• Stress Corrosion Cracking

– Stress corrosion maybe defined as the combined action of sustained tensile stress
and corrosion that may lead to the premature failure of materials. Certain materials
are more susceptible than others. If a susceptible material is placed in a corrosive
environment under tension of sufficient magnitude, and the duration of service is
sufficient to permit the initiation and growth of cracks, failure will occur at a stress
lower than that which the material would normally be expected to withstand. The
corrosive environment need not be severe in terms of general corrosive attack.

– Service failures due to stress corrosion are frequently encountered in cases where
the surfaces of the failed parts are not visibly corroded in a general sense.

– If failure is to be avoided, the total tensile strength in service must be maintained at

a safe level. There is no absolute threshold stress for stress corrosion, but
comparative stress-corrosion thresholds can be determined for materials subjected
to controlled conditions of test. Estimates of the stress-corrosion threshold for a
specific service application must be determined for each alloy and heat treatment,
using a test piece, stressing procedure and corrosive environment that are
appropriate for the intended service.

• Stress corrosion

• Stress Corrosion Cracking (SCC), defined as the combined action of a sustained tensile stress
and corrosion, can cause the premature failure of metals. The metallic components
proposed for use in most spacecrafts must be screened to prevent failures resulting from
SCC.

• Only those products found to possess a high resistance to stress-corrosion cracking may
have unrestricted usage in structural applications.

• Materials intended for structural applications and likely to be exposed to a long-term

terrestrial storage or flown on the Space Transportation System, fracture critical items, all
parts used or associated with the fabrication of launch vehicles shall possess a high
resistance to stress-corrosion cracking.

• Structural products of a metallic nature shall be selected from the preferred list in Table I of
ECSS- Q- 70- 36.

Constraints on materials

• Temperature

• Vacuum

• Thermal cycling

• Chemical (corrosion)

• Galvanic compatibility
 • Atomic oxygen

• Moisture absorption/desorption

• Fluid compatibility

• Temperature

• The range of temperatures experienced will play a large part in the materials
selection. Extremes are illustrated by the examples of cryogenic tanks and thermal
protection systems for re-entry applications. Temperatures below room
temperature generally cause an increase in strength properties, however the
ductility decreases. Ductility and strength may increase or decrease at temperatures
above room temperature. This change depends on many factors, such as
temperature and time of exposure.

• Materials shall be compatible with the thermal environment to which they are
exposed.

Passage through transition temperatures (e.g., brittle-ductile transitions or glass transition

temperatures including the effects of moisture or other phase transitions) shall be taken into
account.

• Thermal cycling

– Thermal cycling can induce thermal stresses and due to the difference in coefficient
of thermal expansion between fibres and matrix for composites and between base
metal and coating micro-cracks can form which could jeopardise long-term
properties.

• Materials subject to thermal cycling shall be assessed to ensure their

capability to withstand the induced thermal stresses and shall be tested
according to ECSS- Q- 70- 04.

• Chemical (corrosion)

The chemical environment to which a material is subjected in its life span may cause changes in the
material properties. Corrosion is the reaction of the engineering material with its environment with
a consequent deterioration in properties of the material. Corrosion will include the reaction of
metals, glasses, ionic solids, polymeric solids and composites with environments that embrace liquid
metal, gases, non-aqueous electrolytes and other non-aqueous solutions, coating systems and
adhesion systems

• Galvanic compatibility

– If two or more dissimilar materials are in direct electrical contact in a corrosive

solution or atmosphere galvanic corrosion might occur. The less resistant material
becomes the anode and the more resistant the cathode. The cathodic material
corrodes very little or not at all, while the corrosion of the anodic material is greatly
enhanced.
 • Material compatibilities shall be selected in accordance with ECSS- Q-70-71,

• Maximum potential differences shall be in accordance with ECSS- Q-70-71,

• Atomic oxygen

– Spacecraft in low earth orbit (LEO) at altitudes of between 200 km and 700 km are
exposed to a flux of atomic oxygen. The flux level varies with altitude, velocity vector
and solar activity. The fluence levels vary with the duration of exposure.

