Refractories and Industrial Ceramics

Vol. 41, Nos. 11 12, 2000

UDC 666.3.017:620.173.26

EFFECT OF AQUEOUS SOLUTIONS

ON THE STRENGTH OF 22KhS CERAMICS
S. M. Barinov,1 N. V. Ivanov,1 A. V. Kurepin,1 B. Ballokova,1 P. Hvizdosh,1 and . Rudnajova1
Translated from Ogneupory i Tekhnicheskaya Keramika, No. 12, pp. 10 14, December, 2000.
Ceramics based on alumina undergo delayed failure in aqueous solutions as a result of stress corrosion. The effect of the loading rate on the strength of the 22KhS ceramics in aqueous solutions with pH ranging from 1 to
12 is studied. It is shown that acid and alkaline media diminish the resistance of the ceramics to delayed failure
substantially. The parameters of statistical distribution of the strength also depend on the characteristics of the
media. It is shown that the resistance of the 22KhS ceramics to delayed failure can be enhanced by preliminary
chemical treatment.

INTRODUCTION

of crack growth v on the coefficient of stress intensity K is

described by an empirical formula:

The 22KhS ceramics is widely used as a structural material for the production of parts of machines and mechanisms
(gaskets, sockets, seals of various pumps, cocks, etc.) that
work in water and aqueous solutions [1]. In order to form a
grain-boundary phase in such ceramics, the compositions are
enriched with additives based on sodium, manganese, chromium, and silicon oxides that interact with matrix Al2O3
crystals in sintering. It is known that materials based on
Al2O3 a with grain-boundary silicate phase undergo chemical
corrosion, which mainly occurs over the silicate component
[2]. It is assumed that protons and H3O+ ions of the acid substitute for the metal (alkaline) ions of the silicon phase and
cause breakage of the Si O Me and Si O Si bonds,
yielding a silica gel on the surface [2]. Hydrochloric acid is
one of the most corrosion-active media with respect to corundum ceramics with a glass phase. The decrease in the
mass of such ceramics held in 35% HCl attains 1.0 g/m2 a
day [2]. It can be assumed that ceramics with a silicate
grain-boundary phase will be sensitive to stress corrosion,
which causes growth of the structural defects existing in the
material, i.e., microcracks and pores, and is responsible for
the dependence of the strength on the loading rate (a phenomenon known as dynamic fatigue) [3].
The subcritical propagation of cracks in ceramics occurs
in three stages. In the first stage, the dependence of the rate
1

v = AK n,

(1)

where A is a coefficient and n is an exponent that quantitatively describes the sensitivity of the material to the process
of delayed failure; the higher the value of n the more resistant to delayed failure the material is. The duration of this
stage determines the time before failure under load.
The value of n is determined by testing the material under a constant load with measurement of the time before failure (the method of static fatigue) or by performing strength
tests in a wide range of loading rates (the method of dynamic
fatigue). In the latter case, the value of n is found from the
proportion of the measured ultimate bending strength sb to
the specified deformation rate e&, i.e.,
log sb = C +

1
log e&,
1+ n

(2)

where C is a constant that depends on the properties of the

ceramics [3, 4].
It has been shown earlier that the value of the exponent n
for a ceramics tested in the given medium depends on the
composition of the grain-boundary phase [5 7]. We found it
interesting to evaluate it for the 22KhS ceramics widely used
in industry. In addition, we expected that a preliminary
chemical treatment that causes modification of the grainboundary phase should affect the dynamic fatigue of the ceramics. This became the aim of the present work.

Institute of Physicochemical Problems of Ceramic Materials of

the Russian Academy of Sciences, Moscow, Russia; Institute for
Materials Research of the Slovak Academy of Sciences, Bratislava, Slovak Republic.

