t hei r tolerance limits
is placed in salt solu t ion, t here is a n evolu-
t ion of hydrogen from the specimen while
film format ion is laking pl ace. Visibl e gas
evolu t ion soon sl ops a nd ftlm formation is
presu mably complete. If a new cat hodic
area that can evolve hyd rogen is connected
to the specimen, a hi gh current fl ows, but
not only to the new cat hode. Hydrogen
also begins to evolve from the specimen
again and will continue to do so until t he
external cathode is removed; that is,
protective fLlm formati on makes no head-
way as long as the additional current is
fl owing. As soon as the ext ernal cathode is
removed, protective ftlm formation begins
again and soon stops the hyd rogen evolu-
tion from the local cathodic areas. Thi s
experiment serves to emphasize that the
fi lm on the anodic areas d id not prevent
corrosion whiJe there existed a ny areas on
whi ch hydrogen could evol ve. Boyer
17
and
\'yskocil'
8
have discussed the cause of the
breakdown of the anodic fi lm in terms of a
"catalytic" effect of chl oride ions.
Considerably more work will be neces-
sa ry to aiel in choosing between the various
speculations on the explanation of t he
characteri sti cs of the tolerance-limi t phe-
nomena. The simpl er question of why some
elements act in the direction of accelerating
the corrosion o[ magnesium in salt solution
whil e ot hers do not can be explained in
terms of elect rochemica l properties. T he
ligures in Table 2 have been derived from
the experimentall y measured values given
in Table ' by taking t he difference bet wee n
the soluti on potential s of magnesium and
of the materi al in question and then sub-
t racti ng the hydrogen overvollage of t he
materi al in questi on. T hi s is cl one on t he
assumpti on t hat thi s quantity is some
measure of the driving force tending to
evolve gaseous hydrogen at t he cathodic
spot. For elements that have solid solu-
bility in magnesi um, t he solution potenti al
of the phase t hat would be precipitated
should be subtracted from the solution
potential of the soli d solu t ion phase instead
of from the soluti on polen ti al of magnesium.
Table 2 shows that for aluminum, ma n-
ganese and 7. inc there is either no resultant
dri ving force or onl y one of a bout o .I volt ,
while for iron , cobalt , copper and ni ckel
the d ri ving force is greater than 0-4 volt.
Sil ver shows an intermediate position at
0. 2 1 volt . Thus t he value of the quant ity
P .D .-0. V. serves to correctl y classify each
metal observed according to its corrosive
acti on on magnesium. It is to be noted t hat
there is no correlation of corrosion effect
wit h hydrogen overvoltage.
It is stated by Gatt y a nd Spooner
19
t hat
the hydrogen overvoltage of magnesium is
very low, and a part of their discussion is
based upon this claim. 'Ltble 1 shows that
t he overvoltage of pure magnesium is high
but is greatl y lowered by iron. From the
J. D. HANAWALT, C. E. NELSON AND J. A. PELOUJlET
295
a nalysis for magnesium given in their
paper, it can be seen that t heir determined
overvoltage for magnesium was in error
because of the presence of iron in t heir
specimen.
TABLE 2 in Sol ntion Potenti als
and OvervoUage V alnes for Varions T y pes
of Cells
Anodic
Material
Mg-3AI.
Mg-3AI. . ..
.. 1 Mn .
Mg I. 2Zn.
Mg- 1. 2Zn .
Mg .. ..
Mg .. . .
Mg .... .
Mg-3AI.
Mg .... ..
Mg .... .
Mg-2Ag .
Cat hodi c
Mate-
ria l
--


Mn
MgZn
M!{Zn,
MI{:!Cu
MgCu 2
Fe
Fe A!,
Co
Mg:!Ni
Mg Ag
Differ-
cncc in
Solu-
t. io n
Pot cn-
tials
( P. O. ) ,
Vol ts
---
0 . .)2
u . SJ
0 . 4J
O. t\ 6
0.04
0 . 69
0 . 79
0 . 97
I . 0 11
I . 2 0
0 .78
I . Jy
Hydro-
gen
Over-
voltage
P.O.-
of
o.v ..
