332 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 19, No.

Controllable Variables in the Quantitative Study of

the Submerged Corrosion of Metals'
By 0. B. J. Fraser, D. E. Ackerman, and J . W. Sands
NICKEL
INTERNATIONAL N. J.
Co., BAYONNE,

HE development of laboratory methods for determining exerted over the test conditions, particularly these three :

T the probable life of corrosion-resistant metals and al- (a) composition of the medium, (b) velocity of relative move-
loys has received much attention in recent years. ment between metal surface and medium, and ( c ) temperature.
The ancient "beaker" test is no longer accepted as anything I n the absence of serious interference from compact films of
more than an indication of the manner in which corrosion insoluble products of corrosion accumulating on the metal
may take place. As such it is a valuable means of exhibiting surface, the relationships between rate of corrosion and these
tendencies toward pitting or deep corrosion a t or near the variables are continuous and fairly simple. They have been
solution surface, but quantitative determinations by this determined for the action of aqueous solutions of sulfuric
method of exposing pieces of metal in quiet, unaerated solu- acid upon monel metal.
tions are not in favor with engineers because they represent I n this .case the corrosion rate, a t constant temperature,
conditions rarely met in practice. varies continuously with the concentrations of hydrogen ion
Much confusion has arisen in a search for an accelerated (acid) and dissolved oxygen in solutions of from 0 to 80 Der
test which would give re- cent sulfuric acid, by weight.
liable information in a few With higher acid concentra-
hours. Concentrations of The great influence of controllable variables on the tions than this, the rate is
corrosive components have results of laboratory corrosion tests of the total-immer- also a continuous, but differ-
b e e n changed arbitrarily, sion type is discussed and illustrated by numerous ent, function of the con-
or, even worse, rates of cor- data obtained in a study of the action of sulfuric acid centration. The change in
rosion obtained in solutions solutions on monel metal. Three types of apparatus function is consequent upon
of one reagent have been are described, which provide for control of the variables, an abrupt change in the
used to interpret the resist- and with which satisfactorily reproducible results have nature of the corrosion re-
ance of metals to other quite been obtained. action.
different media. The im- The concentrations of dissolved oxygen and of the I n dilute sulfuric acid the
position of an external cur- active ions of the solution, the velocity of relative corrosion rate, at constant
rent on the metal to be motion between test pieces and solution, and the tem- temperature, is directly pro-
studied as anode, with an in- perature must be controlled closely, because the vafia- portional to the oxygen con-
s o l u b l e cathode, has been tion in rate of corrosion with changes in any of these centration, reaching a maxi-
suggested as a suitable variables is of considerable magnitude. Moreover, mum, therefore, when the
means of acceleration, but such changes in rate of corrosion are not always in the solution is saturated with it.
the reliability and utility of same direction because of the concurrent differences C o n s e q u e n t 1y , the most
the method have so far not in oxygen solubility with changing ionic concentrations effective means for control-
been demonstrated. It is and temperature.
l i n g t h i s v a r i a b l e is to
indicative of what may take m a i n t a i n t h e solution at
place when two metali of saturation with respect to
d i f f e r e n t potential are in air.
contact in the same solution, but not of the normal corro- The corrosion rate increases continuously with the velocity
sion of a single metal. of relative movement between the test piece and the solution.
That there is a general need for acceleration is questionable. The rate of change of corrosion rate diminishe3 as the velocity
I n a majority of corrosive media metals, if they corrode a t all, increases, and approaches constancy a t a velocity of about
are usually dissolved in sufficient quantity in 24 hours, or 200 feet per minute. Obviously, fairly high test velocities
less, to permit accurate determination of rates of corrosion. are desirable so that the effect of variations in velocity during
The quantity and physical structure of solid products of the time of test will be minimized.
corrosion very frequently govern the ultimate course of The corrosion rate, in the manner of reaction velocities
corrosion, so that 24 hours may not always be a sufficient generally, increases logarithmically with the temperature,
time, but it has been found to be more than sufficient for doubling itself within about, 30" C. This relationship is
most metals and alloys which have been studied by the au- maintained only to a maximum a t 70" C., beyond which the
thors. rate decreases because of rapid decrease in the solubility of
The maintenance of a maximum supply of air, and of move- oxygen a t the higher temperatures. The low temperature
ment between test pieces and solution, are not, strictly coefficient, 1.3 for a rise of 10" C., is typical of diffusion proc-
speaking, steps to provide an accelerated method of testing, esses, and is characteristic of reactions in heterogeneous sys-
since these are very frequent conditions of service which any tems.
test should simulate. Finish of test pieces is unimportant in most cases, so long
Conclusions as they are clean and reasonably smooth.
Development of Methods
The principal conclusion to be drawn from the experimental
data recorded herein is that, if accurate information is to be Calcott and Wheteel2 apparently were the first to present a
obtained from laboratory corrosion tests on metals and al- critical discussion of general methods for laboratory study.
loys totally submerged in liquid media, close control must be Following their contribution numerous other articles and
1 Received November 6, 1926. 2 Trans. A m . Insl. Chem. Eng., 16, I, 10923).
March, 1927 INDUSTRIAL A N D ENGINEERING CHEMISTRY 333

