Corrosion Science, Vol. 39, No. 3, pp.

51 I-527, 1997
0 1997 Elsevier Science Ltd
Printed in Great Britain. All rights reserved
001&938X/97 $17.00+0.00
THE EFFECT
PII: 80010-938x(%)001424
CORROSION AND EROSION
MATERIALS
CERAMIC
Q. FANG, P. S. SIDKY and M. G. HOCKING
Department of Materials, Imperial College, London, SW7 2BP, U.K.
Abstract-The effects of corrosion/erosion on the chemical/mechanical properties and microstructures of four
engineering ceramic materials, namely alumina, reaction bonded silicon carbide, sialon and PSZ xirconia, were
investigated and characterised, using a chemical etch bed (hydrofluoric-hydrochloric acid mixtures,
1.5% HF + 5% HCl) and a sand-water slurry erosion test rig. A series of corrosion and erosion tests were carried
out and the morphology, structure and chemical analysis of the samples was investigated using optical microscopy,
SEM, XRD and AAS (Atomic absorption spectroscopy). Under the test conditions, Sic shows the best chemical
and erosion resistance of the four ceramics; and alumina has the highest corrosion and erosion rate. The erosion and
corrosion response, the degeneration of mechanical properties and the micromechanisms of the surface damage for
these ceramic materials are presented and discussed. 0 1997 Elsevier Science Ltd. All rights reserved
Keywords: A. ceramic, B. corrosion, B. erosion, C. acid corrosion.
INTRODUCTION
Engineering ceramic materials, such as zirconia-toughened ceramic, nitride and carbide
ceramics, are finding ever increasing applications in the development of modern industry
and technology and have been playing an active role in erosion resistant applications. One
of the outstanding advantages which ceramics have over other classes of materials is their
good combination of properties, such as high hardness, high melting temperature, good
erosion and wear resistance, and high level of chemical inertness in corrosive environments.
Slurry erosion by the impact of liquid-carrying solid particles reduces the life of mechanical
components used in many industrial and research applications. It is generally accepted that
ceramic materials are eroded in the form of radial and lateral cracking, ring cracking and
ploughing on the surface.rm6 A recent review describes many aspects of the erosion
behaviour and erosion mechanisms of ceramics.5 In many cases, joint effects of erosion and
corrosion in a slurry are inevitable; the surface of components are damaged, not only by the
impact of the solid particles, but also by chemical or electrochemical corrosion. The term
erosion-corrosion (E-C)7,8 applies to the degeneration of a material due to the
simultaneous action of mechanical and chemical forces.
Major advances in the study of the effect of erosion and corrosion have been made in
recent years.+i5 Stephenson et ~1.~ studied the interaction between erosion and corrosion of
C-Mn steel in dry and wet CO* conditions. The use of wet CO2 increases the rate of metal
loss by factor of 2-4, and loss from pure corrosion to erosion/corrosion increases by two
orders of magnitude. Results from Stott revealed that in the dry case, there may be four
Manuscript received 3 August 1995; in revised form 3 June 1996.
511
512 Q. Fang er al
erosion-corrosion regimes as a function of velocity at elevated temperatures. Newman
studied the transitions in erosion-corrosion regimes in slurries containing alumina sands in
NazCO,+ NaHC03 solution at room temperatures, and tried to propose an erosion-
corrosion map for the more complex wet environments. A synergistic effect between erosion
and corrosion is widely observed, namely the total material loss rate may be greater than
that which would be observed from the erosion and corrosion processes operating
separately. Some researchers reported12 that the synergistic effect between erosion and
corrosion in an acidic slurry medium for either carbon steel or stainless steel was very large
(33-99%). Hutchings13 studied the slurry erosion-corrosion effect of aluminium in NaCl,
Na2C03, and phosphate buffer, using electrochemical potential methods. Wood and
HuttonI Stott and Oka et ~1.~ have reviewed the effect of erosioncorrosion on various
alloys under different conditions and gave some possible synergistic mechanisms. It was
shown that predictions cannot be made of the relative erosion--corrosion resistance of alloys
by extrapolation of data from one environment to another especially where velocities of
impact are quite different.
