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> XK1434H09ENC

EUROPEAN
COAL AND STEEL COMMUNITY

IVth CONGRESS

Working Party III

Stress and strain
caused by chemical attack
Theoretical studies

Effect of flow-rate on corrosion in aqueous media

by
Dr. rer. nat. E. HEITZ
Diplom-Chemiker
Leiter der Arbeitsgruppe Elektrochemie
Dechema-Institut
Frankfurt (Deutschland)

Commission
of the European
Communities
1968
EFFECT OF FLOW-RATE ON CORROSION IN AQUEOUS MEDIA
1. INTRODUCTION AND PRINCIPLES

Corrosion phenomena occur on almost all engineering products,

equipment and structures, but they are particularly important in chemical
engineering because it is here that extreme conditions are often encoun-
tered. Every advance in process engineering and plant construction brings
with it new materials problems, predominantly in the field of corrosion.
Therefore it is extremely important to know and understand the processes
involved in metal destruction as they are affected by various factors and
to adapt the measures to prevent or reduce corrosion accordingly

The major factors affecting attack by a corrosive medium are its

chemical composition, concentration, temperature, pressure and flow ve-
locity can be simply explained by the fact that corrosive agents have to
be brought into contact with and corrosion products carried away from the
surface. In addition there is the mechanical action on the surface of the
material, particularly at high flow rates. This causes corrosion due to
erosion, cavitation or impingement, which may be regarded as forms of
flow-dependent corrosion.

From the physico-chemical aspect, the corrosion reaction is a

heterogeneous chemical reaction and can be defined in simplified form as
the succession of the following constituent steps :

1. Supply of the corrosive agents;

2. Reaction at the metal/solution interface (interface reaction);
3 Removal of the corrosion products.

Hence the interphase reaction is related to the preceding and

following transport processes which are directly affected by flow rate.
As far as is known at present, the liquid phase interface reaction is
essentially an electrochemical process in which the anodic dissolution of
the metal and cathodic reduction of the oxidising agent take place at
different points. The anodic and cathodic points are either statistically
distributed over the whole surface only a few atoms apart or divided into
macroscopic anodic and cathodic surfaces; in the former case uniform or
general corrosion occurs and in the latter local corrosion (further in-
formation is given in a paper by H. Kaesche (1)).

The effect of flow on uniform corrosion is easy to study in the

way already proposed for other heterogeneous reactions (2), (3) An example
is the oxygen corrosion of a metal pipe with a common salt solution
flowing through it, where both the delivery and the interface reaction
of the oxygen affect the corrosion rate. It is also assumed that the
other components of the reaction take place quickly. The corrosion rate
is then governed by the two constituent processes :
 2 (solution) 2 (surface) Diffusion

02 (surface) corrosion products Interface reaction

whose Kinetic equations are

(1) V. = k. (0o . - 0- , ) Diffusion
2sol. 2surf.

(2) V
2 = k 2 ^eurf.' Interface reaction

V1n and2 V a r e the r a t e s and k. and k_ the rate constants of the con
stituent steps and 0~ the concentration of oxygen in solution or at the
surface. When reactions take place in rapid succession, the individual
reaction rates soon become the same (i.e. a stationary condition is
reached) and so V- = V_ = V. V then denotes the total corrosion rate.
By eliminating 0_ from equations (1) and (2) we obtain :

2 sol.
(3) V =
1 1
k k
l 2

If the values V, k (0_) and k_ (0_) are expressed in g/sq.m,

d in this equation and the total corrosion rate plotted against the
flow velocity in a tube in m/sec (contained in the "rate constant" k.. ),
the curves shown in Fig. 1 are obtained. The parameter is the inter
face reaction k(0~) for which values of 1 to 100 g/sq.m, d are assumed.
If the flow rate becomes high enough, the measured corrosion rate goes
over to the predetermined values of the interface reaction (limiting
value of equation (3) for k, > CO ). The course of the curves in Fig. 1
indicates the following :

Low corrosion rates (k_(0_)^5 g/m , d) set in at relatively

low flow velocities - the corrosion is virtually independent of the flow.

Average corrosion rates ( 5 ^ k p ( 0 _ ) ^ 30 g/sq.m., d) only

reach their final value at medium flow velocities.
High corrosion rates (k_(0?)^ 30 g/sq.m., d) lead to highly
flow-dependent corrosion.

Interesting practical conclusions can be drawn from this.