• Moisture absorption/desorption

– The properties of composite materials are susceptible to changes induced by the

take-up of moisture. Moisture absorption occurs during production of components
and launch of the spacecraft, desorption occurs in the space vacuum.

• Fluid compatibility

– In some occasions materials are in contact with liquid oxygen, gaseous oxygen or
other reactive fluids or could come into contact with such a fluid during an
emergency situation.

• Anodising

• Chemical conversion

• metallic coatings (overlay and diffusion)

• hard coatings

• Diffusion barriers

• High temperature oxidation protective coatings

• Thermal barriers

• Moisture barriers

• coatings on CFRP

• The surface finish of a component can influence its mechanical and environmental
durability.

• Anodising (chromic, sulphuric, sulphuric+oxalic)

– Anodising is an electrolytic process for thickening and stabilising oxide films on base
metals and anodising grade alloys. It may be used as a pre-treatment for painting
and dying or as a passivation treatment for an electro-brightened surface.

– Hard anodised layers are wear resistant and durable.

• Chemical conversion (chromate, phosphate) -

– Commercial process (alodine , irridite, etc)

– Chemical conversion depends upon the absorption of a protective metal oxide film
into an existing oxide film but may include non-metals in some cases.
 – Chromating involves the formation of a mixed metal-chromium oxide film. It has a
good corrosion resistance and an excellent bond to subsequent organic coatings.

– Phosphating is primarily used as an underlayer for paint finishes. It finds little

application for corrosion protection.

– Chemical conversion coatings can be either electrically conductive or non-

conductive.

– Temporary corrosion protection only

– simple and cheap process

– may be applied by immersion, praying, brushing, wiping or any other wetting

method

• Metallic coatings (overlay and diffusion)

– Metallic overlay coatings can be applied in numerous ways to substrates (e.g.

electroplating, chemical evaporation and ion sputtering).

– Metallic diffusion coatings modify the composition of the surface by enrichment

with Cr, Al or Si and/or formation of their stable oxides.

– Cadmium and Zinc coatings shall not be used because of their high vapour pressure.

– Silver, copper and osmium coatings shall not be used on external surfaces because
they are sensitive to atomic oxygen.

– Electroplated tin can form whiskers

– noble coatings such as gold and silver should be continuous (e.g. corrosion such as
red plague)

• Hard coatings

– Hard coatings are used to improve the abrasive properties of the surface. Also, the
ability to cold weld is greatly reduced. The combination of a hard coating and a soft
substrate is not desirable. The coating can break under pressure.

• Diffusion barriers

– High temperature service operation can result in compositional changes of the bulk
material and of the coating due to diffusion. These compositional changes can result
for example in formation of intermetallic compounds, which are brittle and can
break under cyclic stresses.

– E.G. Cu or Ni layer as diffusion barrier between a brass (Cu-Zn) substrate and a

Sn/Sn-Pb coating

• Moisture barriers

– Coatings can be used to prevent moisture absorption or desorption of dimensionally

stable structures or to prevent the release of organic volatiles which could affect the
performances of some equipments.

• Coatings on CFRP
 – Coatings on CFRP are used as moisture stoppers, as protection against atomic
oxygen or for adjusting optical properties. In most cases these coatings are metallic.
In this dissimilar material contact the CFRP usually behaves as the cathode and as
such can corrodes the coating material.

• High Temp oxidation protective coatings (metallic)

– Protective coatings are important in high temperature applications, such as re-entry

surfaces and propulsion systems. Oxidation protection, thermal shock behaviour and
erosion properties are properties to consider.

• Thermal barriers (ceramic)

– Thermal barrier coatings are used to retard component overheating due to high heat
fluxes. These coatings are essentially ceramic overlay coatings, based on zirconia,
where the coating thickness is approximately 0.4 mm. They are applied to selected
regions only. The coating process can modify the condition of the substrate.