422

1083-4877/00/1112-0422$25.00 2001 Plenum Publishing Corporation

Effect of Aqueous Solutions on the Strength of 22KhS Ceramics

log s (MPa)

MATERIALS AND METHODS OF STUDY

2.6

We studied 22KhS ceramics obtained by hot casting with

subsequent roasting in vacuum. The composition included
(in wt.%) 94.5 Al2O3, 2.5 SiO2, 0.03 Fe2O3, 0.48 Cr2O3,
1.96 MnO, 0.2 Na2O plus impurities (the remainder). The
content of corundum grains in the material was
88 89 vol.% and that of the grain boundary phase was
11 12 vol.%. The microstructure of the ceramics was represented by elongate corundum grains up to 30 mm long and up
to 15 mm thick. The density of the material was 3.78 g/cm3,
and the content of the open pores did not exceed 2%.
The tests were performed by the method of three-point
flexure of specimens with a cross section of 5 5 mm at a
distance between the supports of the loading device equal to
32 mm with the help of a UTS-100 universal testing machine
(UTS Testsysteme GmbH, Germany). The speed of the
crosspiece of the loading device was changed from 0.01 to
15 mm/min. The dependence of sb on e& was measured in
the following media: water (pH = 7), 0.1 mole/liter HCl
(pH = 1), and 0.1 mole/liter NaOH + a buffer solution
(pH = 12). In each series of tests, we tested 14 16 specimens. We also studied the statistical distribution of the
strength in the mentioned media at a constant loading rate of
0.5 mm/min (controlled by the acting standards ASTM
C 1161, JIS R 1601, DIN 51 110, and AFNOR B41-104 [4]).
The data were processed statistically with the help of an estimator of the type
Pi =

i -0.5
,
N

(3)

where Pi is the probability of failure, i is the number of the

specimen, and N is the number of specimens in the series; the
Weibull distribution function is used in a biparameter representation:
V
P = 1 exp V
0

s
0

423

(4)

where P is the cumulative probability of failure, V is the

stressed volume, V0 is the scale factor, s is the stress, s0 is a
normalizing factor, and m is the modulus of the Weibull
function that characterized the uniformity of the distribution
of defects responsible for the strength of the specimens
[4, 8]. In order to find the Weibull function we tested
15 specimens at a constant loading rate.
We determined the values of crack resistance by standard
methods with the use of specimens in the form of bars with a
single side notch (SENB specimens) [4]. The notch was deposited by a diamond cutter about 100 mm thick. The depth
of the notch was 0.5 of the height of the section of the specimen. The crack resistance was calculated for a maximum
load, which corresponded to the beginning of uncontrolled

2.4

2.2

pH = 1
n = 28.4
6

log s (MPa)

1
.2
log e (sec 1 )

2.6

2.4

2.2

pH = 7
n = 32.3
6

log s (MPa)

1
. 2
log e (sec 1 )

2.6

2.4

2.2

pH = 12
n = 24.6
6

1
. 2
log e (sec 1 )

Fig. 1. The strength of the ceramics as a function of the loading rate

in different media.

propagation of the crack in the specimen, by known formulas

and values of calibration functions [4].
In addition, we studied the influence of a 60-day hold of
specimens in 0.1- and 1.0-mole/liter solutions of hydrochloric acid on their dynamic fatigue in subsequent tests in water.
Mechanical tests were performed in a UTS-100 machine
under the conditions of three-point flexure and hard loading.
A special device was created for tests in corrosion-active
media.
Fracture surfaces were studied under a TESLA electron
microscope. The changes in the chemical composition were
determined by the method of energy dispersive x-ray spectral
analysis.
RESULTS AND THEIR DISCUSSION
The strength of the ceramics increases with the deformation rate in tests performed in different water-containing media (Fig. 1). The dependence of the parameter n calculated by
Eq. (2) on the pH of the solution is presented in Fig. 2. It can
be seen that n decreases both in acid and alkaline media.
The value of n in tests performed in water is about the
same as that of other alumina materials with a glass phase,

424

S. M. Barinov et al.
n

ln ln [1/(1 P )]
2

32

1
0

30

1
28

26

4
24

m1 = 8.9
m2 = 11.7

12

pH of the solution

5.5

5.6

5.7

5.8

5.9

6.0

6.1

ln s (MPa)

Fig. 2. Effect of the pH of the solution on the parameter n.

