FRS 581: FORENSIC CHEMISTY

Paint Analysis

MOHAMED IZZHARIF ABDUL HALIM

FRS 581

FACULTY OF APPLIED SCIENCES

UNIVERSITI TEKNOLOGI MARA MALAYSIA
 Learning Outcome
By the end of this topic, students should
be able to:
• describe paint and types of paint
• discuss the layers in automotive
coatings
• explain the proper collection and
sampling method of paint evidence
• identify and describe the possible
analysis method of paint evidence
 Forensic Paint Analysis
Rationale:
A black car is not always “just a black car.” When black
paint from several different vehicles is compared, it
can sometimes look as though they are all the same. If
a person wanted to cover a small scratch or ding, any
black paint might do. However, when the situation is
more serious, such as a hit-and-run, forensic science
can be used to analyze the paint and tell different
shades of black from each other to solve crimes
 Forensic Paint Analysis
Two kinds of forensic paint investigations:
1) identifications/classifications of the paint sample
 performed when only a small sample was found on the crime
scene and the questions given to the forensic examiner are: what
kind of paint is it? what was the model of the car taking part in
the accident? etc. The answers might be given on the basis of a
detailed analysis and search in data bases of car paints.
2) comparison of samples taken from the crime scene and the
suspected object.
 performed in order to answer the question given whether the
two samples could have come from the same object or not.
 What is paint?
• A paint is a suspension of pigments and additives
intended to color or protect a surface.
• Paints contain pigments, fine powders that do not
dissolve but are dispersed evenly across the surface.
• Pigments are intended to color and/or cover a
surface; they may be organic, inorganic, or a mixture.
Paints are classified into the following four major
raw material categories:
• Resins or binders
• Pigments
vehicle
• Additives
• Solvents.
 Resins or Binders
• Resins (film formers or binders) - important components – effect
on the properties of dry film:
 Hardness
 Adhesion
 chemical and solvent resistance
 Durability
• Resins form films - physical and/or chemical mechanisms that
convert liquid films into a dry coating.
• The term binder - refer to a resin since one of its roles is to “bind”
pigment particles in the dry film.
• Resins used for paints and coatings are polymeric materials with
film forming capabilities.
• 3 important example of binders: acrylic polymers, alkyd polymers
and epoxy polymers
 Pigments
• Pigments are finely divided colored (or white) insoluble
particles having a high refractive index, typically >1.70.
• Pigments, when uniformly dispersed in the resin (medium),
impart color and opacity to the cured film.
 color and opacity are the primary functions of pigments. In
addition, some pigments (for example, chrome pigments, zinc
phosphate pigments) exhibit functional properties such as
corrosion resistance, resistance to UV light, and anti-fouling
properties.
• Pigments are classified based on their origin, whether natural
or synthetic, and on their functions as organic, inorganic,
metallic, and special effect pigments.
• Example of organic pigments:
 Azo derivatives
 Phthalocyanine derivatives
 anthraquinone derivatives
• Example of inorganic pigment:
 White titanium dioxide
 finely divided calcium carbonate
 Zinc oxide
 Carbon black
 Additives
• to improve durability and performance
• added in small quantities (up to ~5 % by weight) that substantially improve or
modify properties of coatings.
• Their types and amounts must be carefully selected, as they may have unintended
results when used inappropriately. For their successful performance, the coating
formulator must have good knowledge about the role of additives and their
interactions with other components of coatings.
• Examples of additives
 dispersants - to separate and stabilise pigment particles
 silicones - to improve weather resistance
 thixotropic agents - to give paints a jelly-like consistency that breaks down to a liquid
when stirred or when a brush is dipped into it
 driers - to accelerate drying time
 anti-settling agents - to prevent pigment settling
 bactericides - to preserve water based paints in the can
 fungicides and algaecides - to protect exterior paint films against disfigurement from
moulds, algae and lichen
 SOlvents
• used to control viscosity of the coatings
• volatile compounds that must evaporate from the film after
application
• Many of these solvents are VOCs, which have harmful effects
on human health and the environment
• efforts to reduce VOC emissions, and there are increasingly
stringent regulatory requirements for use of such solvents in
coatings.
• Waterborne coatings, which use water as the primary carrier
replacing organic solvents over solvent based coatings
The components of a hypothetical gloss enamel
architectural paint (from Thornton, 2002, p. 435).
 Types of paint
Architectural • Sometimes called household paints
• Those coatings most often found in
paints residences and businesses

• Those applied in the process of

manufacturing products including
Product automobiles
• The second major category.
coatings • Because automobiles play a central role in
society and, therefore, in crime
Special- • fulfill some specific need beyond protection
purpose or aesthetic improvement, such water
proofing, or luminescence (as on the dials
coatings of wristwatches)

• occasionally encountered in forgery cases.