Cat hodi c
Mate-
Volt s
r ial
(O. V.) .
Volts
--- --
o . Sl 0
o. 70 - u . 17
O. J9 0 . 0 .1
O.J4 0 . 1 2
o. SJ 0 . I I
0. I J o . s6
0 .34 o . 45
o. s6 0 . 4 1
0. 35 0 . 69
0 . 71
0 -49
o . os 0. 7J
I . 19 0 .20
T he results published by Boyer
17
show
that whil e his magnesium specimens were
pure enough for studies of magnesium
metal, they were not of sufftcient puri ty to
use as a base for alu minum-containing
all oys, a nd thi s accounts for ma ny of the
di screpancies between hi results and t ho e
of the present pa pe r. Schu lt zc
9
has made
valuable contributi ons t o the subj ect of the
corrosion behavior of magnesiu m a nd has
give n carefu l conside ra ti on to t he effects
of small a mounts of impurities in mag-
nesium. However, hi s publi cations contain
corrosion results th at arc presumed to be
characteri st ic of magnesium and alloys but
t ha t obviously arc inllucnccd by impuriti es.
lt seems fair to say t hat many of t he
results reported in the li terat ure on t he
corrosion o[ magnesium and its all oys a re
not representat ive of the basic nat ure of
the metal but a re determi ned by t he
presence o[ uncontrolled or insufticientl y
con troll ed met alli c impuriti es, which we re
regarded as negligible. It would be well if
all published results were criti call y exam-
ined from this point of view.
PRACTICAL ASPECTS
While for purposes of establishing the
funda mental factors governing corrosion
behavior of magnesium and its common
alloys it is necessary to begin with very
pure or sublimed magn esium and to keep
every element nil except the ones under
investigati on, this is not necessary for
purposes of producing good corrosion-
resistant magnesium all oys in pract ice. The
present hi gh grade of ingot magnesium
avai lable commerciall y in the United States
can be used as a base for such corrosion-
resistant <t lloys simply by making use of
the insolubi lit y of iron as previously de-
scribed, giving due regard t o selection of
materials a nd exercising adequa te pre-
cauti ons in ha ndling.
It is interest ing a nd importa nt to note
that in t he past, for certain alloys, the
eff ects of some impuriti es have been over-
emphasized, whereas t he data presented
show that these impurities may reall y be
present in amounts in excess of t he usual
specifi cat ions wit hout det rimental effect on
corrosion stability. F or example, t he com-
me rcial speciftcat ions on :Mg-6Al-Mn-3Zn
limi t copper t o o.os per cent whil e o.s pe r
cent would be all owable as fa r as corrosion
is concerned.
All oys with impuriti es below the toler-
a nce limi ts have been produced on com-
mercial scale in the form of sand castings,
die casti ngs a nd wrought shapes. T he corro-
sion ra t es on these all oys a re less than o. 2
mg. per sq. em. per day. Tests o[ the loss in
t ensil e properti es due to co rrosion have
been carried out on st a nda rd l est bars
of some common Mg- Al-Mn-Zn alloys
with the results as shown in .Fi g. 15. T here
a re onl y minor losses in properties over a
period of 1 80 days in salt solution for cast
alloys, though all oys in the wrough t form
a re somewhat more sensitive.
CORROSION STUDIES O:F MAGNESIUM AND ITS ALLOYS
SUNIMARY OF
1.. The basic na lurc o[ magnesium a nd
of il. important alloys is t hat t hey are very
rc islant lo salt - water corrosion bul a rc
' STRENGTH '
1000 PSI

t he hydrogen ovcrvollagc of the cat hodic
materi al.