papers have been presented.J Formerly, the great importance the main volume of solution from a small volume within the
of providing for relative movement between test pieces and enclosed space, which, because of the corrosion reactions,
solution, and of maintaining constant aeration, was not is soon of a composition very different from that of the main
realized. More recently, Thompson and McKay showed body. Through the operation of active concentration cells
that rate of movement and aeration must be controlled if in such an environment, very rapid and deep localized corro-
concordant and useful results are to be obtained. sion can, and often does, take place beneath masses of prod-
Alternate immersion methods were suggested by Rawdon ucts in solutions which corrode the metal initially a t a low
and Krynitsky as being a means of controlling aeration. rate. I n the case of monel metal in sulfuric acid solutions,
These have proved useful in studying the value of metallic there is ample evidence that the structure of the small amount
coatings on iron and steel, but their general utility has not of solid products formed is such as to offer only slight re-
yet been established. Great differences in results may arise sistance to diffusion. Hence the rate determined from a 20-
from such things as uncontrolled drafts, changing humidity, hour test is not a t variance with one from a longer test
and hygroscopicity of salts on the drying surface, so that the period, or with one developed by measuring the weight loss
results must be interpreted with caution. over a final portion of a longer period, as recommended for
general practice by Calcott and Whetzel.
Influence of Controllable Variables Shape and finish of test pieces are often of minor importance,
The principal variables over which control must be exerted particularly where the rate of corrosion is appreciable. The
in order to obtain concordant results are: composition of the pieces should be truly representative of
the material to be used in service, but no great precaution in
(a) Composition of the solution with respect to all partici- surfacing is necessary beyond insuring that they are clean and
pants in the corrosion reactions; which implies constancy in reasonably smooth. There are exceptions, such as the action
concentration of the active components, including oxygen.
( b ) Velocity of relative movement between metal and solution. of strong alkaline hypochlorite solutions on nickel-copper
(c) Temperature. alloys, where a polished surface resists for a considerable time
the initial attack of solutions of much higher concentration
It is essential that the composition of the solution, including than the limit for safe commercial use of such alloys. Another
oxygen, be maintained uniform throughout the time of test, instance is the formation of rust on chromium-iron alloys,
particularly in the immediate vicinity of the test pieces. which is initiated more readily on rough than on smooth sur-
This requires movement between metal and solution, which faces. Test pieces, of course, should be of proper size so that
insures continuous renewal of reactants and removal of soluble weighing errors for small changes in weight will be minimized.
nroducts of corrosion. Absolute control of the rate of move-
mentis not possible, but it may be approached closely. These Composition of the Solution
points are of particular importance if results are to be applied
to the design of equipment to be exposed to continuously re- CONCENTRATION OF PRINCIPAL CORROSIVE CONSTITUEFF-
newed solutions. The temperature influence is of the usual Figure 1 and Table I show the variation of corrosion rate
nature for chemical reactions,
up to the point where decreas-
ing oxygen solubility causes a
sharp depression of the curve
representing the relationship.
The rate of corrosion within
this range, as has been stated,
bears a logarithmic relation-
ship to the temperature.
The duration of a test is .L
important in many instances. 5
C a l c o t t a n d Whetze12 and
Pratt and Parsons3 have drawn 5
attention to the fact that the $
initial rate of c o r r o s i o n i s 2
u s u a l l y considerably greater e
than the later and more uni-
form rate. Cases are known 6
where the opposite is true; the 30 'i:
later rate is much greater t.han $
the initial. I n the one case tD 3
s o l i d p r o d u c t s of corrosion 2
are d i s t r i b u t e d evenly, and 8
have a p h y s i c a l s t r u c t u r e
w h i c h i n t e r f e r e s uniformly IO
with the diffusion of reactants
Figure 1
and resultants to and from O-Corrosion rate curve. O-Hydrogen-ion concentration. A-Oxygen solubility.
the corroding surface. I n the
other the solid products are of a different nature and dis- with acid concentration, a t room temperature. It is evident
tribution, and frequently serve as diaphragms separating that a corrosion rate determined a t one concentration is not
8 Thompson and McKay, THISJOURNAL, 16, 1114 (J923); Rawdon to service at a different concentration*
and Krynitsky, Trans. A m . Electrochem. SOL, 46, 359 (1924); Rawdon, The break in the curve in the vicinity of 80 per cent
Krynitsky, and Finkeldey, Proc. A m . Soc. Testing Material.;, 24, 11, 717 sulfuric acid marks a change in the corrosion reaction. I n
(1924); Farnsworth and Hocker, Trans. A m . Electrochem. Soc., 45, 281
(1924); Wernlund, I b i d . , 45, 294 (1924); Pratt and Parsons, THISJOURNAL,
the lower concentrations it may be represented as
17, 376 (1925); Whitman and Russell, I b i d . , 17, 348 (1925). M + H2SOd + '/202 = MSO4 4-HzO (1)
334 INDUSTRIAL A N D ENGINEERING CHEMISTRY Vol. 19, No. 3