For example, with a pipe flow of 2 m/sec, if the measured corrosion rate
is below 10 g/sq.m.,d no further significant rise is to be expected at
higher flow rates. If for example at 1 m/sec it is already as high as
22 g/sq.m., d then at 10 m/sec it may be three times as high. Naturally
this is only applicable to uniform oxygen corrosion. If H ions are
delivered instead, then the measured corrosion rates under otherwise
similar conditions are less flow-dependent. This is a result of the
higher diffusion coefficient of H ions.

Although uniform corrosion without formation of a surface film

can be quantitatively studied with the help of heterogeneous kinetic
measurements, it is more difficult - if not impossible - to study local
corrosion in this way. Local corrosion is due to inhomogeneities in both
the metal and solution phases. Naturally the inhomogeneities in the
medium are of more interest where flow rates are concerned. They include
 Differences in the concentration of oxygen (aeration cells), hydrogen,
chloride and metal ions and the variable formation of surface and
passivation films.

Differences in temperature manifested by hot-spot corrosion.

As both material and heat transport are causally related to

the flow velocity, many practical corrosion phenomena are "flow-
dependent". One example is the aeration cell. If certain regions of a
metal surface come into contact with a stationary, and others with a
flowing, solution containing oxygen, a concentration cell is set up.
The surface contacting the stationary solution corrodes more severely
because the oxygen originally present is soon consumed and cannot be
supplemented quickly enough. The surface over which the solution
flows, however, is rich in oxygen and to some extent passivated. There
the oxygen is reduced. The aeration cell is also affected by transport
and interface reactions, but to a different extent at anodic and
cathodic points. Finally, conditions also change with time (k) so that
a calculation similar to that used for uniform corrosion is impossible.
Apart from the more indirect effect of flow velocity owing to the
formation of concentration cells and thermogalvanic cells, the metal
surface can also be directly affected by high flow velocities. Either
shearing stresses due to liquid friction occur or high kinetic energies
are released on the metal surface as cavities collapse. In all cases
typical forms of local attack occur; these will be covered in detail
in the next section.

2. FORMS OF FLOW-DEPENDENT LOCAL CORROSION

Fig. 2 shows the corrosion phenomena that may occur at high

flow velocities. Fig. 2 a is an example of cavitation corrosion in-
duced by magnetostriction (5) Cavitation bubbles are formed on the
surface of the metal when the vibrations reach a certain frequency
and amplitude. As they collapse, they destroy the films and protective
layers on the surface and create the conditions for a corrosive attack.
This example is grey cast iron in distilled water at 50C, exposed to
the medium for k hours at 9 kHz and an amplitude of 60yWm. Similar
phenomena occur in service on ships' propellors, turbines and in pumps,
but in such cases the cavitation is caused by fast-flowing media.
Although there is no doubt about the combined action of mechanical and
chemical factors (6) and electrochemical processes have also been de-
tected in a case of cavitation corrosion (7) there is still much to
be learned about the mechanism.

Fig. 2b shows a copper probe attacked by erosion corrosion.

On the surface there are the remains of a lime-rust deposit origi-
nating from sludge-bearing waste water. The horseshoe-shaped depressions
are typical and their shape indicates the flow direction. In other
cases fan-shaped areas of corrosion are formed, particularly in soft
 metals such as aluminium. Despite plausible theories based on the
mechanical and chemical effects (8), the mechanism of erosion corrosion
has not yet been explained experimentally.
Impingement corrosion has long been known in practice (for
nomenclature see (3)) It occurs when fast-flowing liquid media impinge
on metal surfaces, as in the diagram in Fig. 2c. The complicated, tur-
bulent flow produces low-pressure air bubbles, the impact of which at
the inlet to the condenser tube causes permanent damage to the surface.
If the metal does not form a new protective film quickly enough, local
conchoidal pitting will occur. It is typical of this form of corrosion
that no corrosion products are deposited. The mechanism must be similar
to that of cavitation and erosion corrosion (9)

Finally, Fig. 2d shows a rotating disc of carbon steel. The

specimen was rotated at a speed of *f00 r.p.m. for k hours in a
10 n KCl solution containing air at 70C. It is clear that corrosion
is initiated at pits or small holes and spreads in the direction of
flow. The spread of corrosion in the direction of flow must be due to a
reaction between the corrosion products and the metal. Corrosion traces
in the form of a comet's tail leaving deep tracks on the metal are
typical of this. As it can occur even at relatively low flow rates, the
example given here comes midway between the cases mentioned above and
corrosion affected solely by material transport.

