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Corrosion of ceramic materials
Chapter · February 2018
DOI: 10.1016/B978-0-08-102203-0.00009-3
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Fundamental Biomaterials: Ceramics. https://doi.org/10.1016/B978-0-08-102203-0.00009-3
Copyright © 2018 Elsevier Ltd. All rights reserved.
9Corrosion of ceramic materialsP.N. Sudha*, K. Sangeetha*, A.V. Jisha Kumari†, N. Vanisri*, K. Rani*
*D.K.M. College for Women, Vellore, India, †Tagore Engineering College, 
Chennai, India
Abstract
The term ceramic inclined us to think of tiles, pots, and has been accompanied with 
human race from ancient days. The last century has seen an exponential explosion in en-
gineering developments that would not have been possible without ceramics. Today the 
ceramic materials are considered as a special category due to excellent properties such as 
high melting points, low electrical and thermal conductivity values, and high compres-
sive strengths and these ceramic materials have extended their hands in various fields in-
cluding electronic devices, computer, dentistry, biomedical, and aerospace engineering. 
This vast role of ceramic material in day-to-day life makes us to identify the problem of 
corrosion that occurs in ceramic. Even though the term corrosion was generally associ-
ated with metals, ceramic materials also undergo unintentional degradation in contact 
with environment. Generally corrosion is a system property rather than a simple material 
property, and today the impact of corrosion on society and the related deterioration of 
materials lead to the increased complexity and diversity of material system including 
ceramics, which are not susceptible to electrochemical degradation due to its poor con-
ductor property but due to the simple dissolution of the material. In recent years, there 
was significant advancement in the study on the interaction between corrosion and ero-
sion in ceramics. In general, the corrosion in ceramics material is not instantaneous and 
this chapter sheds over some light on better understanding of the mechanism involved in 
corrosion-erosion of ceramicmaterials. This chapter glances over the direct relationship 
of corrosion to the property degradation and also explains in detail the various testing 
procedures adopted for the evaluation of material stability. One of the most important 
properties affected by corrosion was its mechanical strength. The advancement of ce-
ramic material in dentistry was inevitable due to its different microstructures, chemical 
composition, properties, and these ceramics materials were generally corroded in acidic 
medium. Hence, in this chapter, we elaborate the effects of erosion on ceramic on the sur-
face roughness, flexural strength, and exposure to various environments including acidic 
medium. We also discussed the methods adopted to minimize the ceramic corrosion.
Keywords: Corrosion, Ceramic materials, Crystalline, Acidic agents, Environment, Glass.
9.1 Introduction
9.1.1 What are ceramic materials?
In recent years, the commercialization and technical interests on ceramic materials are in-
creasing due to enhanced properties of chemical, mechanical, and thermal performance, 
224 Fundamental Biomaterials: Ceramics
which meet many engineering requirements [1] such as energy production [2] and 
 aerospace engineering [3,4]. Ceramics materials can be defined as inorganic, nonmetal-
lic materials comprising metal, nonmetal, or metalloid atoms held by ionic or covalent 
bonds. The ceramic structure is based on electric neutrality [5]. They are generally pre-
pared using clays and other minerals from the earth or chemically processed crystalline 
oxide, nitride, or carbide powders, i.e., aluminum and oxygen (alumina—Al2O3), silicon 
and nitrogen (silicon nitride—Si3N4), silicon and carbon (silicon carbide—SiC), etc.
Ceramic materials are typically categorized as traditional ceramic and advanced 
ceramic. Traditional ceramic materials include clay, porcelain, feldspar, silica, calcite, 
and nepheline. The history of traditional ceramic with human race is very long, going 
back to around 24,000 BCE. The most common products of traditional ceramics were 
pottery, tableware, refractories, tiles, and so on. Advanced ceramics includes alumina, 
zirconia, silicon carbide, silicon nitride, and titania-based materials, which can replace 
the metals and plastics in the modern era due to their exceptional properties that make 
them highly resistant to melting, bending, stretching and possess unique individual 
properties in their own way [6]. The application of advanced ceramic was expanded in 
various fields and the ceramic industry is now becoming one of the most competitive 
industries in the market.
9.1.2 Types of ceramic materials
Ceramic materials are broadly classified into two types based on the arrangement of 
atoms that constitute the particular substance.
(a) Crystalline ceramic materials:
Most of the ceramic materials have crystalline structure and are more brittle than 
metals. The arrangement of atoms in the crystalline ceramic was highly ordered 
throughout the material. Crystalline ceramics were not amenable to set of processing/
production [7]. These materials were generally synthesized either by compacting pow-
ders into a body followed by sintering at higher temperature to form a solid desired 
shape or by the reaction “in situ.” The techniques adapted to form crystalline ceramics 
include slip casting, tape casting, injection molding, dry pressing, and so on.
(b) Noncrystalline/Amorphous ceramic materials:
The processing of glass is totally different from the crystalline ceramic preparation 
and involves several steps. Noncrystalline ceramic, being glasses, can be usually prepared 
from melts. The glasses were processed into desired shape either by casting them in the 
molten state or by blowing the toffee-like viscosity state into a mold [8]. These noncrys-
talline ceramic materials were also called “Super cooled liquids” because the orientations 
of molecules are random and highly disordered in the frozen solid state (Fig. 9.1).
9.1.3 Classification of technical ceramics
Technical ceramics are classified into three distinct material categories, which are as 
follows:
(a) Oxides: alumina, beryllia, ceria, zirconia
(b) Nonoxides: carbide, boride, nitride, silicide
Corrosion of ceramic materials 225
(c) Composite materials: particulate reinforced, fiber reinforced, combinations of oxides and 
nonoxides.
Each one of these classes can develop unique material properties because ceramics 
tend to be crystalline.
9.2 Corrosion
9.2.1 Corrosion of crystalline materials
Ceramics are inorganic or nonmetallic solids and these materials may have a crystal-
line or partially crystalline structure, which undergoes corrosion when it is in contact 
with solids, liquids, or gases, or any combination of these.
(a) Corrosion by solids
The crystalline materials undergo interdiffusion or chemical diffusion process on 
contact with solids [10]. The driving force for interdiffusion was due to chemical po-
tential gradient, which causes the chemical reaction on the surface and leads to deteri-
oration of the ceramic material.
(b) Corrosion by liquids
The corrosion of crystalline materials in liquid follows the mechanisms of indirect 
dissolution, incongruent dissolution, or heterogeneous dissolution. The corrosive en-
vironment with the liquid medium involves increase in the velocity of the medium, 
thereby causing corrosion [11]. Diffusion through the boundary layer was considered 
as the rate-limiting step during dissolution. The composition of the boundary layer may 
vary depending upon the rate of diffusion across the boundary layer of ceramic [12].
(c) Corrosion by gases
When a crystalline ceramic was exposed to vapor, they rapidly penetrate into the 
material and cause corrosion. Thus, the volume of porosity and the pore size distribu-
tion are most important factors that govern the corrosion in gases [13].
9.2.2 Corrosion of noncrystalline materials
The aqueous corrosion in glasses was classified into two types: Static and dynamic. 