Although much progress has been made in recent years in the understanding of the
erosion-corrosion mechanism, there are some areas, especially slurry erosion and corrosion
of ceramics, which are still not fully understood. Most of the research generally focuses on
metals or alloys, actual research of the E-C effect, is not as common in the field of ceramics
as it is in metallurgy. Only during the past 25 years has a true understanding of the
complexities of corrosion of ceramics begun to develop.16 Most of the research generally
focuses on behaviours in neutral or mild medium such as sand-water slurry, saline water
slurry and wet CO2 slurry where the corrosion plays a less important role in the erosion-
corrosion process. On the other hand, it is difficult to study the synergistic effects of E-C on
ceramics simultaneously not only because of the great number of parameters involved, but
also because some mechanisms of corrosion and erosion processes conceal each other. As
ceramics are much more corrosion resistant than metals and alloys in general, corrosion
effects are not instantaneous. This study aims to assess the corrosion and erosion resistance
of ceramic components in solid-liquid environments with particular reference to offshore
pumping applications. The effect of the cleaning solution (1.5% HF + 5% HCl) used in the
oil industry to clean downhole pipes is investigated. In this paper both simple effects of
corrosion and erosion as well as the combined effect are shown in order to shed some light
on the corrosionerosion mechanism. Identifying the corrosion mechanism is useful as a
first step in understanding corrosion-erosion effects.
EXPERIMENTAL METHOD
Materials
Four ceramic materials have been tested: 85% alumina Kawenit EL, reaction bonded
REFEL F Sic, Sialon 101, and partially stabilised zirconia (PSZ) Technox 1035. The
dimensions of the first three ceramic specimens were 10 x 10 x 5 mm3 while the SIC was
15 x 15 x 3 mm. Table 1 shows some of the physical properties of the four ceramic materials
which were used.
A hydrofluoric-hydrochloric acid of 1.5% HF + 5% HCl was used to simulate the
corrosion environment during downhole cleaning in offshore pumping applications.
The erosion slurries were prepared from rounded silica sand (600-850 urn) and water.
Effect of corrosion and erosion on ceramic materials
Table 1. Properties of the materials investigated
513
Materials Density Grain Size
(g/cm) (pm)
Hardness
JL+
Fracture Toughness
&(MPa rn.)
Brittlenesst
(m-.5Mpa-)
RaS
(urn)
PSZ zirconia
85% alumina
(rest SiO*)
Sialon 101
SIC
6.05 1-2 1489 f 50 6 248 0.03
3.7 56 1169k50 4 292 0.7
3.24 2-3 1675+50 3 558 x=0.01
y = 0.04
3.10 4-6 2255 + 50 2.8 805 x=0.3
y=o.15
*The applied load of Vickers hardness tests of 10 kg for alumina, 50 kg for the rest.
tIndex of brittleness is defined as a quantity (H/k&).2o
$Ra: roughness of specimen surface.
Equipment
The erosion tests were carried out by impingement of a sand/water slurry jet onto the
ceramic surface at an impact angle of 45. Figure 1 is the schematic design of the slurry
erosion test rig. Both the ejector and the exit nozzle (3.7 mm bore) are made of stainless steel.
The system gives a sand/water loading (slurry flow) of 4.6 l/min, feed pressure of 1.4 bar, and
the sand concentration in the slurry was 5 wt%. The jet velocity was calculated and found to
be 7.3 m/s. The sample holder was situated on a stand in the tank and was so designed that
parameters such as the nominal impact angle, the distance between the target and the ejector
pressure Qaug
Q
elector
II
specimen
/
by-pass valve
by-pass line
Fig. 1. Schematic diagram of the sand/water slurry erosion test apparatus.
514 Q. Fang et al
nozzle as well as their relative position, can be easily adjusted. Currently a 15 mm distance is
used between the target and the ejector nozzle. The construction details can be found
elsewhere.6,7
Experimental procedure
Three samples per test were measured for each of the four ceramics under investigation.
