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v1 Jan 2014

Dr Chris Pickles

This work by Lucideon is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike
4.0 International License.

by Lucideon 2
The green agenda continues to dominate
aerospace developments both from the
regulatory perspective and from economic
operating imperatives. The REACH directive and
other regulatory pressures are targeting
chromium removal by 2017 whilst fuel burn
reduction is the main driver behind the use of
composites as a means of light-weighting aircraft
structures and components.
In both these areas new material developments
continue to hold the key to the successful
achievement of the green objectives whilst
maintaining, or improving, the other essential
product performance requirements.
Underpinning many areas of these technological
advances is a need to understand surface and
interface functionality from both a chemical and
physical standpoint. In this paper we give
examples of where surface characterisation
techniques are continuing to make a major
contribution to these endeavours to reduce the
environmental impact of the aerospace industry
in the future.
The picture is changing continuously but a
reasonable estimate of the current use of carbon
fibre in aerospace applications is in the region of
30000 tonnes per annum. According to informed
sources this will rise to 170000 tepa by 2020.
Fuel represents over half of total airline operating
costs and a 30% weight loss would deliver a 6%
fuel cost saving. The 787 ‘Dreamliner’ is 50%
composite, 20% aluminium, 15% titanium, 10%
steel and 5% other materials. Maintenance costs
are also reduced significantly by the use of
composite structures - estimated to be 30%
lower for the 787. Developments continue apace
with thermoset resins coming under the influence
of the REACH directive in terms of the need to
phase out the curing agent MDA. Beyond this the
attraction of thermoplastic resins in terms of their
recyclability and the lower drag available from
thinner wings are just two of the future
developments that will maintain the inexorable
demand for surface characterisation as an
essential component of composite materials
development programmes.
Chromium is a known carcinogen and its use is
limited by the COSHH regulations in the UK.
The replacement of chromium compounds in
anticorrosion coatings is a live topic in the
aerospace and other industries. The complex
chemistry involved in reformulating anti-
corrosion coatings depends critically on the
developer’s ability to understand the interfacial
phenomena occurring between the various
formulation ingredients, between the coating
ingredients and the substrate layer(s) and
between the coating ingredients and the
corrosion challenge. All of these issues can be
informed by surface characterisation techniques
which are able to deliver understanding in terms
of both the chemistry and the physical form of
coating systems.
Composite materials depend critically for their
operational performance on the strength of the
bond between the fibre and the matrix polymer.
Any disruption to this interface will affect the
adhesion and can lead to resin-fibre
disbondment. Similarly, coating adhesion to
composite structures is dependent on both the
physical and chemical nature of the substrate and
of the coating. Whilst the substrate surface
roughness has an optimum value related to the
keying of the coating, the coating outer surface
needs to be as smooth as possible to reduce
drag. The machining of composites is also an area
of potential concern in terms of fibre break-out
and edge finish whether the structure is
In all of these areas surface characterisation
techniques are able to deliver quantitative and
highly spatially resolved chemical and physical
information. Typical examples include the analysis
of a multilayer printed circuit board in which the
glass fibre filled epoxy pre-preg layer was
delaminating. Chemical analysis using surface
mass spectrometry of both the fibre surfaces and
the resin residues, when compared with
conforming material, showed that insufficient
adhesion promoter had been used in the
pretreatment of the glass fibres prior to curing. or
water jet cut.

by Lucideon 3

Electron Micrograph of glass fibre composite
cross section

Chemical profiling of a multi-layer coating
These post-mortem costs are significantly higher
than the costs that would have been incurred
when establishing material properties prior to
In another example a multilayer acrylic/metal
laminate had suffered a different form of
delamination due to compound formation at the
interface. This condition was characterised by
both quantitative 3D surface profiling giving
nanometre resolved topographical images of the
surface discontinuity together with quantitative,
elemental surface spectroscopy to identify the
chemical species present.
The surface characterisation of both carbon fibre
and glass fibre pre-pregs is an important
application of all three analytical techniques
whereby fibre surfaces can be diagnosed for both
inorganic and organic residues as well as for
chemical modification and surface pitting. Gel
coats can similarly be measured for surface
smoothness and/or imperfection with
quantitative statistical data allied to nanometre
resolved 3D images. Surface chemical
characterisation has also been applied
successfully to the analysis of release papers to
investigate potential material transfer and, in an
exercise to study the surface profiles of a series
of treated release papers; valuable data on the
variation in surface smoothness and treatment
distribution was measured.
The performance of chromium compounds as
anticorrosion ingredients in coatings formulations
is well known. There have also been a number of
investigations into alternative systems. In all of
these it is clear that the precise chemical and
microstructural make-up of the coating is of
crucial importance in order to optimise the
galvanic mechanism by which corrosion
protection is achieved. Surface characterisation
techniques, such as surface mass spectrometry
and surface elemental spectroscopy, have been
widely used to study the chemical nature of both
the substrates and coating formulations in order
to optimise coating performance in terms of
corrosion prevention. Quantitative 3D surface
topographical profiling has also been applied to
the specification and control of substrate surface
For current chromium containing coatings the
curing conditions are critical to the development
of the active species both in terms of anti-
corrosion performance and strength of bonding
to the substrate. In particular, the oxidation state
of the chromium is important in terms of its
galvanic activity.