In static aqueous corrosion, there is an entrapment of moisture on the surface of the 
Crystalline solid Amorphous
noncrystalline solid
Fig. 9.1 Schematic structure of ceramic material [9].
226 Fundamental Biomaterials: Ceramics
glass. In dynamic aqueous corrosion, the corrosion solution is replenished due to con-
densation run-off.
(a) Corrosion by solid
The corrosion behavior of noncrystalline materials in contact with solid was similar 
to the crystalline ceramic, which causes degradation of the materials through chemical 
interdiffusion processes.
(b) Corrosion by liquid
The corrosion of glasses by liquid follows chemical dissolution, which was similar 
to that of corrosion in crystalline ceramics [14]. The aqueous media of acids and al-
kalis and even neutral liquid media also corrode the surface of glasses by dissolution 
process.
(c) Corrosion by gas
Ceramic materials undergo rapid corrosion by vapor attack and the severity in the 
degradation was due to the availability of larger surface area for the vapors to contact 
than the liquids or solids [15]. In noncrystalline glasses, the contact of gases to the 
glass surface results in dissolution of the surface, thereby causing corrosion.
In most cases during gaseous corrosion, the oxidation and dissolution processes 
are more prevalent form of attack and in some cases hydrogen reactions are also 
possible [16].
9.3 Corrosion analysis
9.3.1 Corrosion testing
The measurement of corrosion rate of ceramic materials under different physical, 
chemical, thermal, and stress states is a broad subject. Two types of testing can be used 
by researchers to study the rate of corrosion [17]. They are as follows: (a) Laboratory 
tests and (b) Field tests. Undertaking laboratory test was less expensive and provides 
a better control over exposure conditions. On the other hand, in the field test, the 
performance of the material in the environment is well predicted but the results are 
empirical;hence, the combination of both laboratory test and field test is the best way 
to obtain better knowledge on the corrosion mechanism of ceramic materials.
9.3.2 Corrosion test methods
The American Society for Testing and Materials (ASTM) was formed in 1898 to or-
ganize some standard testing procedures to evaluate the corrosion behavior for testing 
ceramic materials. One of the simple methods for measuring the rate of corrosion was 
determining its periodic weight loss by immersing the material in electrolyte at a cer-
tain temperature. The rate of corrosion was determined from its weight loss per unit 
area and time. This method was applicable only for a limited and less corrosive media.
Corrosion of ceramic materials 227
Some of the standard ASTM test methods [18] related to corrosion of ceramic are 
listed in Table 9.1.
9.4 Categorization of corroded glasses based on their 
composition profiles
Hench and Clark in 1978 [19] categorized the corroded glass surfaces into five groups 
based on their composition profiles:
Type I glasses: Vitreous silica exposed to neutral pH solutions, where an extremely thin 
hydrated surface layer (<50 Å) is formed with no significant change in surface composition 
of the pristine glass;
Type II glasses: Ca-rich silicate glass, labeled Type 1 for us, has a silica-rich protective film 
depleted in alkali cations;
Type III glasses: Aluminosilicate or calcium phosphate silicate glass has two corrosion 
layers, one silica-rich and another one composed of aluminum silicate or calcium phosphate;
Type IV glasses: Binary or ternary soda-silica or potassium-silicate glasses undergo the 
formation of a silica-rich film, but the silica concentration is not high enough to prevent the 
loss of alkali or the destruction of the silicate network. Typically, medieval stained glass 
windows, labeled Type 2 or 3 for us, belong to this group;
Type V glasses: Vitreous silica exposed to pH > 9–10 solutions is soluble and displays a 
marked ability to form corrosion pits (Fig. 9.2).
ASTM destination Title
C-151 Autoclave Expansion of Portland Cement
C-157 Length Change of Hardened Concrete (reapproved in 1999)
C-225 Resistance of Glass containers to Chemical attack (reapproved 
in 1999)
C-282 Acid resistance of Porcelain Enamels (reapproved in 1999)
C-283 Resistance of Porcelain Enameled Utensils to boiling acid 
(reapproved in 1997)
C-456 Hydration Resistance of Basic Bricks and Shapes (reapproved 
in 1998)
C-577 Permeability of Refractories (reapproved in 1999)
C-614 Alkali Resistance of Porcelain Enamels (reapproved in 1999)
C-622 Isothermal Corrosion Resistance of Refractories to Molten 
Glass using the Basin Furnace (withdrawn in 2000)
C-724 Acid Resistance of Ceramic Decorations on Architectural Type 
Glass (reapproved in 2000)
C-735 Acid Resistance of Ceramic Decorations on Returnable Beer 
and Beverage Glass Containers (reapproved in 2000)
Table 9.1 ASTM test methods related to corrosion of ceramic
228 Fundamental Biomaterials: Ceramics
9.5 Effect of corrosion and erosion on the properties 
of ceramic materials
Ceramic materials are electrical insulators with a small number of free carriers and 
so the chemical attack on the surface of ceramic material is acid base-type reactions 
rather than electrochemical redox reaction.
9.5.1 Effect of acidic agents on surface roughness of ceramics
Ceramic materials were widely used in dentistry and are considered as chemically in-
ert restorative materials in both anterior and posterior applications, some ceramics are 
not chemically inert even in neutral aqueous environment and easily undergo severe 
degradation in acidic and basic media, which affects the flexural strength. Ceramic 
materials used in dentistry are composed of multiphased silicate glass-phase ceram-
ics, glass-ceramics, or monophased glasses with varying compositions [21]. However, 
when exposed to acidic agents or aqueous solutions, the dental ceramics were de-
graded. In recent studies, contact and noncontact methods were used for measuring 
surface roughness [22]. In noncontact method, a light beam or a laser beam was used 
to study surface profile but this method fails if the surface of the ceramic material is 
shiny, and sometimes it was very difficult to measure due to the scattering effect of the 
reflected light. This results in false values being documented. Hence, contact method 
with a profilometer was most popularly used to study the surface roughness [23].
The investigation of corrosion behavior of ceramic materials has been studied 
extensively by various researchers from very long back. One such study of Bennet 
[24] was discussed here. Bennet selected eight commercial ceramic materials (two 
red shale, two fire clay, a carbon, a silica, a fire-clay-bonded-silicon carbide, and a 
pH
Acid
Region of ion
exchange
Region of
greater
durability
Region of
matrix
dissolution
Neutral Basic
D
is
so
lu
ti
o
n
 (
m
g
/m
l)
Fig. 9.2 Effect of pH on glass dissolution [20].
Corrosion of ceramic materials 229
high-alumina brick) and noticed its action on contact with hydrochloric acid. The test 
samples were exposed to hydrochloric acid of 20 wt% at 50°C, 70°C, and 90°C, re-
spectively; similarly, another set of test samples were exposed to 30 wt% of hydro-
chloric acid at 70°C for 110 days. He concluded from his observation the ceramic 
materials undergo degradation in the acidic environment of hydrochloric acid. The 
increase in acid concentration increases the leaching rate of ion and the weight loss 
of the sample.