Two main sets of experiments were carried out. The first involved corroding the sample for
various lengths of time (up to 115 h) followed by erosion while the second was concerned
with eroding the samples without any prior treatment. The average error in erosion tests was
about lo%, while that in corrosion tests was less than 5%. In all cases monitoring by the
following techniques was carried out.
(1) Weight loss: in all corrosion experiments, the sample was weighed periodically.
Weighing was also carried out before and after erosion.
(2) Hardness measurements: were carried out prior to and after corrosion as well as prior
to and after erosion. The indentation marks and cracks which were made on the sample
prior to corrosion were amplified as the corrosive solution found its way through the cracks.
This was very useful in identifying two modes of cracking which in essence form an integral
part of the erosion mechanism. This is amplified later on in this paper.
(3) Optical microscopy and SEM were used to examine the surface morphology at each
stage.
(4) X-ray diffraction was used to investigate any phase changes, or preferential attack on
phases due to corrosion.
(5) Atomic absorption spectroscopy (AAS) was used to determine dissolved elements
from the ceramic in the corrosive liquid.
35
30
25
20
15
I O
5
0
0 20 40 60 60 100 120
Corrosion time (h)
Fig. 2. Weight loss of alumina against corrosion time.
Effect of corrosion and erosion on ceramic materials 515
EXPERIMENTAL RESULTS AND DISCUSSION
Corrosion resistance behaviour of ceramic specimens
Figures 2 and 3 show the dependence of corrosion resistance of the ceramic samples,
after immersion in 1.5% HF + 5% HCl solution in room temperature, on corrosion time.
Figure 2 shows the weight loss for AlzOs, while Fig. 3 is for Sialon, PSZ-zirconia and Sic. It
can be seen that there is a great difference in the corrosion resistance of the various ceramic
materials. The corrosion rates, which were plotted from the slope of the weight loss-
corrosion time curves (Figs 2 and 3), for all specimens is also seen to decrease with corrosion
time (Figs 4 and 5). Sic has the best corrosion resistance of the four ceramic specimens; the
corrosion rate for Sic is only about 0.001 mg/cm2 h after 115 h; while alumina (85% Al,O,)
has the least corrosion resistance with a corrosion rate about 0.3 mg/cm2 h after 115 h of
immersion in the corrosive solution. There are many factors, which influence the corrosion
resistance of ceramic samples. The main factors are discussed below:
Acidic and basic character of the ceramic materials. According to the Lewis acid-base
theory, in general, acidic oxides and compounds resist attack by acids and are prone to
attack by bases. Pure A1203 and ZrOz are amphoteric, whereas Sic and S&N4 are weakly
acidic. The properties of mixed compound ceramics tend to be intermediate between those
of their constituents; in the case of sialon, its acidic character is stronger than that of A1203,
but weaker than that of S&N+ The ranking obtained from the experiments shows the
corrosion resistance of the various engineering ceramics to be SIC > Sialon > Zr02 > AlzOs.
This is in line with theoretical predictions.
Minor constituents. The criterion of acidity or basicity can only give a rough indication
of the corrosion resistance of ceramics, because it can be greatly altered by the presence of
minor constituents. These are commonly added to engineering ceramics in order to improve
their properties and performance. In the case of the ceramics used in the experiment,
0.9
N-
5 0.8
2 0.7 0.6
2
9 0.5 .
T
0 20 40 60 80 100 120
Corrosion time (h)
Fig. 3. Weight loss of ZrO*, sialon and Sic against corrosion time.
20 40 60 80
Corrosion time (h)
100 120 0
Fig. 4. Corrosion rate of alumina against corrosion time.
0.016 1
1.5% HF + 5% HCI
0.014 -~
room temperature
0.012 -- M
Urn I
I
I
0.01 -- I
A
0.006 .-
A A
IZro2
A Sialon 1
l SiC j
1
I
0.006 --
A
0.004 .~
A
A
0.002 A A
0. 0 0 0
04.