S On l he basis of melallogra phic a nd
ot her l ypes of exami nat ion, a n assumption
28
-
MG-6AL .2MN- 3ZN
MG_I9AL .2MJ.7ZN
ULTIMATE
--
I
24
ULTIMATE
20 - ---
16
f-. MG- 9AL- .2 MN- .7ZN YIELD
Y
1
1ELD
12
1-
I ;. ELONG I
IN 2 IN.
8
MG- 6AL- . 2MN- 3ZN
ELONGATION
4

0
0 20 40 60 80 100 120 140 160 180
I DAYS I
F1 <: . I
5
.- CORROSI ON- T E NSI I.E PROPERTI ES O F CAST :MA.(: l\' t: Si l "i\1 - A I . l 'J\1 1 Nli M_- l\I AN GJ\t\E.SE- ZINC.
cxl rcmcly sensiti ve lo certain clcmcnls and
com binalions of clcmcn ls.
2 . The speci rtc effect on the sall -waler
corrosion resistance of magnesium clue l o
t he elemen ls aluminum, manganese, zinc,
iron, nickel, copper, silicon and lead
singly and in all combinations has been
determined.
3 The existence o[ " tolerance limits" or
discontinuities i n the ra te of corrosion as a
function of t he percentage present of cer-
tain elements has been demonstrated.
4 It is shown t hat the element studied
can be classified in t heir gross effect on t he
corrosion resista nce of magnesium accord-
ing to t he excess of t he eli fierence in solution
potentials of t he magnesium or anodic
material a nd of the cathodic material over
of a critical concen lralion of cathodic
particles is used l o expl a in l he ori gin o[ t he
corrosion disconli nui lies.
6. i\ lloy composit ion l hal meet t he
purity re(] ui remenls for good corrosion
stabili t y, and which rcpre cnt the range of
com mercia] usage, ha ve been prepared on
product ion scale in t he for m of ingots,
sand cast ings, die cast ings anrl wrought
forms.
7 The sa lt-water corrosion resistance of
t hese alloy composit ions is [rom 10 to roo
times greater t han t hat of common mag-
nesium alloys. Strengt h t ests on some high-
purit y casting alloys show negligible loss
in properties after 6 mont hs' alternate
immersion in 3 per cent Na CJ.
J. D. HANAWALT, C. E . NELSON AND J. A. PELOUBET
2
97
APPENDIX A.- Analysis Technique
In the analysis two pairs of solid metal
elect rodes II by 35 mm. were cut from the
specimen to be analyzed. T he surfaces
from which the di scharge was to take place
were poli shed on an Aloxite sanding wheel
and carefully cleaned by all owi ng 3 N
hyd rochloric acid to flow over t he area
for IO to I 5 sec. T he elect rodes were t hen
rinsed in dist ill e l water and dried on a
clean cloth . T hi s cleaning treat ment was
given t he elect rodes immed iately before
they were pl aced in t he electrode holder, in
order to reduce cha nces of contaminati on
to a minimum. T he electrodes were placed
in a water-cooled electrode holder wit h a
gap of 5 mm. between the electrodes. In
analyzing magnesium and its alloys for
iron, nickel a nd lead at concent ration
below o. r per cent a nd sili con at concentra-
t ions below o.or per cent , a 2.5-amp. d .c.
arc source was used. T he arc was st ruck
with a pure graphite rod. No lens was used
between t he source a nd t he spectrograph
sli t, t he source being placed at a su fTt cien t
distan ce from the sli t to make sure t hat all
ligh t t hat passed through the sli t also
passed t hrough the spectrograph lens. The
spect ra we re recorded on Eastman poly-
chrome plates by means of a medium
quartz spectrograph .
In t he de ter minations a bl ackening-
logarithm-of -intensity cali brat ion pattern
was placed on each pla te in add iti on to the
spect ra of the specimens. Calibrat ion was
accomplished by photographing a con-
t inuous li ght sou rce through a "Il a nsen
step-diaphragm acco rding to the method of
Thomson and Duffendack.