by Lucideon 4

3D topographical profile
Substrates are often pre-treated prior to coating
by a variety of processes most of which are either
promoting surface oxidation (or nitriding) by
chemical or thermal means. The characterisation
of these treated surfaces is commonly achieved
by surface mass spectrometry and/or by depth
profiling mass spectrometry and also by surface
elemental spectroscopy and/or depth profiling
elemental spectroscopy which latter technique is,
importantly, quantitative. In a typical example an
anodised metal component was characterised by
mass spectrometric depth profiling to establish
the penetration of the treatment and by 3D
surface topography to measure the effect on
substrate surface roughness quantitatively.
In another example the effect of part marking
on the surface condition and potential
susceptibility to subsequent performance was
characterised by quantitative surface elemental
spectroscopy and quantitative surface
topographical imaging.
It has already been mentioned that the oxidation
state of chromium in anti-corrosion coatings is
functionally important. Quantitative surface
elemental spectroscopy operating in high
resolution mode is able to distinguish between
the two oxidation states of chromium with high
precision and this analysis is routinely used in the
characterisation of such coatings. Moreover,
similar capability exists for all metallic elements
to which it could otherwise apply and this will be
important in supporting the development of non-
chromium containing alternative anti-corrosion
The adhesion of coatings, including replacement,
non-chromium anti-corrosion coatings, is
paramount in delivering in-service performance.
The causes of delamination or the adhesive
failure of coatings is susceptible to investigation
by surface characterisation techniques. In a
typical example, a two layer coating was
exhibiting adhesive failure. Surface molecular
mass spectrometry, together with quantitative
surface elemental spectroscopy investigations of
the substrate and coating layers, showed that
ingredient segregation from one of the layers was
affecting the inter-layer bond strength.

Jet engine
Eurofighter Jet Engine by Tony Hisgett is
licensed under a Creative Commons Attribution 3.0
Unported License.

The most common cause of adhesive failure
however is the occurrence of extraneous surface
contamination - often of silicone based materials.
This can be as relevant to coated composites as
it is to coated metals and alloys. Aerospace
manufacturers routinely operate multi-stage
cleaning procedures to ensure substrates are
adequately cleaned prior to being presented to
the coating process. The quality of cleaning is
commonly monitored by a rinse/filter/particle
count procedure with various limit values.
Crucially however this procedure does not reveal
what potential contamination may still be
remaining on the cleaned component. Surface
characterisation can measure part cleanliness
directly and quantitatively. Cleaning processes
can be routinely monitored using prequalified
coupons which are passed through the process
with the components. These can then be
analysed by surface elemental spectroscopy and,
by the use of a bespoke chemical combinatorial
algorithm, a % cleanliness measure can be
generated. This capability allows for both an
unequivocal cleanliness specification to be set
and an ongoing quality control procedure to be
implemented which relate directly to the
cleanliness of the substrate surface to be coated.

by Lucideon 5

The aerospace industry is committed to
developing and adopting technologies which
reduce its environmental impact in both the
short and long term. In particular the use of
composite materials for lightweighting to reduce
fuel burn and the replacement of chromium in
anti-corrosion coatings are just two areas where
this policy is already being implemented. In this
paper we have considered how techniques for
both the chemical and topographical
characterisation of surfaces and interfaces can be
applied to ensure that both these developments
benefit significantly therefrom.

by Lucideon


Lucideon is a leading international provider of
materials development, testing and assurance.
Through its offices and laboratories in the UK, US
and the Far East, Lucideon provides materials
and assurance expertise to clients in a wide range
of sectors, including healthcare, construction,
ceramics and power engineering.
The company aims to improve the competitive
advantage and profitability of its clients by
providing them with the expertise, accurate
results and objective, innovative thinking that
they need to optimise their materials, products,
processes, systems and businesses.


Chris holds a Degree in Chemistry, a PhD in
Polymer Science, and a Postdoctoral Fellowship.
Chris has been supplying surface analysis
capabilities to the aerospace industry for over
three years with particular emphasis on carbon
reduction programmes involving composite
developments, coating analysis and lubricant
developments in relation to the introduction of
Chris has worked in both the aftercare sector as a
Company Technical Manager and in tier one
supply chain manufacturing as Managing
Chris has been responsible for the plastic
injection moulding and blow moulding
manufacture of automotive component systems
including highly technical mouldings such as fuel
tanks and 3D spoilers. In addition Chris has also
managed an integral supply chain utilising Toyota
production system protocols.
During his career, Chris has spent four years
researching copolymer design for bulk property
manipulation and the statistical mechanics of
PVC to determine conformational sequencing.
Chris's knowledge also encompasses plastics
manufacturing, including injection moulding of
glass-filled nylon and co-extrusion blow moulding
of complex 3D components.
In the field of surface science, Chris has
conducted research projects on alternative
material sources for surfactants and detergent
product re-formulation. These include the re-
launch of a branded fabric washing product in
Brazil and the design of a surfactant system
utilising renewable resources. As Technical
Manager in the automotive aftercare industry he
has managed the development and quality
control of spray paints for high speed aerosol