where M represents both copper and nickel. I n the higher reason that the maximum in the corrosion rate curve occurs
concentrations a second reaction intervenes, which is prob- at an acid concentration lower than that of maximum hydro-
ably analogous to that stated by Piekering’ for copper in gen-ion concentration.
concentrated sulfuric acid, namely:
5 c U f 4HzS04 = c U & 3cUso1$- 4Hz0 + (2)
Table 11-Influence of Rate of Aeration on t h e Corrosion Rate of
Monel Metal i n 5 Per Cent Sulfuric Acid Solutions, a t Room
A corresponding reaction for nickel would be Temperature
4Ni +
4H2S04 = NiS f 3Nis04 f 4H20 (3) AERA-
TION
No. OF
TEST
CORROSIONRATE Av.
PEKE-
Av. D E W
ATION FROM
This explanation f& the break in the curve is supported by RATE PIECES Max. Min. Av. TRATION MEAN
the fact that irregular patches of sulfides were formed on the Cc./min./l.
test pieces in the 93.5 per cent solution. It is noteworthy soh. Mp./sg. dm./day In./yeau Per cent
0 2 0 0 0 0.0000 to.0
that the two test pieces in 75 per cent solution were the only 25 2 129 114 121.5 0.0197 t6.2
ones throughout the study which did not check closely. 75 2 141 140 140.5 0.0228 10.4
100 4 170 160 165 0.0267 *2.6
150 2 159.5 157 158 0.0256 11.6
260 2 164 161 162.5 0.0263 *0.9
450 4 182 165 171 0.0277 *3.1
Period of test, 20 hours.
Test pieces in constant motion at 12.6 feet per minute.

I n the range of concentrations from 15 to 75 per cent sulfuric

acid the corrosion rate curve is a straight line. I n this range
i t has a slope differing only slightly from that of the assumed
curve for hydrogen-ion concentration. The oxygen solu-
bility curve becomes much less steep in this region, leaving
the hydrogen-ion concentration as the principal variable.
AERATION: OXYGEN-The influence of the rate of aeration
is shown by Figure 2 and Table 11. For the run with zero
air input, the solution was made up with freshly boiled water,
cooled out of contact with air, and subjected to the passage
of a stream of nitrogen throughout the test. The complete
resistance of the alloy to corrosion in sulfuric acid in the ab-
Figure 2 sence of oxygen is of special note.
It is evident that it is not enough just to add “some” air.
The values for hydrogen-ion concentration, up t o 38.03 There must be sufficient to maintain constantly the saturation
per cent sulfuric acid (10 N ) , were calculated from the data concentration in the main body of solution, and hence a uni-
of Jones.5 I n 95 per cent solution sulfuric acid is dissociated form rate of diffusion through the liquid layer a t the metal
to the extent of 1 per cent16which furnishes the last point on surface. An air supply of a t least 100 cc. per minute per
the hydrogen-ion curve. This point has been joined arbi- liter of solution is necessary in the case under discussion. Of
trarily by a straight line to the remainder of the curve, in course, only a very small proportion of the total oxygen in
the absence of data for intervening concentrations. The this amount of air is actually consumed in the corrosion re-
oxygen solubility curve, which is for pure oxygen under at-
mospheric pressure, was constructed from Seidell’s data.’
Table I-Influence of Acid Concentration on Corrosion Rate of
Monel Metal in Aerated Solutions of Sulfuric Acid a t R o o m
Temperature
No. OF CORROSION
RATE Av. Av.Devr-
Has04 TEST PEN& ATION F R O M
PIECES Max. Min. Av. TRATION MEAN
Per cent M g . / s g . dm./day In./year Per cent
0.1 4 95 87 93 0.0151 t3.2
1 4 144 130 139 0.0226 k3.8
2 4 212 188 202 0.0326 14.3
4 12 250 157 219 0.0356 15.6
5 4 227 216 221 0.0358 *1.6
10 4 221 206 215 0.0349 t2.0
15 4 202 193 196 0.0318 t1.7
25 4 144 135 139 0.0226 *2.3
50 4 61 55 56.5 0.0092 14.0
75 4 31 18 23.5 0.0038 -21.3
83 2 32 31 31.5 0.0051 *1.6
85 2 65 67 66 0.0107 *1.5
93.5
._ . 4
~ 727 585 668 0,1085 *6.1
Period of test 20 hours.
Test pieces in’ constant movement in circular path at rate of 16.75 feet
per minute.

