Pilling-Bedworth ratio

The Pilling-Bedworth ratio (P-B ratio), in corrosion of metals, is the ratio of the
volume of the elementary cell of a metal oxide to the volume of the elementary cell of the
corresponding metal (from which the oxide is created). On the basis of the P-B ratio, it
can be judged if the metal is likely to passivate in dry air by creation of a protective oxide

The P-B ratio is defined as:

where:

 RPB is the Pilling-Bedworth ratio,

 M - the atomic or molecular mass,
 n - number of atoms of metal per one molecule of the oxide
 ρ - density, and
 V - the molar volume.

Intermetallics

Intermetallics or intermetallic compounds is a term that is used in a number of

different ways. Most commonly it refers to solid-state phases involving metals. There is a
"research definition" adhered to generally in scientific publications, and a wider
"common use" term. There is also a completely different use in coordination chemistry,
where it has been used to refer to complexes containing two or more different metals.

Although the term intermetallic compounds, as it applies to solid phases, has been
in use for many years, its introduction was regretted, for example by Hume-Rothery in
1955.[1]

Note that many intermetallic compounds are often simply called alloys, even
though strictly speaking they are not. For example, complex metallic alloys are
intermetallic compounds with large unit cells.
Research definition

This was stated by Schulze in 1967,[2] and defines intermetallic compounds as solid
phases containing two or more metallic elements, with optionally one or more non-
metallic elements, whose crystal structure differs from that of the other constituents.
Under this definition the following are included

 Electron (or Hume-Rothery) compounds

 Size packing phases. e.g. Laves phases, Frank-Kaspar phases and Nowotny phases
 Zintl phases

The definition of a metal is taken to include:

 the so-called poor metals, i.e. aluminium, gallium, indium, thallium, tin and lead
 some, if not all, of the metalloids, e.g. silicon, germanium, arsenic, antimony and
tellurium.

Alloys, which are a homogeneous mixture of metals, and interstitial compounds such as
the carbides and nitrides are excluded under this definition. However, interstitial
intermetallic compounds are included as are alloys of intermetallic compounds with a
metal.

Common use

In common use of the research definition, including poor metals and metalloids, is
extended to include compounds such as cementite, Fe3C. These compounds, sometimes
termed interstitial compounds can be stoichiometric, and share similar properties to the
intermetallic compounds defined above.

Complexes

The term intermetallic is used [3] to describe compounds involving two or more
metals such as the cyclopentadienyl complex Cp6Ni2Zn4.

Intermetallics involving two or more metallic elements

Intermetallic compounds are generally brittle and high melting. They often offer a
compromise between ceramic and metallic properties when hardness and/or resistance to
high temperatures is important enough to sacrifice some toughness and ease of
processing. They can also display desirable magnetic, superconducting and chemical
properties, due to their strong internal order and mixed (metallic and covalent/ionic)
bonding, respectively. Intermetallics have given rise to various novel materials
developments. Some examples include alnico and the hydrogen storage materials in
nickel metal hydride batteries. Ni3Al, which is the hardening phase in the familiar nickel-
base superalloys, and the various titanium aluminides have also attracted interest for
turbine blade applications, while the latter is also used in very small quantities for grain
refinement of titanium alloys.

Properties and examples

 magnetic materials e.g. alnico; sendust; Permendur, FeCo

 superconductors e.g. A15 phases; niobium-tin
 hydrogen storage e.g. AB5 compounds (nickel metal hydride batteries)
 shape memory alloys e.g. Cu-Al-Ni (alloys of Cu3Al and nickel); Nitinol (NiTi)
 coating materials e.g. NiAl
 high temperature structural materials e.g. nickel aluminide, Ni3Al
 dental amalgams which are alloys of intermetallics Ag3Sn and Cu3Sn

The formation of intermetallics can cause problems. Intermetallics of gold and

aluminium are a significant cause of wire bond failures in semiconductor devices and
other microelectronics devices. There are 5 of them. AuAl 2 is known as "purple plague".
Au5Al2 is known as "white plague".

Embrittlement

Embrittlement is a loss of ductility of a material, making it brittle. Various materials

have different mechanisms of embrittlement.

 Hydrogen embrittlement is the effect of hydrogen absorption on some metals and

alloys.

 Sulfide stress cracking is the embrittlement caused by absorption of hydrogen

sulfide.

 Liquid metal embrittlement (LME) is the embrittlement caused by liquid metals.

  Metal-induced embrittlement (MIE) is the embrittlement caused by diffusion of
atoms of metal, either solid or liquid, into the material.

 Neutron radiation causes embrittlement of some materials, neutron-induced

swelling, and buildup of Wigner energy. This is a process especially important for
neutron moderators and nuclear reactor vessels (see ductility).

 The primary embrittlement mechanism of plastics is gradual loss of plasticizers,

usually by overheating or aging.

 The primary embrittlement mechanism of asphalt is by oxidation, which is most

severe in warmer climates. Asphalt pavement embrittlement can lead to various
forms of cracking patterns, including longitudinal, transverse, and block
(hexagonal). Asphalt oxidation is related to polymer degradation, as these
materials bear similarities in their chemical composition.