• Modern art paints are similar in many
Art paints respects to architectural paints, but many
artists formulate their own paints, leading
to potentially unique sources
• Modern art paints are
mass-produced, but
many artists formulate
their own paints.
• The application process
for art paints is
obviously more varied
and unstructured than
for product coatings.
• Courtesy: Paul Martin,
CRAIC, Inc.
 Coatings Definitions
Many of the words used to describe coatings, such as “paint,” “varnish,” and “lacquer,” in reality
have very specific technical definitions used by the coatings industry. To avoid confusion between the
casual and professional meanings, some of these definitions are listed here:

Architectural • Coatings encountered around a typical household

Paint
• A coloring agent that is soluble in the medium in which it is
Dye dispersed.
• A pigmented coating that has a high gloss (luminous
Enamel reflectivity) when it dries
• Clear or pigmented coatings that dry quickly through
Lacquer evaporation of the solvent
• A suspension of a pigment in a water-based emulsion of any
Latex of several resins
• A suspension of a pigment in a liquid vehicle; more broadly,
Paint any surface coating designed for protection and/or
decoration of a surface
• A fine powder that is insoluble in the medium in which it is
Pigment dispersed
• A solution of melted lac, a resinous excretion of the Lac
Shellac insect (Coccus or Carteria lacca) dissolved in alcohol used as
a sealant, adhesive, or insulating varnish
• A solution of dye or a suspension of a pigment designed to
Stain color, but not protect, a wood surface. Technically speaking,
a stain colors the wood but does not coat it
• A clear solution of oils and organic or synthetic resins in an
Varnish organic solvent
 Automotive Finishes
• One of the most commonly encountered kinds
of paint evidence is automotive paint.
• Automotive paints are also a good example of how
manufacturing styles and variation contribute
to the significance of forensic evidence.
• The automotive finishing process for vehicles
consists of at least four separate coatings.
– Pretreatment
– Primer
– Topcoat
– Clearcoat
 Pretreatment
• The first is a pretreatment, typically zinc electroplating,
applied to the steel body of the vehicle to inhibit rust.
• The steel is then washed with a detergent, rinsed, treated
a second time, and then washed again.
• The significance of this coating is for the forensic paint
analyst to be aware that any zinc found during
elemental analysis may come from this coating and
not necessarily the paint itself.
 Primer
• The second coating is a primer, usually an epoxy resin
with corrosion-resistant pigments;
• the color of the primer is coordinated with the final
vehicle color to minimize contrast and “bleed-
through.”
• The steel body of the vehicle is dipped in a large
bath of the liquid primer and plated on by electrical
conduction.
• The primer coating is finished with a powder
“primer surfacer” that smooths the surface of the
metal and provides better adhesion for the next
coating.
 Topcoat/Basecoat
• The topcoat is the third coating applied to the vehicle
and may be in the form of a single color layer coat, a
multilayer coat, or a metallic color coat;
• This is the layer that most people think of when they
think of a vehicle’s color.
• Topcoat chemistry is moving toward water-based
chemistries to provide a healthier atmosphere for
factory workers and the environment.
• For example, heavy metals, such as lead or chrome, are
no longer used in the formulation of topcoats.
• Metallic or pearlescent coatings, growing in
preference for new model vehicles, have small metal or
mica flakes incorporated to provide a shimmering,
changing color effect.
• Metallic pigments, including zinc, nickel, steel, and
gold-bronze, give a glittering finish to a vehicle’s color,
while pearlescent pigments, mica chips coated with
titanium dioxide and ferric oxide, try to replicate the
glowing luster of pearls.
• The topcoat is often applied and flashed, or partially
cured, and then finished with the next and final coating,
the clearcoat.
 Clearcoats
• Clearcoats are unpigmented coatings applied to
improve gloss and durability of a vehicle’s coating.
• Historically, clearcoats were acrylic-based in their
chemistry, but nearly half of the automotive
manufacturers have moved to two-component
urethanes.