If the oxygen availability did not decrease as the acid con-

centration increased, it would be expected that there would be
little change in the slope of the curve until the maximum
hydrogen-ion concentration was reached. However, the oxy-
gen availability, which is governed by its diffusion rate, does
decrease as the acid concentration increases, not only be-
cause of the decreasing solubility of oxygen but also because of
the increasing viscosity of the solution. It is probably for this
4 J. Chem. Soc. (London), 33, 112 (1878). action. The excess passes off in the bubbles which escape
5 Z . p h r s i k . Chem., 66, 385 (1906).
6 Smith, “General Chemistry for Colleges,” 1 s t ed., p. 228.
from the solution.
7 “Solubilities of Inorganic and Organic Substances,” 2nd ed., 1919. The maintenance of complete aeration is warranted be-
March, 1927 I S D USTRIA 11 A N D ESGINEERIYG CHE-MISTRY 335

cause, as has been stated already, this is a very frequent, and

almost invariably the most severe, condition of service for
metals and alloys in all kinds of liquid media. Moreover,
it is much easier to maintain a solution completely saturated
with air than a t some lower concentration.
Figure 3 and Table I11 show the effect of varying the oxy-
gen-nitrogen ratio in the saturating atmosphere, other con-
ditions remaining constant. All atmospheres except that
containing 21 per cent oxygen, which was the normal air
supply of the laboratory, were meter-controlled mixtures of
oxygen and nitrogen led into a mixing chamber, from which
the gas mixture flowed into the corrosion vessels at the rate of
100 cc. per minute per liter of solution.
Table 111-Influence of Concentration of Oxygen in t h e Saturating
Atmosphere on Corrosion R a t e of Monel Metal in 5 Per C e n t Sulfuric
Acid Solutions, at R o o m Temperature

C ~ ~ ~ ; ~ & G No.
G A OF
S CORROSIONRATE Av. Av.
TEST PENE- DEVIATION
PIECES Max. &fin. Av. TRATION FROM MEAN / / I
0
INrlUfME OF TEI-IPERA
TURE ON
R b y vol. 70by vol. Mg./sq. dm./day In./year Per cent -- 7H€ ORROS/ON OF /'?O#€L &TAL
0
in
._
100
sn
..
2
4
0
9:3.6
.. .
0
87
0
90
0.0000
0.0146
10.0
13.2 E INAERATED S%H,SO,Sorurim , , , , , ~

21a 79 4 170 160 165 0.0267 12.6

50 50 2 295 289 292 0.0473 Al.0
100 0 2 561 548 554 0.0898 12.3
aNormal air supply of the laboratory.
Period of tests, 20 hours.
Test pieces in constant motion at 12.6 feet per minute.
Rate of input of gas mixture, 100 cc. per minute per liter of solution.

The rate of corrosion is a linear function of the concentra-

tion of oxygen, and hence of its partial pressure, in the satnrat-
ing gas mixture, except for concentrations approaching zero.
-4s the rate of diffusion of a gas through a fluid mediurr is
proportional t o its concentration or partial-pressure gradient.
the corrosion rate-oxygen concentration curve of Figure 3
is indicative as well of the influence of oxygen concentration
in the saturating atmosphere on its rate of diffusion to the
metal surface. Evidently this rate of diffusion is the limiting
factor in the corrosion of monel metal in sulfuric acid solutions,
as it is in so many other cases of corrosion.
The curves of Figures 2 and 3 are quite different in char-
acter. The form in Figure 2 is undoubtedly due to variation
in absorption efficiency with increasing air input, and not
directly t o the effect of changing concentration, which de-
termines the forni of the curve in Figure 3.
I n Table I11 the ratio of corrosion rate with pure oxygen to
that with air is 3.4. Speller8 states that the concentration of
Figure 4
oxygen in gases dissolved by water in equilibrium with air is
35 per cent, the enrichment from the normal 21 per cent in air
being due to the greater solubility of oxygen. The data of
' "Corrosion: Causes and Prevention," p. 1 4 1 ( 1 9 2 6 )
Figure 5
Solid products of corrosion may or may not have an im-
portant influence on the rate of diffusion of oxygen, depending
upon their quantity and physical structure. If they had.
in this case, the relationship between corrosion rate and
oxygen concentration would not be linear, because as the
amount of corrosion increased with increasing oxygen the
thickness of the layer of products would increase, and rate.
of diffusion would be retarded to an increasing extent. h
continuous, tightly adherent, nonporous envelope of products
would be expected t o produce such an effect. I n the case of
monel metal in sulfuric acid such an envelope is not formed.
This statement is based upon other tests not reported herein,
in which the influence of time was studied. There is a very
small amount of brown product, probably hydrated oxideb.
which increases in quantity with increasing weight loss as
the concentration of oxygen in the saturating atmosphere
is increased. The layer of product apparently is of an open
structure, very easily rubbed off, and does not offer serious
resistance to the diffusion of oxygen. Such a condition
is far from general in the corrosion of metals, nor is it true
for monel metal in all media. I n acetic acid solutions monel
metal acquires a coating of products of quite different physical
characteristics, which interferes to a marked degree with dif-
fusion. Although no study of the point has been made
in acetic acid, it is believed that the relationship between
oxygen partial pressure and rate of corrosion would not he
linear.
The rates of corrosion with a sufficient supply of normal air
are lower in Tables I1 and I11 than the corresponding d u e
for the 5 per cent sulfuric acid solution in Table I. This is
0 Seidell, "Solubilities of Inorganic and Organic Compounds " p 458,
472
336 INDUSTRIAL AND ENGINEERING CHEMISTRY VOl. 19, No. 3