Hydrogen embrittlement

Hydrogen embrittlement is the process by which various metals, most importantly high-
strength steel, become brittle and fracture following exposure to hydrogen. Hydrogen
embrittlement is often the result of unintentional introduction of hydrogen into
susceptible metals during forming or finishing operations.

Hydrogen embrittlement is also used to describe the formation of zircaloy hydride. Use of
the term in this context is common in the nuclear industry.

Process

The mechanism starts with lone hydrogen atoms diffusing through the metal. At high
temperatures, the elevated solubility of hydrogen allows hydrogen to diffuse into the
metal (or the hydrogen can diffuse in at a low temperature, assisted by a concentration
gradient). When these hydrogen atoms re-combine in minuscule voids of the metal matrix
to form hydrogen molecules, they create pressure from inside the cavity they are in. This
pressure can increase to levels where the metal has reduced ductility and tensile strength
up to the point where it cracks open (hydrogen induced cracking, or HIC). High-strength
and low-alloy steels, nickel and titanium alloys are most susceptible. Austempered iron is
also susceptible.[citation needed] Steel with an ultimate tensile strength of less than 1000 MPa
or hardness of less than 30 HRC are not generally considered susceptible to hydrogen
embrittlement. Jewett et al.[1] reports the results of tensile tests carried out on several
structural metals under high-pressure molecular hydrogen environment. These tests have
shown that austenitic stainless steels, aluminum (including alloys), copper (including
alloys, e.g. beryllium copper) are not susceptible to hydrogen embrittlement along with
few other metals.[2] For example of a severe embrittlement measured by Jewett, the
elongation at failure of 17-4PH precipitation hardened stainless steel was measured to
drop from 17% to only 1.7% when smooth specimens were exposed to high-pressure
hydrogen.

Hydrogen embrittlement can occur during various manufacturing operations or

operational use - anywhere that the metal comes into contact with atomic or molecular
hydrogen. Processes that can lead to this include cathodic protection, phosphating,
pickling, and electroplating. A special case is arc welding, in which the hydrogen is
released from moisture (for example in the coating of the welding electrodes; to minimize
this, special low-hydrogen electrodes are used for welding high-strength steels). Other
mechanisms of introduction of hydrogen into metal are galvanic corrosion, chemical
reactions of metal with acids, or with other chemicals (notably hydrogen sulfide in sulfide
stress cracking, or SSC, a process of importance for the oil and gas industries).

Sulfide stress cracking

Sulfide stress cracking (SSC) is a form of hydrogen embrittlement which is a cathodic

cracking mechanism. It should not be confused with the term stress corrosion cracking
which is an anodic cracking mechanism. Susceptible alloys, especially steels, react with
hydrogen sulfide, forming metal sulfides and atomic hydrogen as corrosion byproducts.
Atomic hydrogen either combines to form H2 at the metal surface or diffuses into the
metal matrix. Since sulfur is a hydrogen recombination poison, the amount of atomic
hydrogen which recombines to form H2 on the surface is greatly reduced, thereby
increasing the amount of diffusion of atomic hydrogen into the metal matrix. This aspect
is what makes wet H2S environments so severe.[citation needed]

Since SSC is a form of hydrogen embrittlement, it is most susceptibile to cracking at or

slightly below ambient temperature.

Sulfide stress cracking has special importance in gas and oil industry, as the materials
being processed there (natural gas and crude oil) often contain considerable amount of
hydrogen sulfide. Equipment that comes in contact with H 2S environments can be rated
for sour service with adherence to NACE MR0175/ISO 15156 for oil and gas production
environments or NACE MR0103 for oil and gas refining environments.

"High Temperature Hydrogen Attack" does not rely on atomic hydrogen. At high
temperature and high hydrogen partial pressure, hydrogen can diffuse into carbon steel
alloys. In susceptible alloys, the hydrogen combines with carbon within the alloy and
forms methane. The methane molecules create a pressure buildup in the metal lattice
voids, which leads to embrittlement and even cracking of the metal.

Sulfidic corrosion, also known as sulfidation, is the term used for the high temperature
(above 450F) in contact with sulfur.[citation needed]

Liquid metal embrittlement

Liquid metal embrittlement (also known as liquid metal induced embrittlement) is a

phenomenon of practical importance, where certain ductile metals experience drastic loss
in tensile ductility or undergo brittle fracture when tested in the presence of specific
liquid metals. Generally, a tensile stress, either externally applied or internally present, is
needed to induce embrittlement. Exceptions to this rule have been observed, as in the
case of aluminium in the presence of liquid gallium.[1] People have studied this
phenomenon from the beginning of the 20th century. Many of its phenomenological
characteristics are known and several mechanisms were proposed to explain it. [2][3] The
practical significance of liquid metal embrittlement is revealed by the observation that
several steels experienced ductility losses and cracking during hot dip galvanizing or
during subsequent fabrication.[4] Cracking can occur catastrophically and very high crack
growth rates have been measured[5].

