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loss, the data from these coupons was used to target the corrosion test
objectives to metal loss and to determine the most severe corrosion localities
for captive fleet testing and future survey evaluations. The following map is a
composite picture of the corrosivity differences observed in that study.
This map shows macroscopic differences between areas, with coastal regions
(especially in humid tropical conditions) and regions under the influence of
corrosive de-icing salts being the most severe. The high corrosion rates in the
Gulf Coast and Florida can be attributed to the corrosive marine environment.
In the North Eastern regions, de-icing salts applied to road surfaces in winter
are primarily responsible for the high corrosion rates.
Smart Coatings:
Fiber optics
waste incineration
Thermodynamic Principles
The stability of materials at high temperature has been traditionally introduced through
plots of the standard free energy of reaction (G0) as a function of temperature,
commonly called Ellingham diagrams. Such diagrams can help to visualize the relative
stability of metals and their oxidized products. The values of G0 on an Ellingham
diagram are expressed as kJ per mole O2 to normalize the scale and be able to compare
the stability of these oxides directly, i.e. the lower the position of the line on the diagram
the more stable is the oxide.
For a given reaction (M + O2 = MO2) and assuming that the activities of M and
MO2 are taken as unity, the following equations can be used to express the
oxygen partial pressure at which the metal and oxide coexist, i.e. the
dissociation pressure of the oxide:
The table visible here lists the coexistence equations, temperature ranges and
standard energy changes that can be used to construct such diagrams.
Ellingham diagrams may, of course, be constructed for any class of compounds.
Vapor species that form in any given high temperature corrosion situation often
have a strong influence on the rate of attack, the rate generally being
From evaluation of the thermodynamic data presented in this figure, it can be seen that at
1100oC, Al will oxidize in an environment that has an oxygen partial pressure of 10-32 atm
or greater, while chromium will oxidize in an oxygen partial pressure of 10-19 atm or
higher. In general, a vacuum environment will be oxidizing to these elements unless a
reducing species such as hydrogen is present. If inadequate oxygen is present, a nonprotective oxide film may be formed which could promote alloy depletion and loss of
strength.
Coexistence Equation
(K)
(Oxidation Reaction)
(J)
900-1154
Pd + 0.5 O2 = PdO
884-1126
-113,360 + 92.0 T
298-1300
-183,200 + 148 T
892-1302
-130,930 + 94.5 T
1396-1723
-166,900 + 84 T
878-1393
-164,400 + 82 T
967-1373
-246,800 + 141.8 T
1489-1593
2 Cu + 0.5 O2 = Cu2O
-166,900 + 43.5T
1356-1489
2 Cu + 0.5 O2 = Cu2O
-190,300 + 89.5 T
924-1328
2 Cu + 0.5 O2 = Cu2O
-166,900 + 71.1 T
992-1393
-222,540 + 111 T
1160-1371
Pb + 0.5 O2 = PbO
-190,580 + 74.9 T
772-1160
Pb + 0.5 O2 = PbO
-215,000 + 96.0 T
911-1376
Ni + 0.5 O2 = NiO
-233,580 + 84.9 T
1173-1373
Co + 0.5 O2 = CoO
-235,900 + 71.5 T
973-1273
10 WO2.90 + O2 = 10 WO3
-279,400 + 112 T
973-1273
10 WO2.72 + O2 = 10 WO2.90
-284,000 + 101 T
973-1273
-249,310 + 62.7 T
973-1273
-287,400 + 84.9 T
949-1273
-311,600 + 123 T
770-980
Sn + 0.5 O2 = SnO2
-293,230 + 108 T
903-1540
Fe + 0.5 O2 = FeO
-263,300 + 64.8 T
1025-1325
-287,600 + 83.7 T
1050-1300
-313,520 + 78.2 T
693-1181
Zn + 0.5 O2 = ZnO
-355,890 + 107.5 T
1300-1600
-371,870 + 83.7 T
1050-1300
-360,160 + 72.4 T
923-1273
Mn + 0.5 O2 = MnO
-388,770 + 76.3 T
1539-1823
Mn + 0.5 O2 = MnO
-409,500 + 89.5 T
1073-1273
-402,400 + 82.4 T
1050-1300
Nb + 0.5 O2 = NbO
-420,000 + 89.5 T
298-1400
-539,600 + 83.7 T
1380-2500
923-1380
1124-1760
Ca + 0.5 O2 = CaO
-642,500 + 107 T
1760-2500
-795,200 + 195 T
Pilling-Bedworth Ratio
Physical metallurgy relies on a set of guidelines to identify protective oxide
coatings for corrosion protection. Such coatings should be pinhole-free, exactly
as the IC industry requires for high-k metal oxides. Accordingly, guidelines
developed for protective oxide coatings in physical metallurgy can be applied
to the protective metal oxides in integrated circuits.
In their 1923 paper "The oxidation of metals in high temperature" presented to
the Institute of Metals, N. B. Pilling and R. E. Bedworth first correlated the
porosity of a metal oxide with the specific density1. The Pilling-Bedworth ratio,
(P-B ratio) R, of a metal oxide is defined as the ratio of the volume of the
metal oxide, which is produced by the reaction of metal and oxygen, to the
consumed metal volume:
M and D are the molecular weight and density of the metal oxide whose
composition is (Metal)a(oxygen)b; m, and d are the atomic weight and density of
the metal.
Pilling and Bedworth realized that, when R is less than 1, a metal oxide tends
to be porous and non-protective because it cannot cover the whole metal
surface. Later researchers found that, for excessively large R, large
compressive stresses are likely to exist in metal oxide, leading to buckling and
spalling. In addition to R, factors such as the relative coefficients of thermal
expansion and the adherence between metal oxide and metal should also be
favorable in order to produce a protective oxide.
