Forensic Analysis of Glass and paint

PRESENTED BY: NASIR JAMAL

Glass and paint as forensic evidence

• In house breaking,automobile
accident,shooting,hit and run cases
glass pieces or fragments are likely
to be found on the clothes, hair,
shoes etc of the suspect.

• Thus glass fragment found on

suspect's clothes can link the
suspect to crime scene.
• Paint evidence is usually encountered
in the form of chips(usually all the
layers of paint) or smears(top layer of
paint) in burglary, hit and run and
other offences against property.

• In case of house breaking case,paint

chip will usually be found on the
clothings, shoes as well as on the
tools used in crime.
 What is Glass?
• Fusion of sand (SiO2), soda (Na2CO3) & lime (CaO)
that produces a transparent solid when cooled.
• A 3D network of atoms which lacks the repeated,
orderly arrangement typical of crystalline materials.

• Physical properties: hard, elastic, brittle, non-

conductor of electricity, density, refractive index, etc.
• Chemical: resistant to all but fluorine and very strong
bases.
 What Types of Glass Are There?
The primary uses for glass are in windows,
containers, light bulbs and eyewear.

• Borosilicate Glass (pyrex): 5% borax (Na2B4O7) is

added to resist breaking when heated or cooled.

• Colored Glass: metal oxides or colloidal iron (Fe) &

sulfur (S) are added to change its color.

• Lead glass: Pb increases refractive index & density

What Types of Glass Are There?
• Flat glass: made by a “float glass process”;
molten glass is floated on a pool of tin while
cooling. Commonly found in doors and windows.

• Laminated glass: used in windshields, two sheets

of glass with plastic between them.

• Tempered safety glass: used in car side windows

and designed to break into tiny pieces; potassium
(K) replaces sodium (Na) on the surface.
 Forensic Examination of Glass

• Goals in examining glass evidence:

– Determine the types of glass at the scene
– Determine how the glass was fractured
– Use physical characteristics to classify it
– Individualize the glass to a source

• Compare physical and chemical characteristics:

– Optical properties: color and refractive index
– Non-optical properties: surface wear, striations
from manufacturing, thickness, surface film or
dirt, hardness, density
– Chemical properties: additives or trace elements
 How Do Glass Windows Break?
• Each force causes a deformation that may leave a
visible mark or fracture the glass. This can be used
to determine the direction and amount of force.

• Glass acts initially as an elastic surface and bends

away when a force is applied. When the force
increases beyond its tensile strength, it cracks.
 How Does Glass Break?

• Radial cracks form first and are propagated in

short segments on the side opposite the force.
• Concentric cracks come later from continued
pressure on the same side as the force applied.
 How Does Glass Break?
• Edges of broken pieces of glass will show
rib (“stress”) marks.

• In a radial crack, the rib marks are

perpendicular to unloaded side and
parallel to loaded side. The arrow shows
the side that received the impact.

• 3R rule:
– Radial cracks give rib marks that make
– Right angles on the
– Reverse side from where the force was
applied
 Exceptions to the Three R Rule

Tempered glass
“dices” without forming ridges

Very small windows held tightly in frame

can’t bend or bulge appreciably

Windows broken by heat or explosion

no “point of impact”
curved, smooth edges at break points
Types of Fractures by Projectiles
• Bullets are a projectile force (load) that can pass
through glass.
– Load side is the entrance side; unloaded side is
the exit side.
– Low-speed projectiles: rib marks may indicate
where breaking force was applied
– As the bullet’s velocity increases, the central hole
becomes smaller, cracking patterns become
simpler, and the exit hole becomes wider than the
entrance hole.
 Fractures by Projectiles
Which side was the bullet fired from?
Exit (unloaded) side
is wider than entry
(load) side.

•Stress lines on the glass edge of radial cracks form a

right angle on the reverse side from the force.
•Stress lines on the glass edge of concentric cracks
form a right angle on the same side as the force.
 Which Bullet Hole Was First?

• The sequence of impacts can be determined since

crack propagation is stopped by earlier cracks.

In the figure above, which impact occurred first?

 Putting it Back Together Again?
• Examiners can fit together two or more pieces of
glass that were broken from the same object.
• Because glass is amorphous, no two glass objects
will break the same way.
 Learning Check

In the figure below & left, which impact occurred

first?

In the figure above & right, from which side did the
impact occur?
 Collection of Glass Samples
• The glass fragments should be packaged in boxes
to avoid further breakage.