due to the influence of temperature, and will be discussed as easily displaced than those closer t o the metal surface, where
such in a later paragraph. the electrical and surface tension forces exert a maximum in-
VOLUMEOF SoLuTIox-Calcott and Whetze12 concluded, fluence, preventing complete destruction of the stationary
for quiet, unaerated tests, that a volume of 200 cc. per test layer. Sometimes, particularly a t high velocities, there
piece, measuring 2 X 1 X 0.01 inches (0.508 X 0.254 X would be a tendency also to throw off interfering solid prod-
0.00254 dm.), was sufficient. The exposed surface of such ucts of corrosion, or to avoid their formation on the metal
a piece is approximately 0.26 sq. dm. The test pieces for surface by separating the metal from soluble products before
this study were disks 1 inch (0.254 dm.)in diameter and their precipitation in an adherent form could take place.
0.25 inch (0.063 dm.) thick, having a total surface area per Where hydrogen evolution accompanies corrosion the in-
test piece of approximately 0.15 sq. dm. These were cor- fluence of velocity upon the overvoltage of hydrogen is im-
roded in pairs in baths of either 2000 or 4000 cc. volume- portant. This has been discussed thoroughly by Whitman,
very large in comparison with those suggested by Calcott and Russell, Welling, and Cochrane.lo
Whetzel. Such an excess provides for a large reserve of the The curve of Figure 4 is very similar in shape t o those of
corrosive components and avoids the building up of concen- Whitman and Russell3 for the influence of velocity on the cor-
trations of soluble products of corrosion to dangerous levels. rosion of copper in aerated sulfuric acid solutions. Their
The acid contents of the baths remained constant, within the curves for copper in aerated acetic and hydrochloric acid
limits of analytical error, during the tests. The maximum solutions were of quite different shape, however, for which
amount of metal dissolved in any of these tests, had it all they advanced an extended explanation.
remained as soluble products, would have given a final metal
content in the solution of only 0.04 gram per liter. This was
in one of the 73" C. tests of Table V.
Velocity of Movement between Metal and Solution
The influence of velocity on corrosion rates has been studied
by others.I0 There is a general tendency toward increasing
rates of corrosion with increasing velocity, and Figure 4 and
Table IV illustrate the tendency in the case of monel metal
in 5 per cent sulfuric acid solution, a t room temperature.
Table IV-Influence of Velocity of Solution Flow o n t h e Corrosion
Rate of Monel Metal i n 5 Per C e n t Sulfuric Acid Solutions, a t R o o m
Temuerature
\r
NO, OF RATE
CORROSION AP. xv. Figure 6
VELOCITY TEST PENE- DEVIATION
PIECES Max. Min. AV. TRATION FROM h l E A N
The tests of which results are given in Table IV were run in
Fl./min. Mg./sq. d m . / d a y In./year Per cent
0 4 116 103 108 O.Oli5 13.5
a different type of apparatus from those of the preceding
11 4 141 130 134 0.021i *2.6 tables, to which is due their generally lower rates of corrosion.
13 4 134 119 128 0 0207 *3.7
82.5 2 296 294 295 0 04i8 h0.3 This apparatus is of a continuous-flow type with stationary
131 2 331 319 325 0 0526 +l 8 test pieces, while that used in the other tests provides for
142.5 2 329 317 323 0 0523 *l D
240 2 388 370 379 0 0614 -2 4 test-piece movement. The apparatus is described in a later
Period of tests, 20 hours. section. The lower rates in the tests of Table IV are believed
Rate of aeration, 100 cc. minute liter of solution to be due actually to differences in absolute velocities be-
tween solution and metal, which, in the moving test piece
Velocity changes are generally considered to influence rates type of apparatus, are probably not the same as the known
of diffusion of reactants and soluble products of corrosion to rate of movement of the test piece.
or from the metal surface. I n every case of submerged
corrosion t'here is held to be a stationary layer of liquid im- Temperature
mediately adjacent to the metal surface. If corrosion is to Figure 5 and Table V show the influence of temperature
proceed, dissolved metal ions must diffuse outward through upon the corrosion rate. A logarithmic relationship exists
this layer to the main volume of olution and corroding ions over a major part of the total range, or up to 70" C. The
and oxygen must diffuse inward. The net rate of reaction equation connecting the two is of the type
will be governed by the slowest rate of diffusion. Diffusion
rates are proportional to the concentration gradients through,
Log R = a + bT (4)
and inversely proportional t o the thickness of, the stationary where R is the corrosion rate, a and h are constants, and T is
liquid layer. As the solubility of oxygen in sulfuric acid solu- the temperature in degrees Centigrade. I n this case a =
tions is small, the rate of diffusion of oxygen through the 2.097 and b = 0.0103.
stationary liquid layer is the controlling factor. The effect' Calcott and Whetzel noted that the influence of teniper-
of increasing the oxygen concentration gradient, as shown in ature in many corrosion reactions could be represented by the
Figures 2 and 3, is ample supporting evidence. Any decrease type equation for velocity of homogeneous reactions :
in the thickness of the fixed liquid layer should result in a LogR = a + -b (5)
proportional increase in the rate of diffusion of oxygen. A ra