3. TRANSPORT INFLUENCES AND TESTING METHODS

A few physical explanations are necessary to clarify the

methods used for the experimental determination of material transport
(see V.G. Levich (10)).
Owing to a concentration gradient, ions and molecules may
reach the corroding surface by molecular diffusion. However, as the
diffusion coefficients in fluids are very small, the resulting reaction
rate is very low in a completely still solution. When the particles are
moved by a flow of fluid, also known as convection, the amount of materi-
al arriving at the surface increases greatly and the reaction rate
rises appreciably. This type of transport is known as convection dif-
fusion. As its name indicates, its two components are convection in the
interior of the solution and diffusion on the surface.

Convection flows can be further subdivided from the purely

phenomenological aspect. If they are due to external action, such as
stirring, they are called forced convection. If they are due to differ-
ences of density at the interface or to temperature differences, they
are known as natural convection. In fact, there is almost no system in
which natural convection at least will not occur after some time.

At the turn of the century, attempts were already being made

to determine the principles of material transport. Nernst (11) and
Brunner (12) were the first to start from the idea of a stationary
diffusion layer. They distinguished between a stationary diffusion layer
of specific thickness at the surface and the flowing solution and drew a
sharp distinction between diffusion and convection transport. Although
this theory was useful for the qualitative description of the processes
in convection diffusion, it has been discarded in the last twenty years.
It has been proved experimentally that the thickness of the Nernst dif-
fusion layer is not accurate nor is the assumption of a stationary layer
correct. In the case of laminar flow around a surface, a flow interface
is formed in which almost the whole drop in velocity takes place. The
flow interface in turn causes a diffusion interface in which the con-
entration gradient always extends over about one-tenth of the flow inter-
face. The mechanism of material transport in the case of a surface over
which there is a laminar flow is therefore as follows : the agents reach
about nine-tenths of the hydrodynamic interface mainly by convection and
reach the tenth adjacent to the fixed surface by molecular diffusion.

Conditions are different in the case of turbulent flows, which

are encountered far more frequently in practice. By turbulent flow is
meant an unsteady, random motion of fluids in which the velocities
fluctuate about a mean value and the flows are in the form of eddies.
The main direction of flow can only be found by summing all velocity
vectors. The change from streamline to turbulent flow is defined by the
critical Reynolds' Number. This number, originating from the hydro-
dynamic theory of similarity, indicates the flow rates above which tur-
bulence occurs for a given surface geometry and a given kinematic vis-
cosity. Some values are given in Table I.

The mechanism of material transport in turbulent flows can be

described as follows : relatively far from the surface there is complete
turbulence and constant concentration. In the turbulent interface the
mean velocity and mean concentration gradually decline according to a
logarithmic progression. In the next viscous stratum the eddies are very
small, but turbulent material transport still predominates. Only in the
diffuse stratum next to the surface does molecular diffusion dominate.

In investigating transport effects it is important to start

from hydrodynamically defined flows. Fig. 3 shows a few common methods
for the production of typical flows.

Both laminar and turbulent flows can be set up by the rotating

disc system. In its conventional form it is a circular disc which is in-
serted in the base surface of a rotating cylinder. The condition of a
circular surface subjected to a three-dimensional flow in a fluid con-
tinuum is approximately fulfilled by the inert zone near the edge. The
material transport can be quantitatively calculated in the laminar region
from the angular velocity of the disc, the diffusion coefficient of the
transported material and the kinematic viscosity of the solution, as
Levich has shown (13) The method was further developed by Frumkin and
his school (1*0.

The rotating disc with a shaft passing through it (fig. 3b)

is more suitable for corrosion experiments in the laboratory. The material
transport equations are still valid if the ratio of disc diameter to
shaft diameter is not less than 5 : 1 (15) The advantage of this design
lies in its experimentally simple construction which makes it suitable
for series of experiments and also in the possibility of obtaining higher
material transport velocities. On the other hand, the critical speeds of
rotation for the laminar *- turbulent change behave inversely to the
squares of the disc radii. Thus the laminar flow range is considerably
restricted.
 Another body of rotation is the cylinder, which is also used
for metal dissolving processes (16). If it rotates freely (Fig. 3c), a
constant hydrodynamic interface occurs in the timewise middle - and thus
constant material transport - but the flow is always turbulent. Therefore,
unlike the rotating disc, the mass transport cannot be calculated from
physical values starting from first principles. However, there are exact
solutions to the imaterial transport problem if the cylinder rotates in-
side an outer one (Fig. 3d). This system represents the limiting case of
a flow produced between a stationary wall and a wall moving parallel
thereto, known as Couette flow. There is a laminar, a turbulent and a
transitional zone (17) which make this flow model particularly inter-
esting for material transport problems.