0 0 :
0 20 40 60 80
Corrosion time (h)
Y
100 120
Fig. 5. Corrosion rate of ZrOz, sialon and SC against corrosion time
-
RB SIC contained 2-10% non-reacted Si, which is insoluble in HF and HCl.
- PSZ ZrOz (95%) is stabilised by the addition of MgO, Yz03, and Si02.
-
Silica is added to suppress grain growth during manufacture and to improve the
mechanical properties, but it will confer a reduced corrosion to HF and HCl solution. MgO
as a basic ingredient will reduce resistance to acids, while SiOz has good resistance towards
acids but is easily attacked by HF; the substitution of HF molecules in solution with a
surface complex ion was suggested as the surface reaction.*
-
A1203 is mixed with 15% SiOz. As mentioned above, the presence of SiO;, can be
predicted to reduce the corrosion resistance of A1203 in HF + HCl solution and indeed this
is corroborated by our results.
Effect of corrosion and erosion on ceramic materials
517
Porosity in ceramics and roughness on surface. Reaction bonded Sic (RB Sic) is
produced by the reaction of either liquid or gaseous silicon or SiO with carbon in a silicon
carbide/carbon compact. This results in a porous body with a continuous silicon carbide
phase, however these pores can be filled with non-reacted Si (2-10%) yielding a dense
product that results in excellent mechanical properties and corrosion resistance. This is
confirmed by the results which show good corrosion resistance of Sic. In the case of A1203,
it is possible that the sintering agent, 15% SiOz (which is included during manufacture) is
preferentially attacked by the corrosive solution which contains hydrofluoric acid. Etching
would increase the penetration of solution and result in the formation of a surface layer
which is depleted in Si02 and hence mechanically weaker. This is confirmed by XRD and
AAS (see below). It is worth noticing that the corrosion rate of A1203 decreases with time at
a higher rate than for the other three ceramic materials. As the corrosion time increases the
depleted layer thickness increases. Access of the corrosive solution would thus be via
diffusion through this layer and thus slow down with time. Another factor for the decrease
in corrosion rate with time for AlzOs compared to the other ceramics could be due to the
initial surface finish which was rough. A rougher surface would increase the exposure area
to the corrosive solution at the start of immersion. In this case Al203 had a start surface
finish of Ra =0.7 urn, while the other materials had a smoother surface of 0.3401 urn.
Strictly speaking, using the rate of ceramic weight loss as a criterion for corrosion rate is
not accurate because there are two different corrosion processes: one is that the outer surface
can dissolve into solution, while the other is due to corrosion of one phase leaving a porous
and fragile outer layer which is then easily undermined by erosion. The weight loss in the
latter case may not be as high as in the first case but the top layer material strength is lost all
the same. Figure 6 shows the undermined surface layer on the A120s surface after corrosion
for 115 h. ZrOz and sialon also behave in a similar manner while such a top surface
degradation is not obvious in Sic.
XRD analysis
X-ray diffraction peaks of the tested ceramic specimens are shown in Figs 7-9.
Figure 7 shows the X-ray diffraction peaks for alumina (85% AlzOs, 15% SiO$ before
and after immersion in 1.5% HF + 5% HCl solution for 35 h. Prior to immersion of the
sample in the corrosive solution, other peaks, apart from A120s, which are mainly due to
SiOz, exist. These decrease remarkably, as the immersion time increases indicating
preferential attack by the corrodent on the SiOz. This means that silica is particularly
Fig. 6.
518 Q. Fang et al.
1000
[ countal
900
I---
-._!___....._..s
700
1
Cd)
1 .-..J
(cl
600
500
I--+
_ J =
4.J
Fig. 7. X-ray diffraction peaks for alumina. (a) Before corrosion; (b) after corrosion of I h; (c)after
corrosion of 6 h; (d) after corrosion of 30 h.
[countal
1400
1200
1000
800
600
400
200
0.0
- -
u
0
Fig. 8. X-ray diffraction peaks for sialon. (a) Before corrosion; (b) after corrosion of 30 h
prone to hydrochloric-hydrofluoric acid mixtures solution attack. In engineering ceramics,
additives are added to aid the sintering process of the ceramic and improve various
properties, such as increased fracture toughness, phase stability or wear resistance. This
Effect of corrosion and erosion on ceramic materials 519
kountml
iaoo
1600
1000
600
I--
600
400
1
200
0.0
[count6l-
1600.
w
m
600.