• If evidence is to be examined for glass fragments, it

should be taken whole and each item individually
wrapped in paper and boxed.

• If even the remotest possibility exists that glass

fragments may be pieced together, every effort
must be made to collect all glass fragments.

• Submit glass evidence along with a representative

sample of each type of glass from the crime scene.
Quantitative Properties of Glass
 Why Measure Density?
• Can be used as a screening technique with large
numbers of fragments.

• Useful in identifying multiple sources present in the

known and/or questioned samples.

• It is nondestructive and an intensive property (not

dependant on sample mass).

• Need to measure very precisely in parts per

hundred or thousand or better.
 Glass Density
• Density can be measured by:
• directly determining mass and
volume (usually by displacement)
• comparison by flotation
• comparison using a density gradient
column

• Density gradient column method:

• Fragments of different densities
settle at different levels in the
column of liquid of varying density.
• Technique is not accurate for
fragments that are cracked or
contain an inclusion.
 Density by the Flotation Method
• A glass particle is immersed in a liquid. The density
of the liquid is adjusted by the addition of small
amounts of another liquid until the glass chip
remains suspended.

• At this point, the glass will have the same density

as the liquid medium and can be compared to other
relevant pieces of glass which will remain
suspended, sink, or float.
 Why Measure Refractive Index?
• Refractive index: ratio of the velocity of light in a
vacuum to the velocity of light in any other medium

• For example, at 25oC the refractive index of water is

1.333. This means that light travels 1.333 times
faster in a vacuum than it does in water.

• Like density, refractive index is an intensive

property but it can be measured very precisely
(±0.0002) and does not destroy the sample.

• Refractive index of glass varies with small changes

in composition or by how it is manufactured.
 Snell’s Law

N=1.52 N=1.33

The higher the n, the more the light bends

Problems with Refractive Index

The measurement of RI alone can be of limited use

because RI distributions of flat glasses and
container glasses overlap.
Histogram = flat glasses
Curve = container glasses
 FBI Refractive Index vs Density Data

•The FBI has compiled density and refractive index data

for glass from around the world.

•The FBI has identified a relationship between their

refractive indices and densities for 1400 glass
specimens that is better at classification.
 Chemical Analysis of Glass
• Fluorescence
– Under UV radiation, many glasses exhibit
fluorescence (glow)
– Caused by heavy metals (including tin) from
“float” process or organic coatings

• Scanning Electron Microscopy Energy Dispersive

X-ray Analysis
– Can determine many elements simultaneously
– Surfaces of samples (>50 mg) can be analyzed

• Atomic Absorption Spectroscopy

– You must first know which elements are present
– Can analyze ppm levels of elements present
Quantitative Properties of Glass
The Wave of the Future: Laser Ablation

• Laser Ablation Inductively Coupled Plasma Mass

Spectrometry (LA-ICP-MS)
– Laser burns off a microscopic sample
– Elements are ionized by plasma
– Detects 46 trace elements and their isotopes
simultaneously in glass at < 1 ppb
A paint is formulated as a mixture of four ingredients.

• Binder (Resin)

• Solvent

• Pigment

• Additives
 Type of binders

• Alkyd resins are prepared by the condensation

polymerization in the reaction of fatty acid and polyols
(commonly glycerol) with polybasic acids.
• Acrylic resins are prepared by polymerization of acrylic or
methacrylic esters.
• Latex (PVA) is a vinyl polymer prepared by free radical vinyl
polymerization of the monomer vinyl acetate.
• Phenolic resins are thermosetting polymers prepared by the
reaction of simple phenol with aldehydes (eg. formaldehyde).
• Urethane resins (polyurethanes) are prepared by the step-
growth polymerization of isocyanates reacting with
monomer molecules containing hydroxyl (alcohol) groups.

• Epoxy resins is a thermosetting polymer formed as a result

of cross-linking a resin containing short molecules in the
presence of a hardener.
 2. Solvents of paints

• Solvent (water or organic solvent) is a medium

where the binder, pigment and additives are
dispersed.

• Solvents (thinners) are also used for modification of

the paint viscosity required for the application
methods e.g. brush, roller, dip, spray.
• Types of solvents
• Water
• White spirits (mineral turpentine spirits). White spirit is a
mixture of saturated aliphatic and salicylic
hydrocarbons.
• Xylene is a pure aromatic solvent having benzene ring
structure in its molecule (C8H10).
• Toluene is also a pure aromatic solvent with benzene
ring structure (C6H5CH3).
• Alcohols (n-butanol, isopropanol) are organic
compounds having a hydroxyl groups (-OH) bound to
the carbon atoms of an alkyl group.
• 3. Pigments

• Pigment is a solid substance dispersed throughout the

coating to
• impart it a color. Pigments may protect the substrate from UV
light.