To test the effect of material transport, use is also made of

an arrangement in which the corrosive agent flows through a tube of the
metal to be tested. Unlike the case of the rotating disc or rotating
inner cylinder, the flows obtained are turbulent down to low velocities,
although here to a small laminar region known as Hagen-Poseuille flow is
adjacent to them. For the measurement of material transport, however,
this is only of interest in connection with specific problems. Pipe flow
is the most frequent type of technical flow and consequently there has
been much published on it. Some important works will be mentioned in
section k.

If the corroding surface is not the inner wall of the pipe,

but a plate along which there is a laminar flow, then a laminar or
turbulent interface can form at the plate. Such plates are frequently
used as specimens in pipe flows. As these flows are generally turbulent,
the principles applicable to material transport on the inside wall of a
tube are also valid for a longitudinal flow over such plates. Experiments
with this method are rarely mentioned in the literature (l8).

It is at first surprising to find that a definite flow may

form during the continuous immersion test. The experiment consists of
suspending rectangular specimens of sheet material in a stationary
solution. As a result of corrosion, differences in density occur in the
zone immediately adjacent to the surface and these cause a liquid flow
(Fig. 3f) This flow is an example of natural convection, differing from
the cases of forced convection discussed earlier.

A number of laws have been found for natural convection on

vertical surfaces. Experiments by C. Wagner (19) on the solution of
common salt crystals in water showed that the average rate of solution
increases as the fourth power root of the distance from the top. Con-
sequently in continuous immersion tests the height of the specimen must
have an effect on the corrosion rate. By doubling the height of the
specimen while keeping the total area constant, a reduction of 20 % can
be obtained in the corrosion rate per surface unit. This is a far from
negligible order of magnitude in view of the relatively good repro-
ducibility of transport-controlled cases of corrosive attack.

The mathematical formulae for material transport cannot be

given in their full form here. However, they are exact for the rotating
disc and flat plate with laminar flow, the laminar Couette flow and the
Hagen-Poiseuille flow. The turbulent flow systems are, however, defined
by semi-empirical functions of non-dimensional quantities wich often
still leave the value of a proportionality factor to be determined ex-
perimentally (10).
 Table I gives the most important properties and parameters of
the flow systems described so far. It is interesting that the material
transport on a rotating disc subject to laminar flow is independent of
the radius, that it enters the material transport equation with an ex-
ponent of - 0.1 for a turbulent flow through a pipe and in other cases
has exponents > 0 . 6 6 . There is generally a direct proportionality
betwe.en speeds of rotation or flow velocities and material transport,
with the exception of a laminarnflow on the rotating disc (n ) and a
laminar floWpthrough a tube (U ) The,_relation between specimen
height (h -?) and concentration ( A C * p ) for a vertical plate with
natural convection is also striking.

The functional relationships mentioned show the multiple

properties of various flows and it is easy to see that knowledge of a
relative metal/medium velocity alone is not sufficient to define a
flow. This is particularly true of model tests to determine flow de-
pendency.

In conclusion a few processes will be described that do not

fit into the above scheme but are nevertheless of significance.

The magnetostriction method of testing for cavitation cor-

rosion was described in Section 2 (20). There are also experiments with
venturi nozzles in which liquid cavitation is produced by supercavi-
tating media. Another process is based on the use of drop impingement
apparatus producing a rapidly flowing jet of water through wich metal
testpieces are periodically passed. A summary together with a biblio-
graphy is given in the work of Wiegand and Piltz already mentioned (5)

There are other methods in addition to these testing processes

that are akinto practice, but their results are less significant. In
one method specimens of any desired shape are mounted on the circum-
ference of large rotating discs to test their susceptibility to erosion
corrosion (21). In other cases the specimens are placed in loops or a
strong jet of the medium with entrained air bubbles is directed on to
them (22). The experimental results give reliable information on a
specific practical case but cannot be generalised.

k. THE EFFECT OF FLOW ON THE CORROSION OF VARIOUS METALS AND ALLOYS

It is convenient to divide this section into ferrous and non-

ferrous metals, as their behaviour differs.