rapid movement of solution past the metal surface evidently
decreases the thickness materially, for the rate of corrosion
increases progressively, though a t a diminishing rate, as the
velocity is increased. The diminishing rate may be explained
by considering that the outer portions of this layer are more
10 hlcKay, Trans. A m . Elecfvochern. Soc., 41, 201 (1922); Friend and
Dennett, J . C h e m . Soc. (London), 121, 41 (1922); Calcott and Whetzel,
loc. c d . ; Whitman and Russell, loc. c i f . ; also, with Welling and Cochrane,
THISJ O U R N A L , 15, 672 (1923); Speller and Kendall, [ b i d . , 15, 134 (1923).
where T, is the absolute temperature. The curve in this
case may be evaluated in terms of such an equation. TVhit-
man and Russell3 found values for the corrosion of steel and
aluminum in 50 and 96.5 per cent sulfuric acid, within the
range of 20" to 50" C., which comply with similar laws. I n
6 per cent acid neither metal complied with such a law, nor
did steel in 20 per cent, nor copper in 6, 20, or 96.5 per cent
sulfuric acid.
Above 70" C. the oxygen solubility decreases to such a
 e the I:LW
-mall ~ a l u tliat is not obeyed. ,411idea of the miinner
i n which the solubility of oxygen decreases as tlie tempera-
ture increases mny he had from examination of Fiwre 0,
which gives the relationship for water. A similar relationship
probably holds for a 5 per cent solution of snlfnric acid.
Speller," from whose book tlie curve of Fignre 6 was talien,
found that the corrosim rate oi iron in natural water reached
a lnaximum a t 80" (!. and tllen decreased at higller teinpcr-
nt,urcr, 1)cc:tiise of decreasing solubility of oxygen.
'roble \.. -Influence of Tern erafure on Corrowion Rate of Munel
Mofnl In 5 Per &mt Sulfuric Acid Soluiion
A".
I'ilNt.
..I word of esplniiation may now be offered for tile difforent
corro?ion rates in 5 per cent acid solutions ill Tables I to 111.
The tempcratincs Twre not controlled thennostatically for
tlie determinations recorded in these t.ahIes. Those of Table I
were obtained in the summer, when the temperature ran8e
over the 20-tiour test periods was roughly 18" to 30" C.
Those of Tables I1 a.rid 111 u-ere found during the winter,
when the laboratory t.emperature was as low as 10" C . during
tlie night, and about 25" C. during the day. On inserting
in equat,ion (4) the logarit.1ims of the corrosion rates for 5 per
cent sulfuric acid from Tables I to 111, respectively, it is found
that the valne of 221 lug. per sq. dm. per day, from Table I,
corre,spondsto a temperature of 21"C., while tliat of 165 mg.
per sq. dm. per day from Tables I1 and 111 corresponds to a
temperature of 12" C. There is, therefore, no conflict among
tlie data.
Table VI- -Influence of liinieh of Teat Piecea o n Corrosion Rare of
Monel M e t r l in 5 Per Cent Sulfuric Acid Solution, B f 30° C.
NO. COBP-OSION K A T S
<:a\DE OY llNeKv OY
....
..
P.i*,-l+ M:lx~
~ ~~ ~~ Min.
~Mg/iu.dm./ilor
xo. 1 commercial 3 202 211
00 commercial 4 261 2S8
0 Iluhert'E 3 278 243
000 Hubert'a 4 284 240
Feriod of teats 20 hours.
xrte a [ .erati& 100 CE. per minute per liter of +tion.
veiucity of test piece movement, 18.81ieet per m7nuir
Finish of Test Pieces
Finid> is not important, within limits. Ctdeott and
\\'lictzel2 demonstrated this for cast iron, copper, and alu-
niiiiuiii against sulfuric, acetic, and nitric acids, respectively.
It is :ilso triic for monel inctal in snlfuric acid solutions. Four
differentfinishes, from that obtaiaable with No. 1 comriiercial
to tlie much finer finish produced by No. 000 Hubert's
i emery paper, were given to members of a series of
Sourtcerr test pieces. These were all corroded in aerated
.5 JW cent sulfuric acid solutions at 30" C. The range of
iletcrmiried corrosion mtes bears no posit.ive refercnce to the
siirface finish of the pieces. Tliere is a slight, gradual in-
crease in indicated values witli decreasing coarsenes? of
finish, but the endire range vf values shows an average devi-
ation from tlie mean of only *5.5 per cent. This isnot uni-
I-ersally true, for in certain solutions monel metal after being
wet-polislied to a mirror finish is, as has been stated already,