A green vehicle paint

chip, showing the layer
structure common to
most automotive paints.
Courtesy: Mark
Sandercock, Royal
Canadian Mounted
Police.
 • https://youtu.be/sUqKUbmdOr0

1. Electrocoat primer—applied to steel body of

car, provides corrosion resistance,
pigmented gray-black
2. Primer Surfacer—smooths out and hides
seams or imperfections (different pigments)
3. Basecoat—color coat; different additives add
different effects (pearl luster, metallic look)
4. Clear coat—unpigmented layer, improves
gloss, durability, and appearance
 Trends and technique for
Forensic Pain Expert
• Keep up-to-date - latest trends and
techniques in the paint industry.
• Aware previously used formulations and
manufacturing techniques
• Old car far more likely to be encountered in a
forensic case than the newest model car
• Repaired and repainted vehicles are an
additional consideration.
 Vehicle substrates
• Vehicle bodies - no longer made exclusively of steel; various plastics are now
commonly used.
• For example
 fenders may be nylon, polymer blends, or polyurethane resins
 door panels and hoods may be of thermosetting polymers;
 front grills and bumper strips have long been plastic or polymer but now
may be colored to match the vehicle.
 Braking systems, chassis, and even entire cars (BASF unveiled an entirely
plastic car in 1999, as an extreme example) are now constructed from plastics.
• It wouldn’t be unusual for forensic paint examiners to encounter steel,
aluminum, and polymer parts on the same vehicle, each colored by a very
different coating system.
 Collection
• Samples from the crime scene (questioned) should include all
loose or transferred paint materials.
• any object or surface may retain a paint transfer - tools,
glass fragments, fabrics, hairs, fingernails, roadways and signs,
vehicles.
• Evidentiary items with paint transfers should be packaged
and submitted to the laboratory in their entirety, if
possible.
• Depending on the size of the object, packaging and submitting
could prove problematic, so often sampling of paint
transfers must take place in the field.
• It is also important to remember that cross-transfer could have
occurred.
• Known and questioned samples should be collected from
both surfaces.
• Paint evidence should be first photographed and then
removed manually with non-metallic tools, such as small
Paint fragments must be handled
with care; being too aggressive in
their collection can damage or
contaminate them.