As early as 1931, the corrosion of rotating steel cylinders

in tap water was tested. The experiments showed that the solution rate
first rose with the speed of rotation and then passed through a minimum
(23). Later Evans and his colleagues carried out the well-known drop
tests in which the rate of attack was calculated as a function of the
oxygen content of solutions (2*0. According to these experiments,
 oxygen on the one hand stimulates corrosion in the sense that it in-
creases the rate when a corrosive attack occurs (possibly as a result
of varying aeration). On the other hand, as the oxygen partial pressure
increases, there is less probability of corrosion starting, because of
the increased tendency of the steel to become passive. As the flow
velocity governs the oxygen concentration on the iron surface, the
corrosion rate first increases with the flow then declines at medium
velocities as a result of passivation and rises again at relatively
high flow velocities. This behaviour is illustrated by the curves in
Fig. *f (13) The experiments were made with rotating discs (dia. 5 nun)
in sulphate solutions of varying concentrations. With low sulphate con-
centrations the effect of flow is slight, but with high concentrations
it is great. This effect corresponds to low and high interface reaction
rates, as discussed in connection with Fig. 1. The steep rise in the
corrosion rate at high sulphate concentrations and flow velocities is
partly due to the mechanical effect of the medium which strips off the
corrosion products that do not adhere firmly.

The attainment of a minimum at medium flow velocities appears

to be typical of all unalloyed grades of iron. For example, it was also
observed on perlitic cast iron in an aerated 35 10 n NapSO. solution
of a pH value of k (26)*. As speeds of up to only 1500 r.p.m. were used
in these experiments (rotating concentric cylinders of 12 mm dia.),
the renewed rise in the corrosive attack following the passivation
region could not be obtained.

Comprehensive experiments on steel corrosion in water of

varying composition have been carried out by Butler and colleagues (27).
Fig. 5 shows the corrosion rate against the pipe flow velocity at two
temperatures and for various NaCl contents. The initial rise and fall
in the corrosion rate is again found when no chloride is present. If
NaCl is added, then the removal curves climb monotonically with the
flow rate. As is to be expected, increasing NaCl contents and high
temperatures intensify this effect,. If the flow-dependency exponent is
determined, it is found to be u for maximum chloride concentrations
at 25C and u at 55C. This agrees with the fundamental observations
in Sections 1 and 3
The steady increase in the solution rate with the flow rate
in solutions containing chloride was observed by various authors in
sea water (28) and 3 % NaCl solution (29). The former case was a pipe
flow. The measurements gave the following flow-dependency exponents :
u * ' for pipe flow and n ' for Couette flow. The value u = 1.2 is
somewhat too high; possibly this is connected with the fact that the
measuring points were relatively close to the laminar ^- turbulent
transition point and surface films were stripped off by the start of
turbulence.
The flow-dependency of iron corrosion in acid media has been
the subject of several research papers. Ross and colleagues (30) carried
out electrochemical tests on pure iron and iron.-carbon alloys in dilute
sulphuric and hydrochloric acid. Their flow model was a flat plate
flowed along in a parallel direction, and they developed various
material transport equations as functions of non-dimensional quantities.

A problem of practical importance is the behaviour of cast

iron and steel in concentrated sulphuric acid. Using rotating discs,
it was found that steel corrosion was highly flow-dependent, but not
the solution of cast iron (31) However, the corrosion of cast iron is
affected by composition and structure, and the exposure period is also
important as passivation is a time-dependent process.
10
 There has as yet been no experimental research on the erosion
corrosion of low alloy steels in completely desalinised water although
a number of cases of damage have become known recently and a plausible
theory has been developed by Homig (8). The reason may be that the tur-
bulent flow rates of up to 200 m/sec required for such corrosion tests
are difficult to simulate in the laboratory. The corrosion behaviour of
high-alloy steels such as 13 % chromium cast steel (33) or 18/8 CrNi
steel is little affected by flow velocity provided certain minimum
velocities are observed. A good example of this is CrNi 18/8 in sea
water, whiph should only be used above 1.7 m/sec (x) (32). Below this
critical flow velocity there is a danger of corrosion under deposits or
of pitting owing to the dissolved chloride. This inverse effect of flow
velocity, particularly in the range of stagnant to slow floating media,
is also often found with other metals such as zinc, copper and nickel
and their alloys. Little systematic research on this subject is known.

The corrosion of alloy CrNi 18/10 is highly flow-dependent

when the medium contains solids. For example, the material's corrosion
behaviour in an aqueous suspension of thorium dioxide and uranium
trioxide was tested in a loop apparatus at 305C (conditions in a nuclear
reactor circuit). The steel sheet specimens were in a turbulent pipe
flow which could be increased up to velocities of 30 m/sec (3*0 Under
these conditions the rate of removal does not increase in proportion to
the flow velocity, as would be expected, but shows an extreme rise above
a critical flow velocity lying between 20 and 30 m/sec.

The only interpretation of this result is that the passive

layer is destroyed by the mechanical action of the solid particles and
cannot repair itself because of the continued erosion. In addition the
attack is intensified on rough surfaces, probably due to the more in-
tensive turbulence.