Kukiattrakoon et al. [25] evaluated the effect of acidic agent by testing it on 83 
ceramic disk specimen made from 4 types of ceramics (VMK 95, Vitadur Alpha, IPS 
Empress Esthetic, and IPS e.max Ceram). They conducted the experiment by immers-
ing the ceramic specimen in a set of acidic agents such as citrate buffer solution, 
pineapple juice, and the contact method was used to study the surface roughness be-
havior. They concluded from their study almost all the acidic agents show negative 
effects on the surface of ceramic materials; hence, it should be considered on restoring 
the eroded tooth with ceramic materials in patients possessing higher risk of erosion 
conditions.
Cotes et  al. [26] studied the flexural strength of feldspathic ceramic stored at 
different pH’s. Fifty bars of ceramic materials were taken and grouped into five 
categories based on pH and stored for 30 days (a) acidic, (b) basic, (c) neutral, 
(d) control, and (e) alternating between acidic/basic pH for 15 days each. The feld-
spathic ceramics stored in acidic pH undergoes severe deterioration, which results 
in numerous porosities and small cracks on its surface. They conclude from their 
work the patients ingesting acidic foods or has bulimia have faster corrosion in the 
ceramic restorative materials. They also concluded that the greater amount of corro-
sion was possible only in acidic medium compared to basic or neutral environmental 
conditions.
Sintered dental ceramics are mainly silicate-based ceramics, which generally un-
dergoes degradation in acidic environment. They are characterized by a continuous 
glass matrix composed of different volume fractions of crystals and particles are inter-
spersed [26a]. Based on sintering temperature, dental ceramic materials are tradition-
ally categorized into two types, namely, high- and low-fusing porcelains. In general, 
the high-fusing feldspar porcelains are regarded as being more corrosion resistant than 
ceramic materials with a lower sintering temperature [27].
Schacht et al. [28] compared the corrosion behavior of alumina ceramics in aque-
ous acidic solution (Hydrochloric acid, Sulfuric acid, Phosphoric acid) under hydro-
thermal conditions. The authors found that the corrosive effect of the acids on alumina 
ceramics decreases in the order H3PO4 > HCl > H2SO4. Mikeska et al. [29] investigated 
the corrosion resistance of ceramics in aqueous hydrofluoric acid. The authorsfound 
that corrosion in the case of polycrystalline alumina ceramics with 99.9% Al2O3 oc-
curred primarily at the grain boundaries. Conversely, single-crystal sapphire (Al2O3) 
did not corrode and showed good resistance to the hydrofluoric acid. The action of 
acetic acid solution on porous alumina ceramic was carried out by Tuurna et al. [30] 
and concluded from their work the major reason for corrosion in alumina ceramics 
was due to the presence of additives or impurities such as MgO, CaO, SiO2, and Na2O, 
which exist at the grain boundaries.
230 Fundamental Biomaterials: Ceramics
Another ceramic material, which was extensively reported by researchers, was 
 silicon-nitride and it is composed of multiphase system in which each phase under-
goes individual corrosion characteristic and possible reactions at the grain boundaries. 
The silicon-nitride-based ceramics shows dissimilar corrosion behavior depends on 
the method adopted for the manufacturing procedures such as powder processing, cold 
and hot consolidation technique, structure composition, degree of crystallinity of the 
grain boundary phase [31], which reciprocate on the different effects on its structural 
and functional properties [32].
Monnterverde et  al. [33] studied the degradation of hot-pressed silicon nitride 
in aqueous solution of sulfuric acid. The erosion process follows a progressive dis-
solution of the amorphous grain boundary phases. Seipel and Nickel [34] analyzed 
the corrosion behavior of silicon-nitride ceramic in aqueous acidic solution of sul-
furic acid. They reported the sintered silicon nitride ceramics undergoes corrosion 
due to presence of additives such as Y2O3 and Al2O3, which undergoes combined 
hydration-leaching- dissolution process, resulting in critical corrosion and the break-
ing of the ceramic material.
Young and Duh [35] studied the corrosion of aluminum nitride substrates in acidic, 
basic solution, and water. On comparing the corrosion rate in the entire three media, 
the aluminum nitride undergoes faster and rapid corrosion in the basic medium (so-
dium hydroxide and potassium hydroxide) than those in acidic solutions (Acetic acid, 
formic acid, hydrochloric acid, nitric acid, and sulfuric acid) and in deionized water. 
The surface morphology of the corroded aluminum nitride in alkaline solution is more 
due to its intensive chemical reaction forming a series of intermediates with more 
etched surface degradation.
The corrosion behavior of the ZrB2-SiC-Graphite (ZrB2-SiC-G) ceramic in strong 
alkali and strong acid solutions containing different aggressive anions such as chlo-
rides and sulfates after immersion for 1 h, 3 days, and 12 days was investigated by 
Wang et  al. [36,37]. The detailed investigation about the corrosion behavior of the 
ceramic is as follows:
(1) When immersed in corrosion solution, the ceramic undergoes an electrochemical corrosion 
attack on the ZrB2 phase and SiC phase, while graphite shows chemical inertness.
(2) When the ceramic was immersed in corrosion solution containing chloride, the insoluble 
ZrO2 is formed on the surface of ZrB2, which can prevent ZrB2 from corrosion. While for 
immersion in corrosion solution containing sulfates, the ZrO2 film will further react with 
sulfates to produce soluble ZrO SO4 2
2( ) - , which accelerate the corrosion of ZrB2-SiC-G 
ceramic.
(3) On comparing the corrosion behavior of the ZrB2-SiC-G ceramic immersed in strong alka-
line solution containing sulfates and chlorides, strong acid solution containing sulfates, the 
ZrB2-SiC-G ceramic undergoes faster corrosion in alkaline medium.
9.5.2 Performance of ceramic in severe environments
Environmental degradation limits the utility of ceramic materials in industries and 
almost all materials can be attacked by some environment. Ceramic materials can be 
easily accelerated by altering the environment in which it was subjected. The most 
Corrosion of ceramic materials 231
common effects of environment corrosion of ceramic were its dissolution property. 
The presence of humid air and water can act as hostile environment by adsorbing on 
the surface of ceramic, which acts as a solvent oxide ceramics and as an oxidant for 
nonoxide ceramics. Hence, it is necessary to study the corrosion and reliability per-
formance of ceramics under extreme environmental conditions such as temperatures, 
pressures, and aggressive chemical attack [29].
Even though ceramic materials are considered to be more stable in corrosive envi-
ronments than common metallic materials, it is important to investigate the chemical 
resistivity under severe environments. The dream of ceramic heat engines still faces 
many challenges; here the ceramic was not only exposed to high temperature but also 
to the aggressive gases and deposits. When the ceramics like silicon carbide and sili-
con nitride were exposed to severe oxidizing medium a thin layer of silica (SiO2) was 
formed on their surface and for silicon nitride an additional layer of silicon oxynitride 
(Si2N2O) was formed below the silica layer [38].