• Pigments change the paint appearance (gloss level) and

properties.

• Pigments may be natural, synthetic, inorganic or organic.

• Fillers and extenders are also referred to pigments. 

• Pigments commonly used in paints

• Titanium Dioxide (TiO2) :Titanium oxide is the most widely used

pigment.

• Zinc Oxide (ZnO): a white synthetic inorganic pigment

• having refractive index 2.01.

• Zinc Yellow (Yellow 36): known as Zinc Chromate (ZnCrO4).

 4. Additives for paints
• Examples of additives
• Driers accelerate the paints drying (hardening) by catalyzing the
• oxidation of the binder.
• Plasticisers: increase the paints flexibility.
• Fungicides, Biocides and Insecticides: prevent growth and attack
• of fungi, bacteria and insects.
• Defoamers: prevent formation of air bubbles entrapped in the
coating.
• UV stabilizers: provide stability of the paints under ultra-violet light.
 PAINT:
• Coating consisting of

• Pigments

• a polymeric film former (binder)

• a suspending medium or solvent

• 3 classes of paint

• Oil based
• Water based
• Solvent based ( varnish)
 Paint is an example of trace
evidence
• Transferred by:
• Car accidents
• Car-car
• Car-victim
• Wet paint leaving a mark or imprint
• Microscopic transfer on to a tool used to commit a
crime
• Ex: crobar used to break open a door
Paint is an example of trace
evidence

• Analyzed by:
• Layers of a chip
• Ingredients
• Custom coloring
• chromatography
 Paint is a mixture
• Pigment (color)
• Blues and greens are organic
• Reds, yellows, whites: inorganic
• Modifiers (change pigment)
• Control the property of the paint
• Gloss, flexibility, durability, toughness
• Extenders (keep pigment)
• Add bulk and covering capacity
• Inorganic
• Binders (help paint stick to the
surface)
• Natural or synthetic
• Stabilizes the mixture
• Forms a film when spread
• Which layer of paint is most
informative?
• Undercoat more than any other
property, gives paint its most
distinctive forensic characteristics.
• contains most pigment
 Collecting paint from a crime
scene
• Found on a variety of objects
• Clothing
• Vehicles
• Tools
• Furniture
• Mixed with dirt or grease
• Undermost layer is the most informative
• Matching chips with flakes individualize evidence
therefore preservation is extremely important
• Use of dental drills and scalpals are the most often used
tools
 Paint analysis

• Electron microscopy
• Inorganic pigments
• Excellent for single, top layer analysis and paint
smears
• UV-visible spectrophotometry
• Must be able to separate pigment from film
former and dissolve it
 Analysis of paint

• FTIR
• Will determine type of film former
• Does not show pigments unless they are
organic
• Is a bulk method: if more than one layer
is present, IR will be a composite
 Paint analysis

• Solubility
• Use solvents such as acetone,
dichloromethane, pyridine. Acrylic
lacquers are soluble in acetone
• Pyrolysis GC
• Analysis of film formers
• Bulk technique, all layers analysed together
 Paint chip and flake analysis

• The number of layers is determined by

variety of microscopic technique
• Compare flakes to known or control
samples easiest technique is to match
fractured edges to an area of paint loss
• Investigators use light microscopes,
stereomicroscopes and sometimes scanning
electron microscopes to look for jigsaw fits
 Analysis of paint

• Stereoscopic microscopes
• Compare known specimens
• Color
• Surface texture
• Color laying sequence
• Layers of different colored paint are very helpful
in matching an unknown to a known sample
 Analysis of paint

• Micro-spectrophotometry

• Helps determine nature of pigments by reflecting light

through them

• Infrared spectrometry: determines organic components

• X-ray powder diffraction determines microcrystalline

components
• Top four: cross sections of different samples and
underlying layers of red paint of different red
automobiles

• Bottom Four: cross sections of common red

household paint
 Pyrolysis
• Pyro: Fire
• Lysis: to break
• Gas chromotography
• Chromotography: separates paint
according to color

• Paint is vaporized and injected into a gas

chromotograph which separates paint
into its components