mi Freuenti".," i'.112 (lY2ti).
initially inucli more resistant to attack than the same met.al
with a ground surface. The rcsults of the group of tests
referred to in this paragraph are recorded in Table VI. These
were also included in Table V for the rate of corrosion at 30"C.
Apparatus
Tlrrcc differentsets of apparahs were employed, with all of
w l i i c l ~a siandard size of test piece, in the form of a disk I
inch (0.254 dm.) diameter by 0.25 ineh (0.063 dm.), is usually
iised. l.'ignre 7 shows what is called the circular path ap-
paratus, with which the data of Tables I, V, and VI were ob-
A". tained. It is a development from an earlier apparatus of
DI:YIITLOS
Tliampson and k 1 ~ K a y . ~ The type of motion oi the test.
pieces has !ieen (:hanged from a vertical, reciprocating move-
mciit in t,lic earlier apparatus to a uniform mot-ement on a
circular pntli, in a vertical plane. The test pieces are sup-
ported on glass stirrups, and w e set a t an angle bo tlie plane
of tlroir orhits. This insures positive flow of solution past
every point oil the metal surface at some part of each revolu-
tion. l'he absolute velocity of movement between solution
and metal is greader than the rate of linear travel of the test
piece because of the angular orientation described above, and
because of vertical currents r e s u l h g from tlie manner of
aeration. Except for bearings and gears, the apparatus is
h i l t of monel metal rod and shapes. Two crank shafts,
driven by lielical gears from a common drive shaft are sup-
ported on 5 frame of angle sections. Tlie cranks have a
tlirow of 1.5 inches, and are connected by a cross arm, from
four points in wliicti fire hung yokes, adjustable vertically, ior
a.itac1imeiit of the glass stirrups on which t,lie test pieces rest.
TIx soiirce oi power is a '/,-horsepower motor, connected
t.lirougli reduction gears and cliain and sprockets to the
comnioii drive sliaft. T l i e reduction gearing is adjustable
for speed to a, rnaxirninn of NO r, p. i n . , which gives a niaximum
A".
246
249
2iti
264
Fieure ?-Circular Parh Apparatus
liiiear speed for tlie test pieces oi 60 ieet per miiinte. Tllc
tliermostatically controlled water bath is contained in a sheet
nickel tank, and is heated electrically. The corrosive solu-
tions are held in Nonex glass battery jars and are usually of
4000 cc. volume. For tlie more concentrated solutions of
Table I the >-olnnies were 2000 ce. Air, or other gas, is snp-
plied througli porous alundum crucibles beneath funnels, in
tlie manner described by Thompson and McKay.3 Air or gas
\.olmne is controlled by flowmeters when necessary. Timttlly
it is easy to jiidge by tlie violoncc oi the aeration whet,lier
ufticirlit i h being provided. For high-temperature tests the
jars are covered by glass strips, except for slots in whicb the
glass supporting stirrups travel. Evaporation losses are con-
pen*nted for by (iistiiied TTat,er supplied from Mariotte bottles.
Figure n---Rofating Spindle Apparatu~
Figure 8 shows a rotating spindle apparatus, in which the
data of Tables I1 and I11 were obtained. It is a modification
of similar apparatus used by Whitman and Russell.3 A rec-
tangular jar rest.s on a hardwood base and has a hardwood
co\.er anchored to t.he hase by bolts and wing nuts. The
cover is equipped with a central opening surmounted by a
mercury seal, through which the shaft enters. Entry is
also provided for a gas-delivery tube. The cover is paraffined
on the under side and is drawn doivn tight on a rubber
gasket by means of the anchor bolts. A4monel metal shaft is
driven by belt and pulleys from a '/rhorsepower motor.
Speed adjustment is provided for in the pulley arrangement.
All met,xl within the vessel is gold-plated, and usually paraf-
fined. For low velocities an alundum crucible is used as il
gas diffuser. The test pieces are hung, a t a radial distanco
of 1.125 inches, in glass stirrups suspended from diametrically
opposite arms attached to the shaft. Velocities up to 1275
r. p. m., corresponding to 750feet per minute, can be obtained.
Some runs were made with cylindrical tests pieces mounted
