MME 467

Ceramics for Advanced Applications

Lecture 26
Time, Temperature and
Environmental Effects on
Ceramics 2
Ref: Richerson, Modern Ceramic Engineering, Ch17, Marcel Dekker,
1992
Topics to discuss....

1. Chemical effects on ceramics

2. Mechanical effects on ceramics
3. Thermal effects on ceramics
 Chemical Effects

 Resistance of a ceramic to chemical attack depends on:

1. strength of atomic bonding

 weakly ionic bonded ceramics have low resistance.

Examples: NaCl is soluble in water, CaCO3 dissolves in weak acids.

 strongly ionic and covalent ceramics are much more stable.

Examples: alumina and zircon (furnace, crucible and mould lining above 1200 C),
Si3N4 and Si2ON2 (used in contact with liquid metal and liquid ceramics).

2. kinetics of thermochemical equilibrium

between ceramics and surrounding atmosphere at exposed temperature.
 Ceramics are often selected instead of metals for their
superior chemical stability over a wide temperature range.
 alumina, porcelain, many other oxides, borides, nitrides, carbides
are resistant to acids and bases.

 used in many applications (liners, seals, laboratory wares, etc.)

where metals do not survives.

 Selection of ceramics for high-temperature corrosive

applications requires
 knowledge of chemical resistance, and

 other properties, such as thermal conductivity, thermal expansion

coefficient, strength, and creep resistance.
Gas - Solid Reactions
Oxidation
 Oxides and stoichiometric silicates are typically stable at high
temperatures in oxygen and mixed oxygen-nitrogen atmosphere.
 Most carbides, nitrides, and borides are not. At elevated temperatures,
oxygen interacts with any exposed surface of carbides and nitrides.

 For high oxygen partial pressures

(1 mm Hg and above), a protective
layer of SiO2 forms on SiC and Si3N4.
This is called passive oxidation .
 Formation of SiO2 is initially rapid, then
parabolic due to diffusion of oxygen
through silica layer.
 Oxidation rate increases as
temperature increases. Fig. 8.10.
 For low oxygen partial pressures (below 1 mm Hg), SiO gas forms due to insufficient oxygen
content. This is called active oxidation .

 Oxidation continues slowly and linearly until all the material is consumed!
Although not common, active oxidation condition can be dangerous. Usually occurs in
nonoxygen environments, such as in closed-cycle gas turbine or a nuclear reactor or in space
applications, where oxygen might be picked up as an impurity.

Depending on
1. ceramic materials,
2. temperature, and
3. initial surface conditions
oxidation can increase, decrease
or not affect the strength of
ceramic materials. Fig. 8.16.
Reduction and other reactions

 Such atmospheres include hydrogen, ammonia, carbon

monoxide, argon, nitrogen, and vacuum.

 Strong reducing atmosphere (H2, NH3)

can remove oxygen from oxides at high T:
(H2) + <SiO2> = (SiO) + (H2O)
Amount of silica loss by this method can be
substantial. Fig. 8.18.

 The degree of reduction depends on the

stability of oxides (following Ellingham
diagram).

 Another detrimental effect is the change

in oxidation state.
Example: Alumina containing Cr2O3 and SiO2.
 Presence of moisture results stress corrosion and hydrolysis,
with a cumulative reduction in strength
<Si3N4> + 6{H2O} = 3<SiO2> + 4(NH3)

 Some ceramics are hygroscopic and incomplete atomic bonds at

the surface attract water molecule to form weak van der Waal bond.
 Some salts actually absorb enough water to dissolve themselves, example NaCl.

 The vapour pressures of most ceramics at low temperatures are

negligible and become appreciable only at very high temperatures.

 Ceramics keeping at high enough temperatures in open containers

may vaporise spontaneously. Some ceramics dissociate rather
than evaporate. Dissociation of SiO2 or Si3N4 are common.

 Decomposition reactions of carbonates, hydroxides, nitrates etc.

during formation of oxide ceramics are also common.
 In such cases, a complete decomposition of these raw materials is mandatory before
densification of parts begins.
Liquid - Solid Reactions

 These reactions are generally referred to as corrosion,

resulting from direct contact of a reactive liquid.
 Can either be a simple dissolution reaction or be more complex.

 Kinetics of reaction is important. Reaction will proceed if

1. fresh reactants can get to the ceramic surface, and
2. reaction products get away from the surface to expose fresh surface

 If the products remain on the surface, they act as

boundary layer and limits further reaction. Diffusion
through the boundary layer controls the rate of corrosion.
 Example: formation of viscous silicate slag of ~1 cm thick on
refractory lining in glass melting furnaces protects and extends
significantly lining life.
Room temperature corrosion

 Ceramics shows a broad range of resistance to corrosion

at room temperature.
 
 Strongly bonded ceramics (alumina, silicon nitride etc.) are
virtually inert in most aqueous solutions, including strong acids
and bases.

 Weakly bonded ceramics (metal salts of nitrates, chlorides,

sulphates etc.) are soluble in weak acids, or even water.

 Silicate ceramics are also very stable in most liquids, except in

HF acids.
High temperature corrosion

 Occurs when oxide ceramics are in contact with liquid

metal or liquid ceramics (as in glass melting furnace).

 Corrosion rate increases

1. as temperature increases
2. for polycrystalline ceramics than single crystals (due to grain boundary effect)
3. if forced convection used

 Corrosion of oxide ceramics is more severe in metal

melting and refining furnaces than glass melting furnaces.
 The atmosphere is, for example in basic oxygen steelmaking (BOS) processes,
extremely severe involving HT (1600 – 1700 C), impact, abrasion, and thermal shock.
 Tar impregnated MgO refractory bricks (of 45 - 90 cm thick) corrode at a rate of
0.08 - 0.15 cm per cycle and have life usually less than 1000 cycles.
Condensed - phase corrosion

 Some constituents in a gas phase condensed on a surface to

produce a liquid phase.
 The volume of such phase is not sufficient to eat away large masses but can result
enhanced corrosion or surface degradation.
 Example: hot corrosion of metals in gas turbine engine. S from fuel combines with NaCl
from seaside air or road salt to form Na2SO4 that condensed onto the surface of Si3N4 or SiC
turbine engine, which is at a temperature of about 650 – 950 C. Severe corrosion results.