400-
200-
m: ZrO, monoclinic phase.
t: ZrO, tetragonal phase.
t
Fig. 9. X-ray diffraction peaks for PSZ zirconia. (a) Before corrosion; (b) after corrosion of 30 h; (c)
increasing diffraction peak of ZrOz-monoclinic phase in 28 = 28.23.
520 Q. Fang er al
phase however is preferentially attacked by the corrosive medium leading to a depIeted and
weak surface layer. Figure 8 shows a similar tendency for sialon.
Figure 9 shows the X-ray diffraction peaks for PSZ zirconia. Before corrosion both the
monoclinic and tetragonal structures are evident. After corrosion the peaks of monoclinic
structures increase dramatically. ZrCl, or ZrF4 was not detected. Increasing the length of
corrosion time, the monoclinic structure is markedly increased. Obviously, the corroded
layer is main source of contribution for increasing monoclinic phase. The doped tetragonal
structure transformed into monoclinic phase; this may be due to the pure monoclinic phase
being more stable than the tetragonal phase in PSZ zirconia at low temperatures. The
possible reaction steps in HF + HCl solution are as follows:
PSZ - ZrOz - m - ZrOz
YzOj + 6HCl R7, 2YCls + 3H20
SiO2 + 4HCl R SiC14 + 2H20
m - ZrOz f 4HCI z ZrC& + 2H20
m - ZrOz + HF R, ZrF4 + 2H20
According to the view point of thermodynamics, a phase structure leans to the
transformation of a metastable phase to the more stable under the attack of a corrodent,
just like that under the impact stress or tensile stress. However, the difference of the two
cases is that induced by impacting stress, part of f-ZrO, transforms into m-ZrOz and
microcracks develop, which consume crack propagation energy and release stress
concentration, whilst t-m transformation in corrosion process forms a porous m-zirconia
layer. From above experimental results, the surface structure of PSZ ZrOz changes and
becomes more porous during corrosion process, not only due to the t-m phase
transformation, in which cracks and void are anticipated owing to 3-5% volume change;
but due to the effect of higher corrosion rate of additives in PSZ ZrOz as well. The
hydrothermal effect of acidic solutions upon the corrosion of yttria (14 mol%) stabilised
zirconia (YSZ) single crystals was investigated and a similar result was given by Yoshimura
et al.9 They found that rapid dissolution of yttria occurred forming an interface of
polycrystalline monoclinic ZrOz in acidic solutions (those containing HCl or H2S04) at
600C and 100 MPa for 24 h.
For Sic, the XRD peak has not significantly changed after corrosion.
Analysis by atomic absorption spectrometry (AAS)
Table 2 shows the results of AAS for the corrosion solution after immersion of the
ceramic samples for 115 h.
Table 2. Chemical elemental analysis of the corrosive solution after corrosion of the ceramics for 1 I5 h (ppm)
Sample Al Zr Si
Mg
Y
Alumina 170+4 482k5
Zr02 1345+10 283k4 IO&O.2 <5
Sialon 7.2kO.2 220+4
Sic 2431-4
Effect of corrosion and erosion on ceramic materials 521
Apart from Sic, the proportion of the chemical elements in solution is different from the
composition of the ceramics themselves. The alumina sample is made of 85% A&O3 and
15% SiOf. The AAS results show that the dissolved Si:Al ratio is higher than that in the
ceramic. This would indicate that SiOz is preferentially attacked by the hydrochloric-
hydrofluoric acid mixture solution. The outer surface layer would thus be depleted of SiOz
leaving mainly Al203 grains and a more porous layer which is necessarily mechanically
weaker. Figure 6 shows the SEM cross-section of the A&O3 sample, which was tested in the
corrosion bed at room temperature for 115 h. The corroded layer (120 urn thick) is more
porous and contains many microvoids. Figure 10 shows a loose corrosion product (white)
dispersed on the ceramic particles.