Corrosion-General

• Four systems for corrosion testing are available, each covering a different area of corrosion
evaluation

• Corrosion Units:

• humidity test chamber, testing according to ASTM

• salt spray test chamber, testing according to ASTM-B117

• stress corrosion test rig, testing according to ASTM-G44

• bimetallic corrosion set-up

• atomic oxygen corrosion

• red plague corrosion test unit, testing according to ESA PSS-01-720

Salt-spray-(foreground) and Humidity Chamber- both have temperature and humidity

regulators
• Corrosion fatigue

– Corrosion fatigue indicates crack formation and propagation caused by the effect of
alternating loading in the presence of a corrosion process. Because of the time
dependence of corrosion, the number of cycles to failure depends on frequency.
Since chemical attack requires time to take effect, its influence is greater as the
frequency becomes lower. No metals or alloys demonstrate complete resistance to
corrosion fatigue.

• Same requirement as with fatigue

• Hydrogen embrittlement

– Metals can be embrittled by absorbed hydrogen to such a degree that the

application of the smallest tensile stress can cause the formation of cracking. The
following are possible sources of hydrogen: thermal dissociation of water in
metallurgical processes (e.g., casting and welding), decomposition of gases, pickling,
corrosion, galvanic processes (e. g. plating) and ion bombardment.

• The possibility of hydrogen embrittlement during component manufacture

and/or use shall be assessed

• Creep

– Creep is a time-dependant deformation of a material under an applied load. It

usually occurs at elevated temperature, although some materials creep at room
 temperature. If permitted to continue indefinitely, creep terminates in rupture.
Extrapolations from simple to complex stress-temperature-time conditions are
difficult.

• Testing under representative service conditions is necessary when creep is

likely to occur.

• Micro-yielding

– Some materials may exhibit residual strain after mechanical loading. The micro-yield
is the force to be applied to get a residual strain of 1x10-6 m/m along the tensile or
compression loading direction. In general, the most severe mechanical loading
occurs during launch.

• Where dimensional stability requirements have to be met, micro-yielding

shall be assessed.

• When it is likely to occur, testing and analysis in relation with the mechanical
loading during the life cycle of the hardware shall be performed.
Sulfide stress cracking, or SSC, is defined by NACE as the “Cracking of a metal under the combined
action of tensile stress and corrosion in the presence of water and H2S (a form of hydrogen stress
cracking).” Through the review of this definition, several factors must be present for SSC to occur.
These factors are 1) a susceptible material, 2) tensile stress, 3) hydrogen sulfide, and 4) water. If any
one of these factors is missing, sulfide stress cracking will not occur.

Hydrogen Induced Cracking (HIC) Hydrogen Induced Cracking (HIC) is defined as a “hydrogen attack
induced by decarburization”. This type of attack occurs at elevated temperatures and is caused by
atomic hydrogen permeating through the steel and reacting to form other gases. Hydrogen reacts
with the carbon in the steel to form methane gas which cannot diffuse out of the steel’s matrix.
Accumulation of this methane at grain boundaries and other steel discontinuities results in localized
high stresses from which cracks can occur. HIC attack generally occurs at temperatures greater than
5000 F and is dependant on the hydrogen partial pressure.

FERRIC CHLORIDE CORROSION TEST – TEST METHOD A - ASTM G48 TEST SPECIFICATION: A cross
section of the welded pipe, 25mm wide x 50mm in length (weld centreline) x full thickness was
prepared with all cut sides polished to a P600 finish in accordance with ASTM G48 Method A “Ferric
Chloride Pitting Test”. As requested both the external and internal weld caps were left as welded
with minimal preparation. It was stated that no passivation or pickling was applied to the coupon
after welding. The specified test duration was for 24 hours at a testing temperature of 22°C. After
completion of testing the same test piece was further tested at 40°C for 24 hours, the machined
sides were repolished and both the external and internal weld caps were left as per previous test
conditions. Sample Size at 22°C: 50.03mm long x 24.93mm wide x 8.77mm W.T (Please note the
thickness is based on the parent material thickness and does not include the weld reinforcement).
Sample Size at 40°C: 50.01mm long x 24.84mm wide x 8.77mm W.T (Please note the thickness is
based on the parent material thickness and does not include the weld reinforcement). Test Solution:
6% FeCl³ Test Duration: 24 hour