2
The blacke n-
ings (defined as the difference bet wee n the
peak of the gal vanometer deflection of a
microphotometer for t he spect ra.! line a nd
the defl ect ion for t he transparent plate) o[
the selected spect ral lines and of t he steps
of the intensit y cali bration pattern were
obtained by means of a nonrecording
mi crophotometer. F rom t he blackenings of
the steps of thi s pattern, a cha racteristi c
cur ve for each plate was drawn and was
then used to determine the logarithm of the
relative intensity of the selected line pair.
This procedu re, carried out for a series of
specimens of known composition in whi ch
the element under analysis varied over the
desired concentration ra nge, yielded a n
analytical cur ve for the analysis of t hi s
element. T he analysis of a specimen of
unknown compositi on was made, applying
the logarithms of t he relative intensities
of t he selected spect ral line pairs deter-
mined in the ma nner described above to t he
appropriate analyti cal cu rve and by read-
ing therefrom t he percentages of the ele-
ments under test.
In t he analysis of magnesium for alu-
minum, calcium, copper , manganese, sili -
con, zinc and cadmium, lead and tin at
concentrations greater t han o.I per cent ,
t he procedure used was similar to that
out lined above except t hat a condensed
spark source was used in place o[ the direct
current arc.
The procuring of satisfactory standard
specimens to be used in const ructing t he
a nalyt ical cur ves referred to above ofi ered
no diff1cu lty in the case o[ metal concentra -
ti ons of o. r per cent or greater. The oblain-
i ng o[ sa t isf aclory sta nda rds in t he
concentrat ion range below o. r per cent did ,
however, present a real problem. /\ II
st andard specimens used in the latter con-
cent rat ion range we re made by adding
known a moun ts of the vari ous constituents
to sublimed magnesium. These specimens
were t hen carefull y a na ly;,cd by the foll ow-
ing chemica l procedures:
T he thi ocyanate and the aa' dipyridyl
met hods were bot h used t.o aid in t he
st a ndardi zati on of the iron ana lysis. T he
aa' dipyr idyl method was less critical to
sli ght cha nges in the a nalyt ical techni que
and , since bot h met hods gave the same
resu lt , it was t he method used in t he
analysis of most o[ the standard samples.
J\t t he beginning or thi s invest igation no
chemical method was developed that
CORROSION STUDIES OF MAGNESIUM AND ITS AJ. LOYS
would yield a satisfact ory a nalysis for
ni ckel in magnesium in the order of o.ooi
per cent. There were satisfactory methods,
however, for the analysis of nickel in the
range o.r to I.o per cent concent ra ti on. To
obtain the standard specimens, a ll oys with
ni ckel contents of o.r to r.o per cent were
ftrst prepared. After satisfact ory chemi cal
a nalyses of these specimens were obtained,
the s pecimens were diluted by known
a mounts with nickel-free magnesium. Since
nickel is completely soluble in magnesium
in t his concentra tion mnge it was possible
to prepa re sati sfactory standards in thi s
manner covering the concentration
of o.ooo25 to o.os per cent. A modif1ed furil
dioxime method for this determination has
since been developed. J<esults obtained by
thi s chemical method :tnd by the spectro-
chemical method based on the standards
prepared in the ma nner described above
a rc in very good agreement. The average
error of the spectrochemi cal a nalysis in the
range of o.oo2 per cent iron and ni ckel based
on triplicate determination is o.ooos per
cent.
T he standard specimens for the analysis
of lead in magnesium were a nalyzed by the
colorimetric dithiazone method.
The chemical silicon determinations
in concentrations below o .os per cent were
made by the molybdate colorimetric
procedure.
The elect roly tic, colorimetric a nd iodide
methods were used for the chemica l
determination of copper. The electrolyti c
method was most satisfactory at concen-
trations of the order of o.r per cent and
higher. Below this figure the colorimetric
and iodide methods were more sensit ive
and accurate.