Fig. 3. Statistical distribution of the ultimate bending strength for

ceramics tested in water (1 ) and in a 0.1 M solution of HCl (2 ).

i.e., for a ceramics with yttrium-alumosilicate glass phase

n = 36, for a material with calcium-alumoborosilicate grainboundary phase n = 32, and for the GB-7 commercial ceramics n = 30 [5 7]. However, the value of n for the 22KhS
ceramics is much lower than for a microlite-type material
with 99.5% Al2O3 and 0.4% MgO (n = 60) [5, 6]. Electron
microscopic studies of fracture surfaces in the ceramics
tested in different media show that the crack chiefly propagates by an intercrystalline mechanism over grain-boundary
phases. Thus, we can assume that the composition and the
properties of the glass phase in the 22KhS ceramics are the
main factors responsible for its behavior when it is loaded in
aqueous solutions.
The main component of grain-boundary phases in all the
studied materials with a glass phase was silica, which actively interacted with water in the process of stress corrosion.
A model of such an interaction mechanism is suggested in
[9, 10] within the theory of dissociative chemisorption. The
model allows for the following stages of the process: adsorption of a water molecule to a Si O Si bridge bond, redistribution of the electron density in the region of the stressed
and strained bridge bond, and breakage of this bond with formation of OH radicals with uncompensated charge. The
model predicts the values of n for silica, which exceed 50.
It can be assumed that the presence of modifiers and
other elements in the grain-boundary phase substantially
complicates the mechanism of stress corrosion. Sodium oxide leaches out of the glass phase in the loading process,
changing the pH of the medium right at the tip of the crack,
and reduces the resistance to stress corrosion. A similar effect has been observed for alkaline-silicate glasses [11] in
which n decreases considerably as a result of leaching in the
loading process. Chromium and manganese form chemical
bonds with oxygen in the glass phase. It is known that chromium and manganese oxides are characterized by a high
solubility in alkalis and that chromium oxide dissolves in

mineral acids. It is obvious that this should decrease the resistance of the glass phase to dynamic fatigue.
The components of the composition used for the formation of the grain-boundary phase are introduced in the following proportion: SiO2 : MnO : Cr2O3 = 2.5 : 1.96 : 0.48.
Chromium and manganese oxides do not possess a glassforming capacity. Their content in the composition in question is such that it can hinder the formation of a continuous
structural glass net, causing the formation of microinhomogeneities. In addition, the dissolution of alumina crystals in
this flux in the sintering process can be accompanied by further intensification of the inhomogeneity as a result of the
segregation of alumosilicate phases, for example, mullite.
Mullite is known to possess a low resistance to dynamic fatigue (n = 27) [12]. An electron microscopic study has shown
the presence of needle-like crystals in the structure of grain
boundary phases. The crystals dissolve both in the acid and
in the alkali directly in the process of the dynamic fatigue
tests. Unfortunately, the components of grain-boundary
phases could not be identified by the method of x-ray phase
analysis because of the low volume of the latter.
Thus, we can assume that the low resistance of the
22KhS ceramics to delayed failure can be a result of the
chemical composition of the grain-boundary phase containing soluble oxides of sodium, chromium, and manganese and
by the inhomogeneity of the structure of this phase.
The ultimate bending strength measured under standard
loading conditions [4] was 230, 224, and 219 MPa in tests in
water (pH = 7), in acid (pH = 1), and in alkalis (pH = 12) respectively. We see that the composition of the medium influences the strength. The crack resistance KIc also decreased
from 4.7 to 4.2 MPa m1/2 when we passed from tests in water to tests in an acid. In accordance with the Griffith criterion, the decline of the strength and crack resistance determined from the conditions of critical equilibrium for the resistance of a fractured specimen can be explained on the basis of the Rebinder effect, i.e., the decrease in the surface

Effect of Aqueous Solutions on the Strength of 22KhS Ceramics

425
log s (MPa)

ln ln [1/(1 P )]
2

2.4

m = 5.8

1
0

pH = 7
n = 93.3

2.2

. 2
log e (sec 1 )

log s (MPa)

m = 33.9

2.4
5.6

5.7

5.8

5.9

ln s (MPa)
Fig. 4. Bimodal statistical distribution of the strength of the specimens tested in 0.1 M HCl.