Du et al. [39] fabricated a special type of textured ceramics using transition met-
als by hot-pressing method. They investigated the corrosion behavior of Ti3AlC2 and 
Ti2AlC ceramics in the hot environment of supercritical water at 500°C and concluded 
from their observation that the corrosion in this textured ceramic was due to the forma-
tion of oxidation product, i.e., TiO2, which is responsible for the formation of cracks 
owing to large volume changes during the transition. This study was carried out to 
tailor the microstructure improvement to enhance the corrosion resistance property of 
textured ceramics.
Hou et al. [40] have chosen the silicon nitride (Si3N4) ceramics with a porosity of 
46% and studied its corrosion behavior under different conditions including dry oxy-
gen, Oxygen containing 20 vol% of water (H2O), and argon (Ar) containing 20 vol% 
of water (H2O) at a temperature of 1200–1500°C. The corrosion behavior was com-
pared in the different conditions and it will vary with respect to the temperature and 
atmosphere. Water vapor can aggravate the reaction by changing the SiO2 network and 
its devitrified effect thereby causing cracks with the disappearance of prismatic mor-
phology under water containing condition. This was due to the simultaneous oxidation 
and volatilization reactions and the ceramic undergoes higher rate of corrosion at the 
environment of water vapor (20 vol% of water).
(a) Corrosion behavior in hydrothermal environment
The corrosion behavior of silicon nitride at high temperatures such as in molten 
salts or gas environments has been extensively studied by various researchers and 
some of them are listed below:
Yoshimura et al. [41] reported that silicon nitride ceramics undergoes corrosion in 
hydrothermal conditions due to the increased solubility of SiO2 during hydrothermal 
process. The corrosion reaction is suspected to proceed as follows:
(9.1)
The weight loss and the degree of dissolution of silicon nitride in hydrothermal 
condition depend on the nature of additive used and the morphology of the Si3N4 grain.
Si N 6H O 3SiO 4NH3 4 2 2 3+ ® +
232 Fundamental Biomaterials: Ceramics
Another similar study under hydrothermal condition was carried out by Galuskova 
et al. [42] and they studied the corrosion behavior of silicon-nitride-based ceramics 
in deionized water and in the 0.5-M sodium chloride aqueous solution. The results 
showed that the SiN bonds in Si3N4 and both the SiN and AlN bonds in SiAlON 
are attacked preferentially under the conditions of the corrosion test and irrespective 
of the corrosion solution used, resulting in severe pitting corrosion. Both the ceramics 
show severe corrosion in the aqueous sodium chloride solution with the destruction 
of surface layer of corrosion products in comparison to corrosion in deionized water.
Sato et al. [43] investigated the degradation of silicon nitride ceramics in thepres-
ence of sintering aids such as yttrium (III) oxide (Y2O3), Aluminum oxide (Al2O3), 
and Aluminum nitride (AlN) under hydrothermal condition of 200–300°C and sat-
urated vapor pressure of water for 1–10 days. The hydrothermal corrosion proceeds 
with the dissolution of the Si3N4 matrix and the formation of a product in which the 
layer consists of original grain-boundary phase and hydrated silica. They infer from 
their work that the corrosion rate of ceramic decreases with the decrease in the crys-
tallinity of the grain-boundary phase.
(b) Corrosion behavior in turbine environment
Klemm [44] investigated the corrosion behavior of silicon nitride ceramic material in 
hot gas turbine environment (i.e., by providing high temperature, high pressure, and the 
water vapor pressure as the corrosive component). In such oxidizing medium, the surface 
of the silicon nitride ceramic is covered by the oxidized product of SiO2 and it has the 
lowest permeability to oxygen, which acts as a protective layer inducing passivity. The 
silicon nitride ceramic follows diffusion-controlled oxidation mechanism results in sur-
face degradation due to the formation and evaporation of silicon hydroxides Si (OH)4 and 
subsequent spalling off the disilicates of the sintering additive formed during oxidation. 
Thus, the author concluded that the ceramic silicon nitride undergoes corrosion in the se-
vere hot environment and it can be minimized by applying environmental barrier coating.
Fox and Smialek [45] exposed commercially available silicon nitride and silicon 
carbide to 1000°C in a high-velocity, pressurized burner rig as a simulation of aircraft 
turbine environment. A small amount of sodium impurities was added to the burner 
flame results in the formation of sodium sulfate deposition, which attacks the ceramic 
surface and forms substantial corrosion product of Na2O⋅x(SiO2). This was due to the 
pitting corrosion in both silicon-based ceramic materials. Here the degradation of the 
ceramic surface was due to the grain boundary dissolution and a long-term exposure of 
turbine environment will affect the corrosion at a faster rate than expected.
(c) Corrosion behavior in combustion environment
When the silicon-based ceramics such as silicon nitride or silicon carbide were 
exposed to severe combustion environment, as it contains substantial amount of water 
vapor as the product of combustion of hydrocarbon fuels, it generally causes five main 
types of corrosive degradation: passive oxidation, deposit-induced corrosion, active 
oxidation, scale/substrate interactions, and scale volatility [46].
There are various studies reporting the effect of rate of oxidation causing corrosion 
in combustion environment [47,48]. In such cases, there is a rapid increase in the rate 
Corrosion of ceramic materials 233
of intrinsic oxidation, which will cause higher solubility of water in the silica scale 
relative to oxygen. Here the increase in the rate of oxidation was reported as a function 
of water vapor partial pressure. The other main effect of corrosion in combustion en-
vironment is that water vapor causes the volatility of silica on material recession rates. 
The equation for the silica volatilizes is as follows:
(9.2)
Himpel et al. [49] conducted the experiment to study the corrosion behavior of alu-
minum nitride ceramics at a higher temperature range of 900–1300°C by coal ashes. 
The researchers explained in their work that the corrosion of ceramic by coal ash 
follows the three main mechanisms:
(1) High-temperature corrosion of AlN in primarily siliceous ash at 1300°C: Here the corrosive 
attack takes place at the interface between the material and the slag, which results in the 
dissolution of AlN and the formation of aluminosilicate. When this dissolution limit was 
exceeded, it will start to precipitate as slag.
(2) High-temperature corrosion of AlN by sodium and potassium oxide between 900°C and 
1000°C: Here the corrosion proceeds on the grain boundaries of the ceramic with the for-
mation of sodium potassium aluminates, followed by nitrogen release in the pores of the 
grain boundary phase. Due to the volatility of the alkaline oxides at 1000°C, this process 
came to a halt over time periods of up to 50 h and was no longer detectable at 1100°C.
(3) High-temperature corrosion of AlN by calcium oxide from 1100°C to 1300°C: Calcium 
diffused into the grain boundaries of ceramic and the formed calcium aluminate released 
nitrogen in the process. This nitrogen moved into the pores of the material. If there are no 
pores in the ceramic, due to this corrosion process new pores were formed and they later 
combined to form crack structures until individual AlN crystallites or entire grain matrices 
became components of the coal ash. Thus, the corrosion of aluminum nitride was well doc-
umented by their work.