In the case of ZrOs-1035 (ZrOz more than 95%), the silicon, magnesium and yttrium
oxides used for doping are more readily dissolved as can be seen by the results in Table 2
which again indicate a higher ratio of doping elements to Zr in solution than in the ceramic.
A change in microstructure is thus expected.
Sialon used in this investigation is made of B-S&N4 and 5% A1203. Because sialon has
the same atomic arrangement as B-Si3N4, its mechanical and physical properties are similar
to those of the nitride with some additional advantages such as lower vapour pressure and
lower sinter temperature. Silicon nitrides are resistant to most acids, but are affected by
hydrofluoric acid just like silica. The AAS result shows a high solubility of the silicon
content. The formation of pores in the corrosion layer on the sialon surface, has been
observed after corrosion testing (Figs 11 and 12).
Erosion resistance after corrosion
Table 3 shows the erosion results of the four ceramic samples before and after corrosion
of 35 h.
From the previous discussion in the last two sections, the corrosion of a ceramic is akin
to a chemical etch of the surface which would decrease the mechanical properties of the
ceramic. Hardness and strength would be reduced. The erosion results con&m this.
Table 3 shows that erosion alone has a bigger effect in terms of weight loss than
corrosion. The combined effect of corrosion followed by erosion enhances the weight loss.
The results are most significant for alumina. Of the four ceramic samples, alumina has the
lowest chemical and erosion resistance, while sialon was found to exhibit greater weight loss
Fig. 10. Loose corrosion product (white) dispersed on the Al203 ceramic particles after corrosion
for 11s h.
522
Fig. I 1. Propagation of cracks and pores of a hardness tested (Hv indented) sialon sample after 35 h
corrosion.
Fig. 12. Magnification of a crack formed on a hardness tested (H, indented) sialon sample after
35 h corrosion.
Table 3. Comparison of weight loss of erosion (60 min) before and after corrosion of 35 h
Samples
Alumina
PSZ-ZrQ
Sialon
Sic
Weight loss due only to Weight loss due to erosion Weight loss due to erosion
corrosion (35 h) (mg/cm*) (60 min) before corrosion (60 min) after corrosion of
(mg/cm2)
35 h (mg/cm2)
4.50 47.50 173.50
0.11 1 .o 1.20
0.05 1.80 8.20
0.01 1.50 1.60
on erosion after corrosion denoting a degradation of the mechanical properties of the
surface. The erosion resistance of SIC and zirconia do not seem to significantly change after
corrosion although the zirconia specimen shows more weight loss due to corrosion than
either SIC or sialon. From the above combined erosion/corrosion results, it can be seen that
corrosion of the ceramics is manifested in two different ways.
In the first case, the corrodent directly etches the surface of the ceramic and the products
from corrosion immediately go into the solution, then the corrosion continues on the next
fresh surface of the ceramic. SIC and PSZ zirconia behave in this way. After corrosion tests,
they always show a fresh surface of the ceramic, where mechanical properties are not much
Effect of corrosion and erosion on ceramic materials 523
reduced, so that their erosion resistance remains as good as that before corrosion. In the
second case, the corrodent attacks the surface of the ceramic, preferentially leaching some
phases and leaving behind a laced layer. This corrosion layer has obviously marked changes
in mechanical properties, so that it has poorer erosion resistance. On the other hand, this
depleted layer on the surface of the ceramic, can partly impede and delay the ingress of
corrosion deeper into the ceramic. This is confirmed by corrosion experimental result for
alumina and sialon (Figs 4 and 5) where the corrosion rate decreases with time (up to 115 h).
The weight loss due to erosion of alumina before and after corrosion is given in Fig. 13.