The behaviour of non-ferrous metals, particularly copper and

nickel alloys, in flowing media is of interest. The experimental results
obtained by LaQue (35) and Wranglen (29) are summarised in Fig. 6. Two
types of curves can be distinguished : corrosion rising monotonically
with the flow velocity and erosion corrosion starting suddenly at
specific critical speeds of rotation. The apparent contradiction in the
fact that erosion corrosion occurs on the CuNi alloys, which in fact are
more resistant, and not on copper and the special brass CuZn 20 Al is
due to the flow systems used. Experiments with the CuNi 70 30 Fe materials
were carried out with rotating discs (dia. 12 cm, 19 r.p.s.) and those
on copper and special brass with concentrically rotating cylinders.
Under the given conditions, the flow on the rotating discs is turbulent
and the intensity of the material transport increases with the radius
from the inside to the outside. The experiments were then interpreted
as follows : by measuring the thickness of the specimen at a given
distance from the centre a corrosion rate is obtained; the respective
flow velocity is measured from the circumferential speed at the point
concerned. Thus the corrosion is obtained as a function of flow.
Naturally the flow velocity calculated in this way does not correspond
to the circumferential speed of rotating cylinders. In addition, due to
the varying flow conditions on the disc surface, concentration cells are
set up, which are not present with rotating cylinders.

(x) The type of flow is not given in the literature source.

11
 The problem mentioned here is typical of many flow experiments.
When results obtained by different methods are compared, it must also be
remembered that the parameters of material transport may vary (see Table I)

Numerous results on CuNi alloys immersed in sea water were

obtained by the jet flow method and with the ai.d of channel, flows (36)
This publication for example gives the following values as the upper
permissible limits of flow rate : copper 2 - 3 m/sec, Admirality brass
3 - k m/sec, aluminium-brass *f - 5 m/sec and 70/30 copper/nickel alloy
5 - 5 - 6 m/sec. As the type of test flows is not precisely defined and
intensified local turbulence cannot be excluded, such data are probably
only of limited use in practice.

Finally, mention must be made of a field in which flows of

fluid media play an important part : nuclear reactor engineering.
Because of the high temperatures and pressures in the circuits, they
are always closed systems in which sometimes highly corrosive media
such as molten salts and molten alkali metals flow along the plant
walls. As the problems occuring here are very complex and research is
still in progress, it will be sufficient to mention a few sources in
the literature (37)

5. CONCLUSIONS

The above paper gives a survey of existing knowledge on the

subject from the theoretical and practical aspects. In brief, it is
fair to say that on the basis of wide practical experience corrosion
due to flow has generally been mastered - for example, there is "de-
signed protection against corrosion". However, in many respects the
results of basic research are still incomplete. The outstanding
problems may be summarised as follows :

1. Lack of knowledge of the basic processes in erosion, impingement,

and to some extent cavitation corrosion.

2. The lack of quantitative relationships between individual testing

methods, to facilitate a comparative assessment of results (see
(15))

3 A shortage of experimental material obtained under hydrodynamically

defined conditions.

Further progress will largely depend on the extent to which

these problems can be solved.

12
 Properties and parameters of various flow systems

DEPENDENCY OF MATERIAL TRANSPORT Critical Rey Meaning and

Type Speed of nolds * Number Dimension of
Flow Systems Radius Concen
of Flow Rotation laminar the Symbols
Geometrical tration
Flow Speed Turbulent Used
values
2
Rotating Disc Laminar n 5 independent C D
Re.
k
=w.r n = Speed of
y rotation
(r.p.s.)
Turbulent n r 0.9 C = 10 to IC? w = 2 angular
velocity
(l/sec)
Concentrically Laminar n r C Rek=U.d C Concentration
rotating cylinder difference
y (mole/cu.cm.)
in interface
Turbulent n r C = f.6.103 Re, Critical
Reynolds'
Number
Freely rotating Turbulent n 0
' 7
n
r 0.7 r C r Radius (cm)
cylinders
u 0.33 0.66 0.66 u Average flow
Flow through pipe Laminar r .x C Re, = u.d
V rate (cm/sec)
Flow rate
0.1
Turbulent u r C =2.3.10"5 U Circumferential
speed (cm/sec)
Longitudinal flow Laminar u05 0'5 C Effective pipe
over plate length (cm)
Effective
plate length
Turbulent u09 x0'9 C h Height of plate
d Inside diameter
of pipe (cm)
h 0.25 c 1.25 y> Kinematic visco
Natural convection Laminar
on vertical plate sity ( sq. cm/sec )
\U
 BIBLIOGRAPHY