9.5.3 Effect of stress corrosion cracking on mechanical strength 
of ceramics
One of the major reasons for the degradation of ceramic materials was stress corro-
sion cracking. Stress corrosion cracking in glasses and ceramic materials was more 
common and the main stress corrosion agent was considered as water present in the 
environment, which causes subcritical crack growth and leads to delayed failure of 
materials. If the stress intensity factor was lower than the critical stress intensity, the 
propagation of crack occurs, which was generally termed as “Subcritical crack growth” 
(SCG) [50,51]. The strength of dental ceramic was directly influenced by the factor 
subcritical crack growth and can be measured by using direct and indirect methods.
In direct method the crack growth velocity was measured as a function of stress in-
tensity, and in indirect methods the crack growth was measured using strength values 
from specimens undergoing varying amounts of SCG prior to unstable crack growth 
[52] including “static fatigue” and “dynamic fatigue” [53].
SiO 2H O Si OHs g g( ) ( ) ( )+ ® ( )2 4
234 Fundamental Biomaterials: Ceramics
Most of the studies based on stress corrosion in dental ceramics concentrate on the 
investigation of subcritical crack growth under cyclic loading in water; hence, Joshi 
et al. [54] are interested in studying the individual contributions of stress corrosion and 
the cyclic fatigue as well as the interaction between the two using pressable fluorapatite 
glass-ceramics. Joshi et al. [54] postulated two hypotheses to conduct this experiment 
(1) both cyclic degradation and stress-corrosion mechanisms result in subcritical crack 
growth (SCG) in a fluorapatite glass-ceramic (IPS e.max ZirPress, Ivoclar-Vivadent) 
and (2) there is an interactive effect of stress corrosion and cyclic fatigue to accel-
erate subcritical crack growth. Joshi and his coworkers concluded from their results 
there was no significant effect of stress corrosion and cyclic fatigue on subcritical crack 
growth on fluorapatite and also no significant interactive effect on dental ceramics.
The stress corrosion behavior of vitreous silica exposed continuously in water and 
nonaqueous environments was studied and reported very long back by Michalske and 
Freiman [55]. The stress corrosion cracking in oxide ceramics occurs in moist envi-
ronment or water at room temperature [56]. Wang et al. [57] investigated the stress 
corrosion cracking BaTiO3 ferroelectric ceramics in different environments of moist 
atmosphere, water, silicon oil, and formamide. They conducted the constant load test to 
examine the static fatigue fracture of the BaTiO3 ferroelectric ceramic and concluded 
that the cracking occurs in all the four environments with the normalized threshold 
stress intensity factor of stress corrosion being 0.78 (for moist atmosphere), 0.63 (for 
water), 0.66 (for silicon oil), and 0.82 (for formamide), respectively, and leading to the 
fracture of the material.
In another similar study, Wang et al. [58] investigated the anisotropy of stress cor-
rosion cracking of zirconate titanate piezoelectricceramics in water and formamide 
by adopting constant load test using a single-edge notched tensile specimen. PZT-5 
piezoelectric ceramics underwent Stress corrosion cracking under constant load in 
water and formamide. During stress corrosion, the stress-induced 90 degrees domain 
switching process exists and this may cause anisotropy of threshold stress intensity 
factor of SCC for poled ferroelectric or piezoelectric ceramics.
Stress corrosion in glasses was first examined by Grenet [59] who noted the 
time delayed failure and loading rate dependence of strength. Even though he fails 
to explain the reason behind the behavior of stress corrosion, the subsequent studies 
demonstrated explain that the fatigue failure on glass surface was due to the combined 
effect of water vapor and applied load.
Wiederhorn and Bolz [60] have studied the stress corrosion and static fatigue 
behavior of six types of glasses, namely, silica, Aluminosilicate I, Aluminosilicate 
II, Borosilicate, Lead-alkali, and Soda-lime silicate. In their study, the fracture me-
chanics technique was adapted to study the stress corrosion. They concluded that the 
crack velocity of all the glasses was strong depending on the composition of glasses. 
Compared to all the glasses studied, silica glass has the greatest stress corrosion resis-
tance followed by low-alkali aluminosilicates and borosilicate glasses and the reason 
for stress corrosion cracking was due to the chemical reaction between water in the 
environment and the glass.
One of the most important properties that were affected in ceramic due to degra-
dation is its mechanical strength. Even though the other properties of ceramics were 
Corrosion of ceramic materials 235
also affected by corrosion, it does not lead to failure and it causes only changes in its 
strength. In some cases, the effect of corrosion led to increased strength, which results 
in healing of cracks and flaws in the surface layer of ceramic and paves the way for the 
impurities to enter the into the bulk surface.
The mechanical properties of many glasses and ceramic material were seriously 
affected with time under static loading and ambient environments. Gogosti and 
Yoshimura [61] analyzed the stress corrosion effect of certain zirconia ceramics and 
reported that water has the ability to deteriorate the ceramics oxides and glasses even 
at room temperature, which was so called as Stress Corrosion.
The extent of corrosion in ceramic material can be more appropriately elucidated 
by measuring its mechanical properties, which will inevitably cause severe degrada-
tion effects such as strength creep or fatigue [62]. Measuring the weight change or 
its sensitivity to the mode of attack will provide only less information regarding the 
extent of corrosion (Fig. 9.3).
9.5.4 Corrosion in glassy materials
Compared to most of the materials used in our day-to-day life glass is considered to 
be much more resistant, so it was easy to think it of as corrosion-proof but actually 
speaking glass is destructible under certain conditions and it will easily corrode and 
even dissolve. On considering the chemical attack of glass, only few chemicals show 
aggressive effect on them. Some of them are listed here: hydrofluoric acid [63,64], 
concentrated phosphoric acid [65] (when hot, or when it contains fluorides), hot con-
centrated alkali solutions [66,67] and superheated water [68]. Hydrofluoric acid se-
cured first position to show a very high corrosion effect on glass and it can easily 
attack any type of silicate glasses. Other acids show a very slight effect on glasses and 
the degree of attack can be measured in laboratory tests, but such corrosion is rarely 
significant in service for acids other than hydrofluoric and phosphoric acid.
On studying the behavior of acid and alkali corrosion on glasses, the corrosion 
process may proceed through different pathways. Alkalis attack the silica directly 
Temperature
Corrosion
dissolution
Stress
corrosion
hydrothermal
corrosion
Water Stress
corrosion of
glass
Mechanical
stress
Creep
SCG
Fig. 9.3 Factors determining the corrosion of ceramics. SCG = subcritical crack growth [61].
236 Fundamental Biomaterials: Ceramics
whereas acids attack the alkali in the glass. When a glass surface was exposed to alkali 
solution, the surface undergoes simple dissolution. This dissolution process continues 
to the fresh surface and shows a uniform rate of corrosion prolonged as long as the 
supply of alkali was ample.
The action of acid attack on glass was quite divergent. The alkali-exposed portion 
of glass shows a porous surface that consists of silica network with holes, and when 
acid was exposed to that portion it removes the alkali. To this porous surface, the acid 
will penetrate to find the alkali to dissolve deeper inside and causes corrosion.
The deterioration of glass by chemicals can be ascribed by the combination of 
three simultaneous partial primary processes (a) ion exchange, (b) hydration, and 
(c) hydrolysis [69–71], and sometimes the microorganism can also deteriorate the 
glass surface (d) Corrosion by microbes. It was generally termed as “Microbially 
Influenced Corrosion (MIC)” and it was often linked to the growth of fungi [72].