Using the P-B ratio, Bruce Chalmers, Gordon McKay professor at Harvard
University (Cambridge, MA), separated "protective" metal oxides from "nonprotective" metal oxides. The table lists "protective" and "non-protective"
metal oxides and their P-B ratios.
Protective oxides Non protective oxides
Be 1.59
K 0.45
Cu 1.68
Ag 1.59
Al 1.28
Cd 1.21
Cr 1.99
Ti 1.95
Mn 1.79
Mo 3.40
Fe 1.77
Hf 2.61
Co 1.99
Sb 2.35
Ni 1.52
W 3.40
Pd 1.60
Ta 2.33
Pb 1.40
U 3.05
Ce 1.16
V 3.18
The list can be readily applied to the protective metal oxides used in
integrated circuits. The intrinsic protective metal oxides, including the oxides
of Be, Cu, Al, Cr, Mn, Fe, Co, Ni, Pd, Pb, and Ce, may be able to replace silicon
oxide. On the other hand, a few popular metal oxides, e.g. Ti oxide and Ta
oxide, are non-protective, suggesting a possible reason why these oxides have
not been successfully used in commercial products after years of research.
Besides oxides of elemental metal, the P-B ratio can be applied to oxides of
metal alloy, metal nitrides and other metal ceramic systems.
Protective metal oxides can be produced by two classes of methods: growth
and deposition. Growth methods include thermal oxidation, plasma oxidation,
anodization, and implantation. Deposition methods include direct sputtering,
reactive sputtering, and CVD. The IC industry does not have much experience
with production of protective metal oxides. Still, manufacturing experience
with sub-10 nm silicon oxide suggests that it is better to form the protective
metal oxide using a growth method, or to form at least a portion of the
protective metal oxide using a growth method and the remaining portion using
a depositing method. Improved oxide thickness uniformity is one added
advantage of such a composite layer.
where:
x is the oxide film thickness (or the mass gain due to oxidation, which is
proportional to the oxide film thickness)
t is time
kp is the rate constant, directly proportional to the diffusivity of the ionic
species that is rate controlling
x0 is a constant
where:
ke is the rate constant
The linear rate law is also an empirical relationship that is applicable to the
formation and build-up of a non-protective oxide layer.
where:
kL is the rate constant
It is usually to be expected that the oxidation rate will decrease with time
(parabolic behavior), due to an increasing oxide thickness acting as a stronger
diffusion barrier with time. In the linear rate law, this effect is not applicable,
due to the formation of a highly porous, poorly adherent or cracked nonprotective oxide layers. Clearly, the linear rate law is highly undesirable.
Metals with linear oxidation kinetics at a certain temperature have a tendency
to undergo so-called catastrophic oxidation (also referred to as breakaway
corrosion) at higher temperatures. In this case, a rapid exothermic reaction
occurs on the surface, which increases the surface temperature and the
reaction rate even further. Metals that may undergo extremely rapid
catastrophic oxidation include molybdenum, tungsten, osmium, rhenium and
vanadium, associated with volatile oxide formation. In the case of magnesium,
ignition of the metal may even occur. The formation of low-melting point
oxidation products (eutectics) on the surface has also been associated with
catastrophic oxidation. The presence of vanadium and lead oxide
contamination in gases deserves special mention, as they pose a risk to
inducing extremely high oxidation rates.
low sulfur flue gases and for some other common refinery and petrochemical
environments, small variations in the composition of a process stream or in
operating conditions can cause markedly different corrosion rates. Therefore,
the most reliable basis for material selection is operating experience from
similar plants and environments or from pilot plant evaluation.
There are several ways of measuring the extent of high temperature corrosion
attack. Measurement of weight change per unit area in a given time has been a
popular procedure. However the weight change/area information is not
directly related to the thickness (penetration) of corroded metal, which is
often needed in assessing the strength of equipment components.
Hot Corrosion
An accelerated corrosion of metal surfaces that results from the
combined effect of oxidation and reactions with sulfur compounds
and other contaminants, such us chlorides, to form a molten salt on
Hot corrosion is an attack via a salt melt. A representative member of the hot
corrosion agents is Na2SO4. Its generation is explained in combustion
environments by
2 NaCl + SO2 + 0.5 O2 + H2O = Na2SO4 + 2 HCl
it is proposed that the Na2O-activity of the sulfate melt, and, hence, the corrosive
attack is controlled by the partial pressures of gas species like O2 and SO3 in the
ambient. In contrast to that it could be shown, that the oxygen partial pressure at
the interface between substrate and sulfate melt is the controlling factor. Due to an
extremely low oxygen partial pressure at the interface between Si-containing nonoxides and the sulfate melt, these materials act as reducing agents and promote the
decomposition of the sulfate and the formation of Na2O. As a result a rather
violent corrosion reaction is observed. In the case of SiO2 a much less violent
reaction takes place which is related to a higher oxygen partial pressure at the
interface.
During the hot corrosion of Si-containing materials by Na2SO4, SiO2-rich Nasilicate melts are formed which are immiscible with the overlying sulfate melt.
Different surface tensions and dynamic processes at the interfaces between both
melts lead to the formation of isolated melt areas at least in the beginning of the
hot corrosion attack. Between these melt areas direct contact between substrate
and sulfate melt exists allowing a local corrosive attack which may be responsible
for pit formation.
To protect non-oxides against hot corrosion by Na2SO4 a direct contact between
the substrate and the sulfate melt must be avoided. Preoxidation of the non-oxide
materials to form thick and dense oxide scales or for example the deposition of
mullite scales could be a suited means.