It can be seen that after about 0.5 h of erosion, the rate of erosion changes and becomes
comparable to the erosion rate before corrosion. This indicates that the weakened surface
layer formed in 5 h due to corrosion has been consumed by erosion in 0.5 h. Such a
measurement indicates, in kinetic terms, the predominance of erosion effects. The slope for
erosion after corrosion in the affected layer also changes. In the first 0.2 h the rate is very fast
followed by a slight decrease between 0.2-0.5 h, after which a comparable erosion rate to the
bulk material occurs. Figure 14 shows that the top layer on the ceramic is very porous
followed by partial incorporation of the corrdent in pores and cracks in the top section of
the bulk material. The underlying matrix is unaffected. The erosion rate after 0.5 h of
erosion is comparable for the alumina before and after corrosion (similar slope of the linear
section). The higher erosion rate exhibited by the corroded surface layer at the onset of
erosion indicates that the erosion occurred at first on the corrosion layer, which produces a
high erosion rate, and when the corrosion layer was consumed, the erosion rate slowed
down on a new fresh interface of the ceramic surface. The facts indicate, that the chemical
etch gives rise to a corrosion layer, which has weaker mechanical properties and is more
easily eroded. The thickness of the corrosion layer is directly dependent on corrosion time,
type of corrodent and properties and composition of materials. The tremendous increase in
erosion rate of alumina and the relatively large thickness of the corroded layer make the
utilisation of this material in such environments quite suspect.
Usually, such a corrosive mixture should be applied for short times of 2-3 h, however in
practice, periods of 24 h and greater can occur; in such cases, care should be exercised in the
selection of materials. It is advisable to test alumina samples from various sources, as the
70
60
0 0.5 1 1.5 2 2.5 3 3.5
Erosion time (h)
Fig. 13. Weight loss of alumina by erosion test before and after corrosion (5 h).
524 Q. Fang et al.
20 KV x750 10um 001203
Fig. 14. S.E.M. ofcross-section of alumina after corrosion for I I5 h.
method of fabrication and additives, together with the sintering process, could have a
marked effect on the performance of the material.
Hardness of the ceramic specimen after corrosion
Hardness is one of the key factors of the mechanical properties of materials. The results
of Vickers hardness indentation of the four ceramics before and after corrosion are shown in
Table 4.
From Table 4, it can be seen that H, values for alumina and sialon show the highest
changes due to corrosion, viz a decrease ca. 83% and 14% indicating a degeneration in
mechanical strength of the surface layer. This agrees with the higher erosion weight loss
after corrosion of 35 h (Table 3), for Al203 and sialon, respectively. The change in hardness
of the ceramic surface after corrosion is due to the corrosion layer, which has a porous
structure and thus exhibits a degeneration in mechanical strength (see also Figs 6 and 10).
Although a sand/water slurry erosion test and an indentation test are different processes,
the dynamic erosion test can be considered, to a large extent, as being a series of static
indentation tests on the microstructural level. The Vickers indentation shapes can also be
used to elucidate the mode of cracking due to the impact of the erodent onto the surface. It
was found that the mode of cracking depends on the brittleness of the material. SIC and
sialon (which are brittle) exhibit radial cracks around the Vickers indentation site whereas in
Table 4. Results of hardness (Hv) of the four ceramics before and after corrosion (35 h)
Sample H, before corrosion H, after corrosion of 35 h
Alumina
Zr02
Sialon
SIC-F
1169k40 200+ 10
1489+50 1431,50
1675+50 1441+50
2255k50 2135150
*The applied load of Vickers hardness tests of 10 kg for alumina, 50 kg for the rest,
Effect of corrosion and erosion on ceramic materials 525
less brittle materials, the cracks are small and extend vertically into the core of the sample.
The manifestation of these cracks which were formed before corrosion is more obvious after
the samples were corroded.
Slurry erosion-corrosion mechanism
The results in Tables 3 and 4 point to the synergistic effect of erosion-corrosion. In
extreme cases such as A1203 and sialon, preferential dissolution of one phase leads to the
creation of a weakened surface layer which is easily eroded. The weight loss due to erosion
after corrosion far exceeds the sum of weight loss due to the individual corrosion and
erosion processes. The observations above indicate that cracks (created in this case by the
microvickers indentation) act as easy diffusion paths for the corrodent into the bulk of the
material. The synergism of corrosion-erosion is thus due to a series of processes viz
undermining of the top surface of the ceramic due to corrosion followed by easy erosion of
this layer coupled with crack formation in the underlying matrix due to the erosion process
which then allows the corrodent further in the material and the loop restarts, i.e. that both
erosion and corrosion processes assist each other to augment the damage so that their effect
is more than the simple sum of the damage caused by each process separately.