(a) Corrosion of glass by ion exchange process
When the glass was exposed to severe acidic environment, the concentration of H+ 
ions is more compared to OH−. Hence the attack of H+ ions on the surface of glass 
was predominant and leads to leaching [73]. The diffusion-directed ion exchange took 
place between the protons of the acidic aqueous environment and the mobile network 
modifiers (Na+, K+, Ca2+ i.e., M+) in the channels that are in contact with the surface 
of glass. The corroded glass contains higher number of H+ channels than the M+ chan-
nels causing the formation of leached layer [74]. The interface between the leached 
layer and the bulk glass is sharp and clearly distinguishable (Fig. 9.4).
(b) Corrosion of glass by Hydration
Hydration describes the diffusion of water molecules into the voids present in the 
glass network. If the size of void is much larger compared to the size of water molecule 
Hydration
Hydrolysis
OH−
H
+
H 2
OK
+ , 
N
a
+ , 
C
a
2+
lon
exchange
Glass
Fig. 9.4 Schematic representation of corrosion of glasses [75].
Corrosion of ceramic materials 237
it results in rapid diffusion and if the void size is minimum or smaller the diffusion takes 
place slowly. When the size of the void is smaller and penetration is not possible, then 
the water molecule reacts with the glass network by breaking the bonds of Si-O-Si pres-
ent in the glass and thereby opening the structure [69]. Continuous exposure of glass 
to water causes the dissolution of the glass matrix. The overall reaction in hydration 
follows two subsequent steps: leaching of mobile ions and uniform dissolution of the 
matrix [76]. Dissolution causes the breaking up of chemical bonds and separates chem-
ical species from the remaining materials. The dissolution process may be uniform or 
in some cases it may be nonuniform due to the attack of preferential dissolution [77].
(c) Corrosion of glass by Hydrolysis
Glass undergoes hydrolysis process in alkaline environment, i.e., OH− rich environ-
ment. The OH− anion together with the water molecules attacks the SiO2-rich islands 
of the glass network motivating the depolymerization process at the glass structure. 
This continuous deterioration can result in dissolving the silicate network, thereby the 
original glass surface will disappear.
(d) Corrosion of glass by microbes
The microbial degradation of historical glass was first reported by Mellor in 1924 
[78], which was due to the lichenous growth on the medieval window panes. This 
work was further surveyed and reported by Newton and Davison [79] and Krumbein 
et al. [80]. The Microbial-influenced corrosion follows the mechanism of either bio-
physical (lichens, fungi) or biochemical (fungi, bacteria).9.5.5 Corrosion of specific glassy materials
From early 1950–1960s the corrosion behavior of glasses was pointed out but these 
first studies were ignored by scientists working in other fields, and similar results were 
obtained again in 1980s. Each corrosion research was actually carried out separately, 
without taking into account the previous studies and only in the 1990s the link be-
tween the different approaches was made [81–83].
The performance of glasses such as silica, alkali boro-, and aluminosilicate 
glasses was easily degraded when exposed to aqueous environment and easily un-
dergoes stress corrosion cracking, selective leaching, and dissolution. For all type of 
glasses, the corrosion takes by means of common reactions as mentioned earlier, i.e., 
Hydration, Hydrolysis, and Ion-exchange reactions. However, the rate of corrosion 
depends on the structural differences between the glasses in which it was composed 
of. In case of simple alkali silicates, the nonbridging oxygens compensate the modi-
fier cations and thus lower the effective crosslinking density of glass. The glass was 
more prone to network hydrolysis, which promotes the structural alterations within 
the leached layer. But in case of aluminosilicate glasses along with nonbridging ox-
ygen, the modifier cations were compensated by BO4− and AIO4− sites [84]. Such 
sites modify both the inherent reactivity and extended structure of the glass. The 
relative rates of observed dissolution mode (selective leaching versus uniform disso-
lution) are critically dependent on the distribution and reactivity of specific sites and 
238 Fundamental Biomaterials: Ceramics
 functional groups within the glass structure. Therefore, to predict the dissolution be-
havior in glasses it is essential in concerning the structure of glasses, its composition, 
and preparation conditions.
In another study, the corrosion behavior of alkali silicates in presence of water was 
explained by Charles and Hillig [85]. The corrosion in silicate glasses takes place by 
these three steps:
(a) H+ from the water penetrates into the glass structure and replaces alkali ion, 
which goes into solution, a nonbridging oxygen is attached to the H+ ion (b) the OH− 
produced in the water destroys the SiOSi bonds, forming nonbridging oxygens, and 
(c) the nonbridging oxygens react with water molecule, forming another nonbridging 
oxygen and the step (b) was repeated. The silicic acid thus formed is soluble in water 
under the correct conditions of pH, temperature, ion concentration, and time.
The corrosion on the surface of the glass materials can be visualized easily by the 
appearance of faint haziness on its surface when viewed in transmitted light. This haze 
or cloud formation is called Weathering. Weathering was due to the result of attack of 
water vapor on the ceramic surface and it has direct influence in creating the tensile 
stresses set up by adapting ion exchange phenomenon of the alkali by hydrogen ions. 
Weathering in soda lime glasses results in the loss of its strength. In soda lime glasses, 
the H+ ions from the water replace the alkali ion and the OH− ions in the solution de-
stroy the Si-O-Si bonds forming nonbridging oxygens [86].
Here we discuss some of the important glasses and their corrosive behavior in con-
tact with the environment.
(a) Borosilicate glasses
One of the most common glassware used in scientific ware and industrial piping was 
borosilicate. The corrosion in borosilicate glasses was based on diffusion-controlled 
hydrolysis, hydration, ion exchange reactions, and subsequent recondensation of the 
hydrolyzed glass network, leaving behind a residual hydrated glass or gel layer [87].
Borosilicate glass was considered as an internationally preferred potential candi-
date for the immobilization of high-level nuclear waste includes excess plutonium 
from dismantled nuclear weapons and highly radioactive liquid/solid waste resulting 
from the reprocessing of spent fuel in short-term laboratory experiments [88,89] a 
parallel study on the interaction of borosilicate nuclear waste glass was also taken into 
account and studied by researchers [90,91].
Sales et al. [92] investigated the corrosion behavior of synthetic monazite and borosil-
icate glass containing nuclear defense waste in distilled water by measuring their leach-
ate conductivity measurements, ion-implanted marker techniques, solution analyses, and 
Rutherford backscattering depth profile analyses. They concluded that the monazite was 
superior as corrosion resistance than the borosilicate glass because there is a rapid increase 
in the dissolution rate of glass network in the higher temperature range of 70°C–125°C.