(1) H . Kaesche:
Die Korrosion der Metalle, BerlinHeidelbergNew York I966.
(2) R.G. Van Name u. D.U.Hill,
Amer. J. Sei. k2 301 (I916).
(3) K. Fischbeck,
Z. Elektrochem. 3_9_ 316 (1933)
(*f) H . Grubitsch, T. Sneck,
Mh. Chem. 86 752 (1955)
(5) H . Wiegand, H.H. Piltz, R. Schulmeister,
Metalloberflche l6 B*+9 (1962).
H. Wiegand, H.H. Piltz,
Werkstoffe u. Korrosion 15_ 212 (196*0 .
(6) H .R. Copson,
Corrosion 16 86t (i960).
(7) H .S. Campbell, V.E. Carter,
J. Inst. Met. %0 362 (196I/62).
(8) H .E. Hmig,
Korrosion 15 *fl (I962) (Verlag Chemie)
Mitt. Vereinig, d. Grosskesselbes. H 76 12 (I962).
(9) U.R. Evans:
The Corrosion and Oxidation of Metals,
S 7591 London, i960 (E. Arnold).
(lO) V.G. Levich:
Physicochemical Hydrodynamics, (Englewood Cliffs (Prentice Hall))
1962.

(il) W. Ner ns t,
. phys. Chem. V?. 52 (190*0.
( 12) E. Brunner,
. phys. Chem. jj 56 (190*)).
(13) V.G. Levich,
Acta Physicochim., UdSSR 7_2 57 (19^2),
Discussions Faraday Soc. _1 37 (19**7)

15
(l*0 A.N. Frumkin u. E. Aikasyan,
Nachr. Akad. Wiss., UdSSR 202 (1959)
' A.N. Frumkin u. G. Tedoradse,
Z. Elektrochem. 62 26l (1958).

(15) E. Heitz,
3 Kongress der Europischen Fd. Korrosion, Brssel, Juni 19631
E. Heitz,
Werkstoffe u. Korrosion 15_ 63 (196*0 ,
E. Heitz,
Electrochim. Acta 10 *f9 (1965).
(16) C.V. King,
The Surface Chemistry of Metals and Semiconductors
(J. Wiley and S., 1959) S. 357.
(17) K. Schlichting,
Grenzschicht-Theorie, S. 69, Karlsruhe, 1965

(18) K. Richard, K. Risch in

"Wandel in der chemischen Technik" S. lol
(Selbstverlag Farbwerke Hoechst AG) I963

(19) C. Wagner,
J. Phys. Chem. 53 IO3O (19^9),
Trans. Electrochem. Soc. 95 lol (l9*t-9)
(20) W.C. Leith, A.L. Thompson,
Trans. Am. Soc. Mech. Angrs. 82 795 (i960).
(21) H.L. Logan,
J. Res. Nat. Bur. Std. k& 99 (1952),
R.L. Hadley, H.J. Smith,
Corrosion 17 9 (I96I).
(22) P.T. Gilbert, F.L. LaQue,
J. Electrochem. Soc. 101 Mf8 (195*0
(23) B.E. Roetheli, R.H. Brown,
Ind. Eng. Chem. 23 1010 (1931)
(2*f) R.B. Mears, U.R. Evans,
Trans. Farad. Soc. 31 527 (1935)
(25) E. Heitz, A. Hauptmann,
(Verffentlichung in Vorbereitung).

(26) E. Fot,
Schweizer Arch. f. Ang. Wiss. u. Techn. 3 329 38*f (196*0.
(27) G. Butler, H.C.K. Ison,
J. appi. Chem. 10 80 (i960),
G. Butler, E.G. Stroud,
J. appi. Chem. 2 325 (1965, British J. Corr. 1 110 (I965)

16
(28) F. Wormwell,
J. Iron St. Inst. 15_*i 119 (19**6).
(29) J. Venzcel, L. Knutsson, G. Wrangln,
Corr. Sci. k 1 (l96*f) .
(30) T.K. Ross, G.C. Wood, I. Mahmud,
J. Electrochem. Soc. 113 33** (I966).
(31) W.M. Nowakowskij, E.F. Lapschina, M.Sch. Bloch,
. phys.. Chem. (Leipzig) 230 313 (1965)
H.W. van der Hoeven,
Werkstoffe u. Korrosion 6 57 (1955)
(32) R.A. White,
Materials Protection k *f8 (I965).
(33) E. Fot, E. Heitz,
Werkstoffe u. Korrosion l8_ 529 (1967)
(3*f) D.C. Vreeland,
Corrosion 17 21t (196I).
(35) F.L. LaQue, J.F. Mason,
J. Proc. Am. Pet. Inst., Div. of Refining 30M 111 (1950).
(36) T.P. May, B.A. Weldon,
S. l*fl "Congr. Int. de 1. Corr. Marine e. d. Salissures", Cannes,
196*f.
(37) M. Atsumo,
Hitachi Rev. 13 3 (196*0,
W.R. Grimes,
Nuclear News, ? 3 (196*)),
R. Gross, H.U. Borgstedt,
Werkstoffe u. Korrosion, l8 777 (I967),
International Atomic Energy Agency,
Corrosion of Reactor Materials, Wien, 1962.