Liquid metal embrittlement effects can be observed even in solid state, when one of the
metals is brought close to its melting point; e.g. cadmium-coated parts operating at high
temperature. This phenomenon is known as solid metal embrittlement.[6]

Characteristics

Mechanical behaviour

Liquid metal embrittlement or LME is characterized by the reduction in the threshold

stress intensity, true fracture stress or in the strain to fracture when tested in the presence
of liquid metals as compared to that obtained in air / vacuum tests. The reduction in
fracture strain is generally temperature dependent and a “ductility trough” is observed as
the test temperature is decreased.[2] A ductile-to-brittle transition behaviour is also
exhibited by many metal couples. The shape of the elastic region of the stress-strain
curve is not altered, but the plastic region may be changed during LME. Very high crack
propagation rates, varying from few centimeters per second to several meters per second
are induced in solid metals by the embrittling liquid metals. An incubation period and a
slow pre-critical crack propagation stage generally precede final fracture.

Metal chemistry

It is believed that there is specificity in the solid-liquid metals combinations experiencing

LME.[7] There should be limited mutual solubilities for the metal couple to cause
embrittlement. Excess solubility makes sharp crack propagation difficult, but no
solubility condition prevents wetting of the solid surfaces by liquid metal and prevents
LME. Presence of an oxide layer on the solid metal surface also prevents good contact
between the two metals and stops LME. The chemical compositions of the solid and
liquid metals affect the severity of embrittlement. Addition of third elements to the liquid
metal may increase or decrease the embrittlement and alters the temperature region over
which embrittlement is seen. Metal combinations which form intermetallic compounds
do not cause LME. There are a wide variety of LME couples. [3] Most technologically
important are the LME of aluminum and steel alloys.

Metallurgy

Alloying of the solid metal alters its LME. Some alloying elements may increase the
severity while others may prevent LME. The action of the alloying element is known to
be segregation to grain boundaries of the solid metal and altering the grain boundary
properties. Accordingly, maximum LME is seen in cases where alloy additions elements
have saturated the grain boundaries of the solid metal. [2] The hardness and deformation
behaviour of the solid metal affect its susceptibility to LME. Generally harder metals are
more severely embrittled. Grain size greatly influences LME. Solids with larger grains
are more severely embrittled and the fracture stress varies inversely with the square root
of grain diameter. Also the brittle to ductile transition temperature is increased by
increasing grain size.

Physico-chemical properties

The interfacial energy between the solid and liquid metals and the grain boundary energy
of the solid metal greatly influence LME. These energies depend upon the chemical
compositions of the metal couple.
Test parameters

External parameters like temperature, strain rate, stress and time of exposure to the liquid
metal prior to testing affect LME. Temperature produces a ductility trough and a ductile
to brittle transition behaviour in the solid metal. The temperature range of the trough as
well as the transition temperature are altered by the composition of the liquid and solid
metals, the structure of the solid metal and other experimental parameters. The lower
limit of the ductility trough generally coincides with the melting point of the liquid metal.
The upper limit is strain rate sensitive. Temperature also affects the kinetics of LME. An
increase in strain rate increases the upper limit temperature as well as the crack
propagation rate. In most metal couples LME does not occur below a threshold stress
level.

Testing typically involves tensile specimens but more sophisticated testing using fracture
mechanics specimens is also performed[8][9][10][11] .

Mechanisms

Many theories have been proposed for LME.[3] The major ones are listed below;

 The dissolution-diffusion model of Robertson [12] and Glickman [13] says that
adsorption of the liquid metal on the solid metal induces dissolution and inward
diffusion. Under stress these processes lead to crack nucleation and propagation.
 The brittle fracture theory of Stoloff and Johnson,[14] Westwood and Kamdar [15]
proposed that the adsorption of the liquid metal atoms at the crack tip weakens
inter-atomic bonds and propagates the crack.
 Gordon [16] postulated a model based on diffusion-penetration of liquid metal
atoms to nucleate cracks which under stress grow to cause failure.
 The ductile failure model of Lynch [17] and Popovich [18] predicted that adsorption
of the liquid metal leads to weakening of atomic bonds and nucleation of
dislocations which move under stress, pile-up and work harden the solid. Also
dissolution helps in the nucleation of voids which grow under stress and cause
ductile failure.

All of these models utilize the concept of an adsorption-induced surface energy lowering
of the solid metal as the central cause of LME. They succeeded in predicting many of the
phenomenological observations. However, a quantitative prediction of LME is still
elusive.
Mercury embrittlement

The most common liquid metal causing embrittlement is mercury. Its spills present
especially significant danger for airplanes. The aluminium-zinc-magnesium-copper alloy
DTD 5050B is especially susceptible. The Al-Cu alloy DTD 5020A is less susceptible.
Elemental mercury spilled can be immobilized and made relatively harmless by silver
nitrate. [1]

On 1 January 2004, the Moomba, South Australia, natural gas processing plant operated
by Santos suffered a major fire. The gas release that led to the fire was caused by the
failure of a heat exchanger (cold box) inlet nozzle in the liquids recovery plant. The
failure of the inlet nozzle was due to liquid metal embrittlement of the train B aluminium
cold box by elemental mercury.