The chemical durability of the borosilicate glasses decreases as the content of 
(Na/B)/Si in the glass increases [93]. The relationship between the structure and the 
dissolution rate for sodium borosilicate glasses was studied by Bunker et al. [94] by 
systematically varying the soda and borate contents. For the glasses with higher con-
tent of B2O3, i.e., (B:Na > 2), the glasses will separate into two phases: silica-rich 
Corrosion of ceramic materials 239
phase and sodium borate phase. The sodium borate phase will readily dissolve in water 
and leads to faster rate of glass dissolution. On the other hand, the rate of dissolution 
in water is lower for the glasses with greater number of 4-coordinated boron incorpo-
rated into the silicate structure.
Shobha et al. [95] studied the degradation behavior of borosilicate glass by immers-
ing the glass samples in acidic and alkaline media as a function of temperature and 
concentration for a long period of 160 h. They concluded from their investigation that 
the degradation in acid medium is less than the alkaline media and the chemical attack 
in the polished surface was initiated from the edges of the sample. At higher tem-
peratures, the surface degradation was nonlinear in acidic medium and the shapes of 
degradation were granular type in acidic media and the blister type in alkaline media.
When the borosilicate glasses were dissolved in acidic solutions they will release 
the Na and B to solution at a faster rate than Si, whereas in case of alkaline medium 
the borosilicate glass performs more uniform release of ions; hence, the borate glass 
undergoes corrosion at a faster rate at higher pH by undergoing congruent dissolution 
but in case of low pH it was selectively leaching the Na and B ions [93].
To understand the reaction between the borate units in borosilicate glasses and wa-
ter, the density functional theory and molecular dynamic approaches were generally 
studied [96,97]. When a proton replaces a Na+ ion on a BO4
− site, the 4-coordinated 
borate unit becomes unstable and bridging oxygen (O) is broken to form a trigonal 
borate unit, as shown in the equation below.
(9.3)
Both the tetrahedral and trigonal borate sites in borosilicate networks are more 
susceptible to attack in acidic (protonated) environments than in neutral or basic en-
vironments [97].
In another study, Antropova et al. [98] demonstrated the comparative study on the 
leaching behavior of two-phase borosilicate glasses in the presence and absence of 
additive lead oxide in 3 M hydrochloric acid solution at 100°C. In the glass containing 
additive PbO, leaching process will lead to the formation of white dendrite-like precip-
itates within the porous layer and it was composed of amorphous hydroxo compounds 
of lead, whereas in the borosilicate without additives it involves boron-containing and 
silicon-containing crystalline phases.
Nath et al. [99] conducted the test to investigate the hot corrosion behavior of re-
fractory by molten glass made of borosilicate at 1200°C under static condition. They 
concluded from their study that the corrosion in the Al2O3-Cr2O3 refractory blocks 
occurs via dissolution of Al2O3 fractions from the Al2O3-Cr2O3 solid solution by 
the molten glass followed by mass exchange.In the Al2O3-Cr2O3 solid solution, the 
Al2O3 fraction was replaced by Fe2O3 thereby forming of Fe2O3-Cr2O3 solid solution 
and plausibly it will acts a barrier to molten glass, which ceases the corrosion rate. 
However, Cr2O3 fraction remained unaffected by the molten glass.
(b) Silicate glasses
The corrosion behavior in silicate glasses was first reported by Wang and 
Tootley in 1958 [100] in which the degradation of silicate glasses was typified by 
Na BO H O H BO NaOH BO OH Na OH+
- + - + -[ ] + ® [ ] + ® + +4 2 4 2
240 Fundamental Biomaterials: Ceramics
 diffusion-controlled alkali ion exchange for H+ or H3O
+, followed by matrix dissolu-
tion as the pH of the solution drifts toward higher values.
(9.4)
(9.5)
The dissolution of silicate glasses is dependent upon the following test conditions 
including time, temperature, pH, and the sample composition. Composition is a basic key 
factor that determines the structure of glasses. Brady and House [101] observed in their 
study that the glasses with rich silica content and highly polymerized dissolved more 
slowly than those containing larger amounts of other cations. Here the highly polymer-
ized nature determines the structure of the glass and it was found to dissolve more slowly.
The dissolution process in silicate glasses can be explained in detail below:
In silicate glasses the modifiers such as Na2O are incorporated into the glass net-
work which results in hydration, or leaching of modifying ions out of the glass.
(9.6)
The dissolution in silicate glass was accompanied by diffusion of water into the 
glass, hydration of metal-ion bonds, diffusion of metal-ions out of the glass, and hy-
drolysis of network bonds. For silicate glasses, ion exchange, or hydration, occurs 
faster than network hydrolysis, which leads to selective leaching of the modifier ions 
out of the glass and hydrogen ions into the glass. The selective leaching can lead to a 
concentration gradient of modifier cations at the glass surface [102]. The leaching rate 
depends on the type of modifier.
In alkali silicate glasses, chemical durability increases in the order of K+ < Na+ < Li+, 
suggesting that field strength and free energy of hydration affect glass dissolution rates 
[103]. Alkaline earth cations increase the durability due to their high field strength and 
lower mobility than alkali ions [104]. The addition of Al2O3 reduces the number of 
nonbridging oxygens, increasing the network connectivity and increasing durability 
due to a decrease in the hydrolysis rate [69].
Dohmen et al. [105] conducted the static glass corrosion experiments with two dif-
ferent silicate glasses, namely, (Glass 1) the ternary borosilicate glass and (Glass 2) the 
U-bearing silicate glass. Based on the observation, they concluded that the corrosion in 
silicate glasses takes place by an interface-coupled glass dissolution/silica deposition 
process. During this process, the rate of silica deposition is coupled to the pH and salin-
ity of the interfacial solution, which in turn are controlled by the dissolution rate of the 
glass and the transport of solute species through the silica reaction layers.
(c) Phosphorus-containing glasses
Biodegradable phosphate glasses can be fabricated as scaffolds for bone regener-
ation, muscle regeneration, hard and soft tissue repairment. Iron phosphate glasses 
are applied as potential hosts for nuclear wastes disposal. The corrosion behavior of 
phosphate glasses was explained by Bunker et al. [106] using Na2O-CaO-P2O5 meta-
phosphate glasses in which the first stage of corrosion was observed as a square root 
Si O Na H O Si OH Na H O- - + ® - + ++ + +3 2
Si O Na H O Si OH Na OH- - + ® - + ++ + -2
º ºSi O Na H O Si OH Na OH- - + ® - + ++ + -2
Corrosion of ceramic materials 241
of time dependence (t1/2) for weight loss and this was controlled by surface hydration. 
In the second stage of corrosion, the weight loss follows a linear time dependence 
controlled by the hydration of intact polyphosphate chains from glass surface. In both 
the stages, the rate of dissolutions strongly depends on the pH of the solution and the 
concentration of other ions present in the solution. The phosphate glass corrosion fol-
lows congruent corrosion, i.e., the thickness of the hydrated layer should be constant 
with time and controlled by the average chain length of the phosphate anions.
Poluektov et al. [107] proposed the model to explain in detail the glass dissolution, 
formation of corrosion layer, species diffusion, and chemical reactions. The sodium 
alumina phosphate glass was used for accounting the corrosion behavior in a closed 
aqueous system similar to typical geological disposal system. Depending on the glass 
corrosion, three distinct phases of corrosion were explained below with schematic 
representation and it was common for all phosphate types of glasses (Fig. 9.5).