REFE RENCES
T. W. R. Veazey: U. S. P atent 1377374.
2. K. B. Thomson a nd 0. S. Duffendack: Jnl . Op-
tical Soc. Amcr. (1933) 23, IO I- I04.
3. L. Whi tby: Jnl. Chem. and Ind. (I93 I) To, 83- 85.
4 H. Vosskf1hler: Magnesium and its Alloys, 43
Beck, 1939.
5 G. I. Finch and A. G. Quarrel: Proc. R oy. Soc.
( 1933) 141-A, 398.
6. G. D. Preston and L. L. Bircumshaw: fJIIil.
( 1935) 20, 706.
7. W. 0. Kroening and S. Pawlow: Korrosion 1wd
Metallschlllz ( 1934) 10, 254.
8. W. Schmidt and W. Schultze: Die Korrosion
Mctalli sche r WcrkstofTe, 445- 4 77 l,eipzig,
Hi rzel , 1938, 0. Bauer.
9. VV. Schultze : Magnesi um and its Atloys. 272-312.
Beck, 1939.
1 0. G. D. Bengough: Tra.ns. Tnst. Chern. Engrs.
( 1933) II, 176.
11 . T. P. H oar: hul. ( Aug. 19J6) 177.
12. L. Whitby : Trans. Fara d ay Soc. ( 19J3) 29, 853,
13 18.
13. M. H ansen: Jnl. Inst. Metals ( 1927) 37, 93- 100.
14. N . J. Ste panow and j. J. Korni!off: Trudi
Nauchno Jssledovatclskego Inst ituta Legkhi
Metallov ( 1932) H. 57.
15. J. W. Jenkin : Jnl. I nst. Metals (1927) 37, 93.
16. J. A. Gann: Trans. A. LM.E. (t929) 83, 309.
J7. j. A. Boye r: Nat. Ad vis. Comm. for Aero. , Rcpt.
248 ( 1926).
18. Vys koci l: Call. Czech. Chcm. Comm. ( 1934)
6, [.
19. Catty Spooner: T he Electrod e Potential Be-
havior of Corroding Metals in Aqueous Solu-
tions. Oxford Uni v. Press, 1938.
DISCUSSION
(P. 1". StroufJ fncsiding)
1' . T. STROUP, * New Kensington, Pa.- This
is a significant contribution in the fi eld of
corrosion studies of magnesium. I think it
rather strikingly illustrates the extensive
damage caused by new of iron and
magnesium and the remarkable effect in
counteracting this t hat is caused by manganese.
E . i\. ANOEll SON, t Palmerton, Pa.- This
paper is so beautifull y and comprehensively
written as to be readi ly understandable without
hard work, yet it encompasses a great deal o[
reall y good research.
The paper illustrates something that we do
not :til think about enough; that is, we do not
really know the properties of an clement. vVc
arc only beginning to grope nearer to
knowledge. We have been talking about mag-
nesium as nonresistant to chloride, with all t he
qualifications these authors have put on that
statement. Now we fmd that when we approach
the elemental form it is a n entirely different
product.
Workers in industri al research laboratories
ought to pay more attention to this basic
problem of trying to produce a metal that is
reall y pure, and try to find out what it really is.
L. W. K E M:PF,t Cleveland, Ohio.- It would
be interesting to know the actual concentra-
* Research Metall urgist, Alumi num Company of
America .
t Chi ef of Metal Sectio n. Research Division, New
Jersey Zinc Co.
t Metallu rgist, Alurninum Research Laboratori es.
DISCUSSION
299
tions of iron and perhaps copper and nickel in
the specimens.
J.D. H ANAWALT (author's reply) .- 1 should
like to further emphasize Mr. Anderson's com-
ments about the importance of knowing t he
inherent charact eristics of pure materials.