 Depending on the nature of condensed phase, a variety of

degradation mechanisms are possible:
1. change in chemistry of SiO2 layer, increasing oxygen diffusion rate
2. bubble formation, disrupting protective SiO2 layer, allowing increased oxygen access
3. decreased viscosity of protective surface layer, which is swept away by high-velocity gas flow
4. formation of molten liquid at the surface, which is soluble to the ceramics
5. localised reducing conditions, decreasing oxygen partial pressure at the surface to initiate
active oxidation
6. formation of new surface flaws, such as pits or degraded microstructure, which decrease
load-bearing capacity
Corrosion in coal combustion environment

 Fluid slag made of ash and other impurities (S, and oxides
of iron, calcium and sodium) of coal can corrode high-
temperature surfaces and stick to low-temperature
surfaces.

 The build-up of slag or ash is referred to as fouling. Thin

fouling layer protects the surface from corrosion and
erosion, and in some cases causes local temperature
reduction. All three of these factors can increase the life of
component.

 A thick fouling build-up, however, is a problem and can

cause airflow reduction through engine and decrease
efficiency.
Solid - Solid Reactions

 This is occurred by solid-state diffusion of

atoms.
 
 Usually extremely low at room temperature, but
can be substantial at high temperatures.
 
 When occurred, the followings happen:
1. localised change in composition and properties
2. bonding at interface
 Mechanically Induced Effects

 Mechanical effects can reduce the life of ceramic by

1. producing surface flaws that are larger than

those defects initially present in the material

2. removing materials from the surface (wear)

Surface Flaw Formation

 Mechanically induced surface flaws are small cracks

caused by localised stress concentration. They can
result from
1. machining
2. impact
3. point/line contact loading at an interface/attachment
4. loading (normal and tangential)
Machining

 Generally done using a diamond cutter/grinder.

 Being the hardest material, very high localised stress and temperature
are generated.
 Ceramic even deform plastically under the tool.
 Median, lateral, and radial cracks are generated due to localised
compressive and tensile stresses. Fig. 8.24.
Impact
 The sudden impact of localised stress to the surface results a
compressive stress directly beneath point of contact and tensile stress
surrounding the circular contact.
 A series of shallow concentric circular cracks around the point of impact
is generated. Fig. 8.26.

 Metals are relatively tolerant to

impact, traditional ceramics don’t.
 Toughened ceramics are some
resistant to impact but not as good
as metals.
 Impact and point loading are common sources of mechanically-
induced damage that reduce the life of ceramic part and are major
reasons why ceramics are not used for structural applications.
 Another source is sliding contact.

 Surface damage and strength reduction are major concerns in

the design and applications of ceramics.

 Ceramics are always susceptible to impact during manufacturing,

assembly, and handling and are exposed to sliding contact or biaxial
stress distribution.

 Common examples:
1. at or adjacent to point of attachment
2. surface irregularities at a shrink fit and the region at the margin of a shrink fit
3. surface being machined
4. contact surface bearing and race
5. contact region of a cutting tool
6. contact surface of heated parts that have different thermal expansion
7. contact surface of seals.
Removal of Surface Materials

 Also known as wear, this is the second major

category of mechanically induced effects.

 Adhesion and microfracture are two of many modes

of occurring wear in ceramics.
Adhesion
 Adhesive wear involved localised bonding of two surfaces,
followed by transfer of material from one surface to other by
pullout when two surface moves relative to each other.
 Surface atoms with unsatisfied bonds and higher energy easily bond with
surface atoms of other component when come in contact.
 
 Ceramics are much less susceptible to adhesive wear than
metals, especially at low temperature due to low mobility and
minimal tendency to bridge the interfaces.
 Diffusion and, hence adhesive wear, increases as temperature increases.
 Temperature increase can be resulted from frictional heating of sliding surfaces.

Microfracture
 Scratching, interference of asperities, impact and contact stress
resulted microfracture and subsequent material removal from
surface of ceramics.
 Wear is a major cause of equipment failure and down
time in military, in industry, and in commercial
products.

 Associated friction is a major consumer of energy.

 Ceramics have been targeted to reduce wear and

friction and avoiding chemical and galvanic attack due
to their
1. high hardness,
2. chemical stability,
3. ability to ground with a very high surface finish and tolerance,
4. strength retention over a broad temperature range, and
5. low cost
 Based on these characteristics, ceramics are
used in a variety of wear applications such as
1. seals
2. sandblast nozzles
3. wear pad
4. liner

 The barrier to more extensive uses of ceramics

include:
1. brittleness
2. low toughness
3. inadequate understanding of design requirements necessary to
overcome mechanical limitations
4. insufficient design database
 Thermal Shock
 It refers to thermal stresses occurred in a component as
result of temperature difference between the interior and
exterior or between various regions of a component.

 For shapes such as infinite slab, long cylinder

(solid/hollow), or sphere (solid/hollow), the peak stress
occurred at the surface during cooling is
sth = thermal stress
E a DT E = elastic modulus
s th = n = Poission’s ratio
1- n a = coeff. of thermal expansion
∆T = temperature difference

 ∆T can be decreased by
1. increasing thermal conductivity of materials (material aspect)
2. configuration modification and heat transfer condition modification (design aspect)