coneentrically on the shaft, hut these did not give concord-
ant results.
Figure 9 is a sketch of a continuous flow apparatus, wit11
~ d i i r hthe data of Table IV were obtained. An apparatus
oi aiinilar nature has been suggested independently by
8peller." It provides for a continuous, straight-line fiow of
'Corrnsion: Causes and Prevention." P. 228.
New Paint Remover from Factory Waste
:\it cKecliue paint arid varnish remover can now be made by 8
discovered by Max Phillips and 31.J. Goss, chemists of
t a u of Chemistry, who have just completed an invcstiga-
tion on the utilization of para cymne, m~hichcomes from a n oil
ublaincd as a by-product in making paper pulp from wood.
Departinent chemists in recent years also liavc worked out
processe~for utilizing such waste3 as straw, rice hulls, peanut
hull-, and corncobs, as well as for the inore profitable utilization
of various cull fruits and vegctables. Several commercial con-
ceiiis arc now making salable commaditics from Parge quantities
of ciidl orances and lemons by these new processes.
Tlic oil iiom ivhich tbc ncw paint and varnish remover is
sohitioii past stirtionmy le& piecea. 'l'lic xilutiou i
i n cither of two 100-gallonstoneware jars, from which it flows
1o an all-porcelain, horizontal centrifugal pump, directly coil-
nectcd to a motor, which is equipped for speed variation over :I
wide range. The pump discharges into a Pyrex glass pipe
line, in two runs, one above the other, which in turn dis-
charges into either of the 100-gallon storage jars. In the
lower run, a short distance from the pump, is a glass Veutiiri
meter connected to a recording differential pressure gage, liy
means of which a continuous record of velocity is kept. The
tipper run of tubing is on the same level BS the top of the 100-
gallon jars. I n i t are placed special sections provided with
tubulures through which test pieces are inserted and held iii
glass stirrups exactly in the center of the tube, and wit11
flat surfaces parallel to t.he direction of flow. Three special
sections, differing in diameter, are used to provide for a wider
range of velocities than the pump motor control will give of
itself. The solution discharge can also be controlled by g1a.s
spigots wliich terminate the line of tubing. Large alundurn
diffusers provide for aeration in the storage jars, and the solu-
tion is heated here as well, with special electric lieaters.
2\11 indicating thermometer is inserted in the tube on the down-
streani side of t,liecorrosion chamber, and a permanent record
of the teinperature in the storage jars is kept by means of
a recording thermometer. KO metal except the test pieces
comes in contact xvitli the solution. Under as nearly similar
coiidit,ions as possible this apparatus gires corrosion rstes
nammm CI -Ta*.ejm:
'xr"mrx/w
rviR
Figure 9~~Confinuouw Flow Apparatus
about 24 per cent lower than those given by t.lie other two.
This is believed to be due principally to differences in the
:Ibsolute velocity, and to irregular velocit,y of flow past the
stationary1test pieces in the continuous fion apparatus.
Acknowledgments
The authors are very greatly indebted to R. J. Mcliay, at
whose suggestion much of this work was conducted, and who
was the first to demonstrate the necessity for controlling mo-
tion and aeration in the laboratory study of submerged cor-
rosion, to P. I). Merica for many helpful suggestions and
encouragement, and to others of their associates for useful
criticisms of the text.
made was until recently alinost wholly an cconomic waste. I t
has been variously estimated that from 750,000 to 2,000,000
gallons of t h i s material are annually produced in the sulfite i,ulp
mills oi the United States. The paint and varnish remover is
prepared by mixing para cymne with grain alcohol, rncthanol,
and acetone, in equal parts by volume.
The most effective method for removing paint and varnish
is to apply the new remover t o the s w h c e to be treated, and
after three to five minutes the softened paint or varnish may be
very e a d y removed by means of a scraper. This reinover has
been patented by Phillips and Goss and dedicated to the peojilc
of the United States.