energy of fracture of a solid body upon its interaction with

the ambient [13, 14]. Another cause can be the subcritical
growth of the defects, i.e., the microcracks responsible for
the strength and the macronotch responsible for the crack resistance of the specimen, due to the stress corrosion. Figures 3 and 4 present the results of statistical tests of ceramics
in water and in acid. The strength distributions in these media differ substantially; the tests in acid result in a bimodal
distribution. The mean modulus of the Weibull function m
increases from 8.9 to 11.7 upon the transition from water
tests to acid tests. Two segments of the distribution function
in acid tests correspond to a modulus of 33.9 (the domain of
low strength) and 5.8 (the domain of high strength). All these
facts indicate that in acid tests the microcracks controlling
the strength of the ceramics grow to a subcritical size, which
agrees with the data of tests for dynamic fatigue.
It is known that the treatment of many silicate glasses in
acids increases their water resistance [15]. Since the studied
ceramics fracture over the grain-boundary phase, we studied
the possibility of increasing the fracture resistance of the ceramics by its preliminary treatment in acids. Ceramic specimens were held in 0.1- and 1.0-mole/liter solutions of hydrochloric acid for 60 days at room temperature and then tested
for dynamic strength. The decrease in the mass as a result of
the treatment did not exceed 0.08%, which, as recalculated
for the content of the grain-boundary phase and under the assumption that only this phase dissolves, corresponds to a
0.8 1.0% decrease in the mass of the grain-boundary phase.
The results of an energy dispersive x-ray spectral analysis
of regions of ceramic surfaces performed on an area
600 450 mm in size are presented in Table 1. It follows
from these data that the acid treatment decreases the concentration of SiO2 and Cr2O3; Na2O completely leaches from
the ceramics; Al2O3 and MnO virtually do not dissolve in
the acid.
Figure 5 presents data on the dynamic fatigue of specimens. The values of n range from 93 to 85 after treatment in

2.2

pH = 7
n = 84.5
6

3
2
.
log e (sec 1 )

Fig. 5. Dependence of the strength of the ceramics on the deformation rate in water tests after a 60-day hold in solutions of 0.1 M
HCl (a) and 1.0 M HCl (b ).

0.1- and 1.0-mole/liter solutions, which is much higher than

in the initial state of the ceramics. It can be assumed that the
increase in the resistance to stress corrosion is caused by the
change in the chemical composition of the grain-boundary
phase. At the same time, the values of the ultimate bending
strength of the ceramics measured under standard conditions
were 209 and 214 MPa after the treatment in 0.1- and
1.0-mole/liter solutions of the acid respectively. It seems that
this is caused by the formation of new pores or the volume
growth of the existing pores due to the acid treatment, which
is confirmed by the change in the mass of the specimens.
Thus, the preliminary acid treatment increases the resistance
of the 22KhS ceramics to delayed failure in water media at a
certain decrease in its short-term strength.
CONCLUSIONS
We studied the influence of aqueous solutions with pH
changed from 1 to 12 on the mechanical properties of the
22KhS ceramics. It turned out that the ceramics possesses a
low resistance to delayed failure in water due to the processes of stress corrosion occurring in the grain-boundary
phase. Acid and, especially, alkali solutions reduce this resis-

TABLE 1. Results of X-Ray Spectral Analysis of Specimens

State of ceramics

Content of oxides, %
Al2O3

Initial
92.036
After treatment in HCl:
0.1 M
92.635
1.0 M
92.712

SiO2

Cr2O3

MnO

Na2O

4.483

0,738

2.599

0.166

3.993
3.732

0.608
0.530

2.740
2.902

0.020
0

426
tance substantially, as well as the strength and the crack resistance of the ceramics. The latter can be caused by the
Rebinder effect and by the processes of dissociative
chemisorption. The pH of the solution determines the parameters of the function of statistical distribution of the strength.
Specifically, when the tests are performed in an acid the
strength distribution becomes bimodal, which is a sign of
subcritical growth of the existing defects of the microstructure. The resistance of the 22KhS ceramics to delayed
failure in a water medium can be increased substantially by
preliminary chemical treatment in an acid. Such a treatment
diminishes the contents of silica and chromium oxide and
completely leaches sodium oxide from the grain-boundary
phase. The decrease in the mass of the phase during the treatment attains 1.0%, which leads to a certain loss in the
short-term strength of the ceramics.
This work has been performed within the program of
academic cooperation between the Russian and Slovak
Academies of Science and with support from the Russian
Fund for Fundamental Research, Grant No. 00-03-32601.
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