ASTM A 262 Practice E

Materials Selection

Materials selection is usually straightforward for uniform corrosion, as the corrosion is relatively
easy to evaluate and monitor. If a material shows only general attack with a low corrosion rate, or if
only negligible contamination is present in a process fluid or on the surface, then cost, availability,
and ease of fabrication may be the dominant influence on the material of choice. An acceptable
corrosion rate for a relatively low-cost material such as plain carbon steel is about 0.25 mm/year (10
mils/year) or less. At this rate and with proper design with adequate corrosion allowance, a carbon
steel vessel will provide many years of low-maintenance service. For more costly materials, such as
austenitic stainless steels and copper and nickel alloys, a maximum corrosion rate of 0.1 mm/year (4
mils/year) is generally acceptable. However, a word of caution is in order. One should never assume
that the higher-alloyed material or the higher-cost material is more corrosion resistant in a given
environment. Proper evaluation is required. For instance, seawater corrodes plain carbon steel fairly
uniformly at a rate of 0.1 to 0.2 mm/year (4 to 8 mils/year) but also severely pits certain austenitic
stainless steels. The same is true for stagnant solutions; the steel becomes passive or protected,
where some austenitic stainless steels will pit due to the formation of autocatalytic corrosion cells.
At times, nonmetallic coatings and linings ranging in thickness from a few tenths to several
millimeters are applied to prolong the life of low-cost alloys such as plain carbon steels in
environments that cause general corrosion. The thin-film coatings that are widely used include
baked phenolics, catalyzed cross-linked epoxyphenolics, and catalyzed coal tar-epoxy resins (see the
section “Protective Coatings and Linings” in the article “Analysis and Prevention of Corrosion-Related
Failures” in this Volume). It is not advisable to use thin-film coatings in services where the base
metal corrosion rate exceeds 0.5 mm/year (20 mils/year), because corrosion is often accelerated at
holidays (pinholes or scratches) in the coating. Thickfilm linings—which include glass, fiber- or flake-
reinforced furan, polyester and epoxy resins, hot-applied coal tar enamels, and various elastomers
such as natural rubber—may be more appropriate.

When investigating the effect of temperature on the corrosion rate of a metal in a liquid or gaseous
environment, the temperature at the metal-corrodent interface must be considered. This
temperature may differ substantially from that of the average of the corrodent. Laminar flow would
permit temperature gradients to exist. This difference is especially important for heat-transfer
surfaces, where the hot-wall effect causes a much higher corrosion rate than might be expected. A
common approximation for chemical activity, called the “10 degree rule,” states an increase of 10 °C
(18 °F) in bulk temperature of the solution can increase the corrosion rate by a factor of two or
more. In atmospheres, the temperature variation is more complex as temperature and humidity
both affect corrosion and they are interdependent. Hot-wall failures are fairly common in heating
coils and heat-exchanger tubes. An example of this hot-wall

Intergranular corrosion is usually (but not exclusively) a consequence of composition changes in the
grain boundaries from elevated-temperature exposure. In general, grain boundaries can be
susceptible to changes in composition, because grain boundaries are generally slightly more active
chemically than the grains themselves. This is due to the areas of mismatch in the grain-boundary
regions relative to the more orderly and stable crystal lattice structure within the grains. The relative
disorder in the grain boundaries provides a rapid diffusion path, which is further enhanced by
elevated-temperature exposure. Therefore, a variety of chemical changes may occur preferentially
in the grain-boundary areas such as segregation of specific elements or compounds, enrichment of
an alloying element, or the depletion of an element when precipitates nucleate and grow
preferentially in this region. Impurities that segregate at grain boundaries may also promote galvanic
action in a corrosive environment.