Stage I:
In stage I the dissolution of glass encompasses zones, which operate through mul-
tiple mechanisms comprising the regimes that are ion exchange interdiffusion con-
trolled, hydrolysis controlled, and a rate drop that is diffusion or affinity controlled.
Corrosion was rapid in stage I due to faster exchange of ions between solution 
(H2O, O, H3O) and glass (Alkali, phosphorus, alkaline earths, etc.) and the hydrolyzed 
part of bounded phosphorus transforms to phosphates.
Stage II:
In stage II, pseudoequilibrium was formed between the alteration and recondensa-
tion reactions. The rate of corrosion decreases due to increased concentration of glass 
components in the water. Diffusion-controlled dissolution of radionuclides during 
Initial rate r0 Decreasing rater(t) Residual rate r(t) Alteration
renewal
Hydrolysis
A
lt
er
at
io
n
End of alteration and/or
secondary precipitation
Diffusion/
Affinity
In
te
r 
di
ffu
si
on
Time
Secondary
precipitation
Stage I Stage II Stage III
Fig. 9.5 Schematic representation of distinct phases in glass corrosion [107].
242 Fundamental Biomaterials: Ceramics
Stage I and Stage II normally follows mathematically a square root of the test duration, 
while other radionuclides are solubility limited, entrapped in the gel layer, or com-
plexed in secondary alteration phases that form on the glass from the leachate solution.
Stage III:
Stage III was characterized by resumption of alteration with a return to a forward 
rate. This stage was not applicable to all types of glasses. It was a poorly understood 
process, which is associated with formation of specific phases on the glass surface 
[108,109]. Stage III was never studied in detail for sodium alumina phosphate glasses.
Ma et al. [110] studied the dissolution behavior of five series of sodium iron phos-
phate glasses, with different O/P and Fe/P ratios, and systematically investigated static 
and semidynamic dissolution tests in water. They concluded from their observations 
the dissolution follows two kinetic stages and the first stage follows 3D diffusion model 
(DM) while the second stage follows a linear contracting volume model (CVM). The 
transition between these two stages strongly depends on the composition of phosphate 
in the glass. Three types of dissolution behavior were followed by sodium iron phos-
phate glasses, type I involves the selective leaching of ions, type II involves congruent 
dissolution in both the stages while the type III involves congruent dissolution during 
the first stage and then selective leaching in the second stage. As the corrosion process 
involves different types of dissolution processes, it will produce different surface mor-
phologies and compositions in the corroded area.
Simon [111] explained the corrosion behavior of alkali calcium phosphate bio-
glasses in aqueous media. The pure phosphate glasses consist only of quasitetrahedral 
PO4 units. If a modifier like alkali and alkaline earth metals were added, the number 
of bridging oxygens in phosphate decreases with increase in its negative charge. Due 
to thepresence of alkali ions in the phosphate network, it diminishes the resistance 
of glass thereby increasing the rate of corrosion [112]. The initial corrosion involves 
leaching process and follows ion exchange process. The other mechanism proposed 
for the dissolution of glass is based on diffusion of water into glass and thereby form-
ing chemisorptions at the nonbridging oxygen sites where alkali and alkaline earth 
species reside in the glass [113].
9.6 Minimization of corrosion
The control of chemical reactivity of ceramics with the environment is a great chal-
lenge for the ceramic industries. Ceramics and glass materials were widely used 
worldwide due to easy availability, cost effectiveness, and can be easily molded to 
desirable shapes. The glasses were used as primary packaging materials to preserve 
medicines and chemicals. However, fluctuations in humidity and pH over time can 
cause some glasses to corrode rapidly and reduce strength. As a result the application 
of glass in pharmaceutical, environmental, and optical industries will be threatened by 
its corrosion nature most particularly in hot and humid climates.
For the past few years there has been an extensive and deep research to find an 
effective coating for glasses and to protect it from damage. In order to minimize cor-
rosion there is a need of ideal coating material that should possess some of the basic 
Corrosion of ceramic materials 243
necessary characteristics including transparency, being thinner, and providing a good 
diffusion barrier to chemical attack. Researchers at the Center for Multidimensional 
Carbon Materials (CMCM), within the Institute for Basic Science (IBS) have demon-
strated graphene coating protects glass from corrosion. Their research, published in 
ACS Nano, can contribute to solving problems related to glass corrosion in several 
industries [36,37] (Fig. 9.6).
IBS scientists adopted the technique previously invented by Prof. Rodney S. Ruoff 
and collaborators to grow grapheme on copper. This grapheme was coated as one- or 
two-atom-thick layers onto the surface of glasses on both the sides. They tested the 
effectiveness of grapheme coating by immersing the graphene-coated glass and the 
uncoated glass in water for 120 days and the surface morphology was studied. The un-
coated glass samples have increased surface roughness and reduced fracture strength, 
while the graphene-coated glass had essentially no changes in surface roughness and 
fracture strength. Thus they concluded from their work that Graphene was one of the 
effective anticorrosion coating agents [114].
The durability of glasses can be improved by incorporating nitrogen into the glass 
structure. The addition of nitrogen to the soda lime silica glasses improves the corro-
sion resistance by minimizing the leaching in water at 60°C over composition contain-
ing no nitrogen [115].
The corrosion rate of ceramic could be minimized by improving the bonding phases. 
Normally bonding phases possess lower melting point and lower corrosion resistance 
than the bulk phase. The corrosion in alumina was minimized by bonding them with 
mullite thereby forming a complete series of crystalline solutions with chromia, with 
Graphene
Water corrosion
GLASS
Fig. 9.6 Coating of glass surface with graphene [114].
244 Fundamental Biomaterials: Ceramics
the intermediate composition having melting point between the end members. Thus 
the bonding phase formed with the solution of chromia in alumina with higher melting 
point than the bulk alumina results in higher corrosion resistance.
The corrosion resistance of ceramic materials can be improvised by adding anti-
wetting additives [116]. The corrosion resistance of silicon carbide and silicon nitride 
can be improved by adding pore-filling materials such as nitrates or oxychlorides. 
The corrosion resistance can also be improved by changing the processing methods. 
In some cases, preoxidation forms a protective coating of oxide layer and thereby 
reduces the rate of corrosion [117].
9.7 Conclusion
Ceramics offers unique set of properties that seek the attention in modern technology 
as “Miracle materials.” Till middle of twentieth century, there was not much impor-
tance of the ceramic materials. A significant progress has been made in the current 
years for the better understanding of the materials, and these materials possess prop-
erties that are superior over the metal and possess some unique properties, which 
were generally lacked in case of metals. Study of Ceramic materials is one of the 
hottest topics and the most promising field in recent era and plays a significant role 
in the wide array of technologies. This chapter glances over the effect of corrosion 
on the ceramic materials and their relationship in the deterioration of properties of 
the ceramic. We also discussed the phenomenal changes that occurs in the ceramic 
due to corrosion. Many new trends and techniques were adopted by the researchers 
to minimize corrosion and to prolong the duration of ceramic materials in our day-
to-day life.
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