Without knowing the drast ic effects of trace
impurities on corrosion resistance in aqueous
media, one is likely to place magnesium in a
class with calcium instead of in a class with
aluminum, and, further, t o assume that the
solubility or the density or some other char-
act eristics of its naturally forming film is
responsible for its behavior and that nothing
can be done about it. i\ctually, its protective
fi lm characteris t ics arc quite adequate in the
absence of cathode electrodes wit h large driving
potentials with respect to magnesium, and the
inherent cha racteri stic of magnesium that is
different from t hat of other corrosion- resis tant
metals is its high anodic solution poten tial. The
problem then becomes one of contact corrosion.
In answer t o Mr. Kempf' s question on the
composition of t he pccimens, the data for
which arc shown in Fig. s, the concentrations
of impurities in these specimens fa ll in t he
range of less than one thousandth iron, less
t han one hund redth copper, a nd less than one
thousandth nickel.
Since the present paper was submitted for
publication, a n a rticle by /\. Beerwald has
appeared in z,itsrli rijt fiir iltttaltkundc f( ' 94 ' )
33, 28] which covers some of the same subj ect
matter as t he present paper and requires
discussion, part icul a rl y in connection wit h the
concl usions of the two papers. The titl e of the
paper is " The I nflucnce of I mpuritics on
the Corrosion Behavior of M agncsium and Tts
All oys wit h Manganese and Aluminum."
The paper presents the analysis of cell
magnesium and of distill ed magnesium, not es
the extreme difference in salt-water stabi li ty
between them and concludes that t he difference
must be ctue t o Fe or Cl. The specimens were
prepared from t he distilled magnesium as base,
and the rate of hydrogen evolut ion during the
frrst few days exposure to 3 per cent ' hCI was
measured. In agreement wit h the present
authors, Beerwald found no detrimenta l eiTect s
due to Cl. However, because of t he way in
which his experiments were carri ed out, he
states hi s conclusion on the eff ect of iron so
that it sounds in absolute cont radiction to ours,
whereas in reali ty, t he two paper are in com-
plete agreement insofar as they :tre related. For
this reason it seems desi rable to discuss Hecr-
wald' s paper at t his time. With respect to iron,
Bccrwald stales in his concl usion that t he cor-
rosion rate is increased hy a trace in t he
order of thousandt hs per cent and increases
with increasing iron content unt il t he per-
centage of iron reaches about o.o3 a nd t hat
hi gher percentages of iron over t hi s amount arc
only of s mall signiti cancc. Bccnv:tl d' s obser-
vations arc limited t o the early stages of
formation and his concl usions, therefore, refer
to the ini t ia l rates of corrosion, whereas our
rates represent a s t eady-stale condition.
Our hypothesis, t hat the initi a l peri od of
corrosion is one in which cathod ic impuriti es
arc being undermined and removed or arc
being covered over hy spread nf t he anodic
fi lm, would predi ct results simil ar lo those of
Hccrwald 's; though with the additiona l condi-
tion t hat, if impuriti es arc below the tolerance
limit, a fi nal st eady stale of low corrosion rate
is reached after about days. T hese resul ts
arc given mon; fu ll y in a recent publicati on h,
R. I:. i\'l cNully a nd j . IJ. ll anawalt [Preprint
Sr- 12, I: lec trochem. Snc. (:\pril 1942) ].
TRANSACTIONS
OF THE
AMERICAN INSTITUTE OF MINING
AND METALLURGICAL ENGINEERS
Volum.e 147
l NS'TI_'TU'TE OF ME'TALS DIVISION
1942
.\t\ D DI SCHSSI ONS PRESI: XTI: D ' I !I E ,\T i\I J: J;T I Nt :S III: I.IJ .\T
I' IIIL.\01-:I.PIII.\
1
OCTOBER 20 22, 194- 1, .\ N D :\'E\\" \'OI(h: ,
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