The strongest evidence of an

association between a paint sample and
a source is a physical match, considered
unique and individualizing. These are
somewhat uncommon and therefore
carry strong probative value. Here, two
paint chips are aligned to show the
common border demonstrating that
they were at one time one continuous
coating.
 Paint Flakes / Chip
• Lifting or prying out loose flakes, cutting samples
of the paint with a clean knife or blade, and
dislodging them by gently bumping the opposite
side of the painted surface.
• If the samples are cut, the blade should go all the
way through the paint layers to the sub-coating
surface.
• The sampling method will vary considerably given
the circumstances of the crime, the evidence
items, their location, and environmental factors; no
single method will work all of the time.
 Paint Smear
• When a painted object strikes a glancing
blow to another object, it can transfer
paint in the form of a smear.
• A smeared transfer can be very confusing
and difficult to work with because
components from several layers of coatings
can be mixed;
• This can reduce the forensic scientist’s
ability to accurately analyze the
smeared paint.
• Even the best collection efforts can confuse
the issue even more.
• When a forensic scientist is dealing with a
smeared paint transfer, it is best to submit
the entire object to the laboratory, if
possible.
 Known Sample
• Collected from areas as close as possible to, but
not within, the point(s) of damage or transfer.
• This is important for two reasons.
– the damaged area itself is usually not suitable for
providing a known sample: other incidental materials may lie
within the damage and confuse analysis.
– manufacturing variation, detectable differences may
exist between parts of an object.
• All paint samples should be clearly labeled as to
origin, with drawings or photographs as
documentation.
• known samples should contain all layers of the
undamaged paint.
• collect known paint samples from several areas
 Analysis of Paint Samples
• The visual evaluation begins with the
packaging and paperwork, looking for signs of
potential cross-contamination between the
submitted samples.
• Note their condition, weathering
characteristics, size, shape, exterior colors,
and major layers present in each sample.
• The examiner’s notes should include written
descriptions, photographs, and drawings,
as necessary.
• document how that sample was received.
 Visual examination
• Microscopic comparisons of paint layers can reveal
slight variations between samples in color,
pigment appearance, flake size and distribution,
surface details, inclusions, and layer defects.
• Any visual comparisons must be done with the
samples side by side in the same field of view (or
with a comparison microscope), typically at the
same magnification.
• samples must be seen next to each other at the
same time so that subtle details are not
overlooked.
 Physical and Microscopic
Examinations
• A combination of microscopes (stereo,
transmitted light, and polarized light) at
magnifications of 2× to 100× are used to
examine the layers in a paint.
• The paint layer structure can be seen by
cutting through the sample with a scalpel
blade at an angle; this technique increases
the visible area of the sample.
• The structure of the layers and any
irregularities and inhomogeneities are
typically easier to see after this sectioning.
 Sectioning
• Very thin sections of the paint can be
accomplished with a steady hand and a fresh
scalpel blade; a device called a microtome
can also be used.
• A microtome is a mini-vice that holds a
sample in place while a heavy and very
sharp glass or diamond-edged knife slices off
sections a few tens of microns thick. Microtomes are useful for paint analysis
by conserving sample consumption and
• Cross-sections of the paint sample, either preserving the samples for subsequent
analyses.
embedded in a material for support or thin-
section preparations, provide information
about the layers, their thicknesses, and
colors, in addition to the size and
distribution of pigments.
• Embedded preparations, work well because
the sample is easily handled and can be
subjected to many analytical techniques Embedding paint chips in an epoxy resin
with a minimum of additional preparation. supports and preserves the sample, allows
for thin-sectioning, and makes a fragile
specimen safer to handle and store.
 Visual Colour
• The gross visual color of paints can be categorized
systematically by one of many color systems currently in use.
• Two of the main systems traditionally used are the Munsell
system (developed in 1915 by Alfred Munsell, an artist) and
the Commission International de l’Eclairage (CIE)
system, which is described in the ASTM International Standard
Method D 1535 and Test Method E 308.
• Color systems are used to classify colors for description and
communication of color information and for databases
only; absorption spectra of any known and questioned paint
samples are compared in forensic paint comparisons.
 Solvent and Microchemical
Tests
• Solvent and microchemical tests (microchemical tests)
- to discriminate between paint layers of different
pigment and binder composition
• The basis for these tests is that the different layers of
paint have a different chemical composition - react
differently with oxidizing, dehydrating, or
reducing agents.
• Microchemical tests are destructive- applied to
known samples first to evaluate their utility to specific
samples.
• Used only when sufficient questioned samples
are available to avoid consuming the entire sample.
 Microchemical Tests cont.
• Performed on the questioned
and known materials at the same
• Applied to peeled individual layers
of paint
 to avoid interactivity with adjacent
layers
 specific reactions clearer
 Microchemical Tests cont.
• When a chemical is applied, the paint chip or layers
may soften or wrinkle, swell, or curl.
• Entire layers may dissolve or disaggregate.
• Pigment fillers may bubble or “fizz” or flake apart