17
 100 |g/m*d) Geschw. der
Pha seng renz reaktion [g/nd]
100

80

60
O

o 50
* AO

IA
30
20

10
5

10 15 20 jm/s ec]

Figure 1 : Overlapping of material transport and.interfacial reaction

in the corrosion of iron in air-saturated neutral media
flowing through a pipe.

19
 1 mm ^ 1 cm
a) Cavitation corrosion on cast b) Erosion corrosion on copper
iron in distilled water (spe
cimen prepared in the Insti
tut fr Werkstoffkunde der
Technischen H ochschule Darm
stadt).

-Rohr boden

Strmungs-^
richtung ^ .31. -
Kondensatorrohr

H 1 cm
c) Impingement corrosion d) Flowdependent corrosion on
(diagram). a rotating disc.

Figure 2 : Forms of corrosion due to fast flows

21

*?
stt
1

cSs> <>
si

rotierende Scheibe rotierender

Y
durchetrmte
t
Doutrtouchveraucri
Zylinder Rohr

Figure 3 : Methods of investigating the effect of transport

5-10"Jm Na2SO
luftgesttigte
Lsung

10"* m

510"5m

20000 30000 40000

[U/min]

Figure k : Corrosion of carbon steel in airsaturated solutions

at 70C (rotating disc, dia. 5 mm).

23
 0.025 0.05 O.t 0.25 0.5 1.0 2.5 C m *3 0. 0025 0.05 0.1 0.25 0.5 1.0 2.5 [mVe*]
r * I 1 -I 1 I 1 - i l l i | * , ^
(/J [j/rid]
(j/nd)

200 . .200 200

NaCl

100 ..too 100

50 .. ..50
50

20.
20

10 - 10

2 . .. 2
't

. .. 1 l i l
0,01 0025 aOS 0.1 025 0.5 1.0 2.5 {W0<' C.025 0,05 0.1 025 0.5 U> 2.5 [m/te]
b
a

Figure 5 ; Corrosion of carbon steel in media containing chloride

flowing through a pipe at 25C (a) and 55C (b).

25
-AO
rot. Scheibe, turbulent
[g/rn^d] Meerwasser
60d
0,06% Fe

30

-20

. Cu 99.9
4 bis 7d
10 Couette-Strmung, turbulent
3*/NaCl- Lsung
". Cu 2n20Al
2 6 8 10 [rh/se]
-+-

Figure 6 : Corrosion of various metals in sea water (according to

LaQue (35) and Wranglen (29)).

27
 S u m m a r

Where corrosions is uniform without the formation of an oxide

layer, the change in weight of metal can be determined by the quantitative
method of heterogeneous kinetics, the effect of flow working out greater
or smaller according to the actual corrosion rate resulting from the
chemistry. In the case of local corrosion, on the other hand, the effect
of flow is more complex and can usually only be determined qualitatively.
In consequence of additional mechanical action, high flow-rates give rise
to specific phenomena such as erosion corrosion, impingement attack and
cavitation erosion.

The effect of flow can be determined experimentally with a

rotating disc or cylinder, a stream tube or a flat plate inserted in a
fluid stream. Other methods approximating more to conditions found in
actual practice are the flow nozzle and drop impingement tests for estab-
lishing flow effects, inducement of cavitation by Venturi tubes and
magnetostriction. Results so obtained are described with reference to
various types of corrosion, viz. of C steel and grey iron in different
aqueous fluids, cast iron in concentrated sulphuric acid, and high-alloy
and Cu and Ni alloys in chloride-containing media and in reactor cycles

The problems may be summarized as follows :

1. Insufficient knowledge of the basic processes involved in erosion

corrosion, impingement attack and cavitation erosion.

2. Absence of quantitative relations between the different tests to

enable results to be comparatively evaluated.

3. Lack of experimental material obtained under hydrodynamically defined

conditions.

29
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14349/5/68/1