Various researchers have tried to investigate the synergism of erosion-corrosion and to
separate the contribution of each process to the overall material performance. In a review14
by Wood and Hutton literature data on steels were used for evaluating the equation:
S=T-(E+C)
where S is the synergistic wear rate; T is total wear rate where corrosion and erosion are
occurring simultaneously; E and C are the erosion and corrosion wear rates, respectively.
Although the experiments performed in this paper are for different corrosion and erosion
times, some information can still be gleaned from them. From Table 3 it can be seen that the
contribution to weight loss by corrosion is minimal although the exposure time is 35 h as
opposed to 1 h for erosion. In some cases, as in AllOX, this is analogous to localised
corrosion in materials where weight loss measurements do not give a true indication of the
corrosion resistance of the material. In ceramics, where corrosion leads to porous layers, it
would seem that measurement of the affected layer thickness would give a better indication
than weight loss. The affected layer thickness in 115 h was 120 pm. The erosion of this layer
was performed in 30 min.
CONCLUSIONS
To gain a better understanding of the corrosion+erosion processes of some engineering
ceramic materials, experimental investigations were performed with corrosion and erosion
tests both separately and then combined in succession. As a result, the following conclusions
can be given:
(1) Under the test conditions, Sic shows the best chemical and erosion resistance of the
four ceramics; and alumina has the highest corrosion and erosion rate.
(2) Corrosion of a ceramic can occur by either dissolution of the entire top surface as in
Sic (whose corrosion resistance is very good) or by preferential dissolution of sintering
agents which leads to a porous surface layer with inferior mechanical properties and reduced
surface hardness.
526 Q. Fang et al
(3) Corrosion weight losses do not show a clear picture of the true degradation
mechanism. Two zones exist via an outer depleted surface layer plus a zone just
underneath where existing cracks or erosion cracks act as corrodent diffusion paths. The
corrosion of a ceramic leads to a decrease in the hardness of the surface.
(4) The different corrosion rates and solubility of the corrosion products for different
ceramic compositions are responsible for the formation of the pores and internal corrosion
layer, which leads to a degeneration of mechanical properties on the ceramic surface. The
solubility of the corrosion products of the ceramic determines its physical and mechanical
surface properties; where the products are all soluble, a fresh strong surface is exposed with
similar mechanical properties to the original material with a consequent decrease in
thickness. In the other extreme, where only certain phases (e.g. binders and sintering agents)
are preferentiahy dissolved or where the corroded products remain on the surface, the
mechanical properties are decreased equivalent to a porous structure.
(5) The synergism in corrosionerosion is due to the creation of the outer porous layer
which is mechanically weak. The erosion process easily removes this layer and creates cracks
in the underlying material which are then easily corroded.
(6) Erosion rates appear higher in materials with a corroded surface layer than in
materials where the etching of the surface leaves a similar surface to the original material.
(7) The erosion contribution to erosion-corrosion was very high in the ceramic materials
investigated.
(8) The slow corrosion rate of a ceramic (compared to metals and alloys) requires a
different approach to the study of corrosionerosion particularly in applications where the
corrosive solution has time to act on the surface.
(9) Further work to follow the rate of erosion of a corroded surface could aid in assessing
the synergistic effects.2
Acknowledgements-The authors wish to acknowledge the Science and Engineering Research Council (SERC) for
funding this research. They would like to thank Dr. D. Harrop of BP for his guidance as well as Dr. H. Xu of Shell
and Dr. R.J. Wood of Southampton University for valuable discussion. Thanks also go to Mr. R. Sweeney and Mr.
M.J.L. Haddon for their technical assistance.
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