(called “flocculation”).
• Apparent color change may be seen in some layers.
• Provide good discrimination at the early stages of
an investigation and may help to initially classify
a paint.
• Every single effect need to be photographed and
documented
Instrumental Methods
 Infrared spectroscopy
• Infrared spectroscopy (IR) can identify binders, pigments, and
additives used in paints and coatings.
• Most IRs used in forensic science laboratories employ a microscope
bench, to magnify the image of the sample and focus the beam on
the sample.
• The bench is a microscope stage attached to the instrument chassis
with optics to route the beam through the microscope and back to the
detector.
• Most modern IRs will also be Fourier transform infrared spectroscopy
(FT-IR) spectrometers, which employ a mathematical transformation
(the fast Fourier transform) that translates the spectral frequency into
wavelength. An infrared spectrometer with a
microscope attachment or “bench.”
Normal IRs require a sample to be
pressed into a pellet or placed on a
special specimen card to which the
instrument is “blind.” The microscope
attachment allows for the handling
and analysis of microscopic samples
too small for either pellets or cards.
This also provides for positional
information about the sample to be
analyzed; in the case of paints,
individual layers or particles can be
analyzed in place with no additional
preparation.
• The analysis of paints by FT-IR can be done in
transmittance (where the beam passes through a very
thin sample and then on to the detector) and reflectance
(where the beam is bounced off the sample and then to
the detector), but transmittance is preferred because
it equalizes the signal as well as the sample
geometry; also, and probably more importantly, most of
the reference information available from publications and
instrument vendors is in transmittance.
 Raman Spectroscopy
• An IR-related technique that is gaining
application in forensic science is Raman
spectroscopy, which is based on light
scattering rather than absorption.
• Because of this, Raman spectra provide
complementary information to that
obtained from IR spectroscopy.
• Can be used as a standard method
Pyrolysis-gas chromatography
• Pyrolysis-gas chromatography (P-GC or PyGC) disassembles
molecules through heat (pyrolysis).
• This destructive technique uses the breakdown products for
comparison of paints and identification of the binder type.
• P-GC is influenced by the size and shape of the samples
and instrument parameters, such as rate of heating, the
final temperature, the type of column, and gas flow rates.
• This can make P-GC vary from day to day and sample to
sample; this has several methodological implications.
• The conditions from one analysis to the next should be the
same and should be run very close in time to each other.
• It is important to select the known samples as carefully as
possible because of the influence of size and shape on the final
chromatographic results.
 Pyrolysis-gas chromatography
cont.
• As little as 5 to 10 micrograms of sample are
required for PGC.
• The patterns of peaks in the known and questioned
sample chromatograms (also called “pyrograms”) are
compared, and the peaks must coincide for the
identification to be determined.
• If the instrumentation is available, pyrolysis products
may be identified by pyrolysis gas chromatography-
mass spectrometry (PGC-MS).
• The resulting reconstructed total ion chromatogram
may help to identify additives, organic pigments,
and impurities in addition to binder components.
 SEM/EDS
• One of the most generally useful instruments in forensic paint
analysis is the scanning electron microscope outfitted with an
energy dispersive x-ray spectrometer (SEM/EDS).
• SEM/EDS can be used to characterize the structure and
elemental composition of paint layers.
• The SEM uses an electron beam rather than a light beam and
changes the nature of the information received from the paint.
• The electron beam rasters over the area of interest; the electrons
interact with the sample and generate a variety of signals,
including surface information (secondary electrons), atomic
number (backscattered electrons), and elemental information
(x-rays).
This SEM image shows a sample of paint
taken from the entrance lobby of the
Osborne House on the Isle of Wight,
bought by Queen Victoria in 1845. The
paint samples were mounted in resin and
polished to show the successive layers of
paint in cross-section. Since the raw
materials used to produce paints have
varied with time, the analytical
information can be used to work out
which paint schemes are contemporary.
The image was taken in BSE mode.
• Mapping of elements across the cross-section of a
multi-layer paint can be useful for explaining or
demonstrating elemental distributions and
elemental associations.
• Another technique that provides good visualization of
elemental differences is atomic number contrast with
backscattered electrons imaging.
• These images can be used to characterize and
compare the structure of paints, including layer
number, layer thickness, distribution and size of
pigment particles, and the presence of contaminants.
• Mapping can also be done using ATR-FTIR mapping.
 Paint Database
• The Paint Data Query (PDQ) project is run by the Royal
Canadian Mounted Police (RCMP) and stores the data from
many databases, such as that of the FBI, the German Federal
Police (BKA), the European Forensic Institute, and the
Japanese National Police.
• Forensic laboratories can obtain the data by participating in
PDQ by submitting fifty automotive paint samples per year,
with some rare entries earning “double points.”
• The database contains information on layer structures,
primer colors, binders, pigment chemistry, and topcoat
chemistry, in both visual and spectrometric formats.
• The technical liaison between participating agencies in PDQ is
the Scientific Working Group for Materials Analysis Paint
Subgroup, an FBI-sponsored group of subject matter experts.