Ink and Paint Analysis

Paint Analysis
 Scope of Paint Analysis
• Paint is an important evidence material, commonly encountered in cases like
motor vehicle accident, theft, burglary or house breaking offences etc.

• Intact paints on houses or machine are also required to be examined at crime

scene.

• Evidentiary value of paint increases, whenever it is recovered from a suspect

vehicle of a hit and run cases, shoe or clothing of an accused person or from
suspected house breaking implements.

• Paints are usually received in the form of flakes, chips, powder or smears.

• Forensic examination of paint can reveal the possibilities and situation under
which paint transfer has taken place from one surface to another.

• Comparative study of two or more samples by various techniques can identify

whether the samples have originated from a common source.
 Paints
• Paint is a coating applied to the surface in form of a
liquid dispersion, which is then hardens forming a solid film.

• The functions of paints:

1. Protection of the part surface from the environmental factors

(Oxygen and other chemically active gases, moisture, dissolved salts
and other chemicals, temperature, bacteria, fungi). Corrosion
protection is the most important function of paints.
2. Aesthetic appearance provided by the paint color and sheen (eggshell,
satin or gloss).
3. Providing a desired ability of reflection-absorption of heat and light.
4. Changing the surface properties: ant-friction, hardness, electrical
conductivity.
5. Identification of products according to the color of the paint.
1. Paint - colored non-transparent protective coating.

2. Varnish - transparent or semi-transparent protective

coating.
– A varnish is made of binder, solvent and additives. Some
varnishes contain small amounts of pigment.

3. Enamel - hard protective coating with glossy finish.

4. Primer - the first coating applied to the surface in order to

enhance the adhesion of the final paint (topcoat) and to
seal the substrate surface.
– Primer may be formulated to impart additional protection to
the substrate (eg. anti-rust primer for steel substrates).
 Paint is composed of

• Binder
• Solvent
• Pigments
• Additives
 Binders
• Binder is the main ingredient of paints.

• Binders are polymers (resins) forming a continuous film on the substrate

surface.

• Binders are responsible for good adhesion of the coating to the substrate.

• The binder holds the pigment particles distributed throughout the

coating.

• The binder is dispersed in a carrier (water or organic solvent either

in molecular form (true solutions) or as colloidal dispersions (emulsions
or sols).
 Common 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.
• Chlorinated rubber is prepared through polymerization of the degraded natural
rubber (in the presence of atoms of chlorine participating in cross-linking.
 Solvents of Paints

• Solvent (water or organic solvent) is a medium where

the binder, pigment and additives are dispersed
in molecular form (true solutions) or as colloidal
dispersions (emulsions or sols).

• Solvents (thinners) are also used for modification of

the paint viscosity required for the application methods:
brush, roller, dip, spray.

• The solid coating is formed due to evaporation of solvent

 Common Solvents
• Water

• White spirits (mineral turpentine spirits). White spirit is a mixture of is a

mixture of saturated aliphatic and alicyclic 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.

• Ketones is an organic solvents, in which carbonyl group (C=O) is bonded to

two other carbon atoms.
 Pigments of Paints
• Pigment is a solid substance dispersed throughout the coating to
impart it a color, opacity (hide the substrate surface).

• Pigments may protect the substrate from UV light.

• Pigments change the paint appearance (gloss level) and properties:

increase hardness and decrease ductility.

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

• Fillers and extenders are also referred to pigments.

– Fillers and extenders are non-expensive commonly natural inorganic
materials added to the paint in order to increase its volume, to increase
the paint film thickness, to impart toughness or abrasion resistance to
the coating.
– Titanium Dioxide (TiO2) is a white synthetic inorganic pigment existing in two crystalline forms:
rutile and anatase. Titanium dioxide has high refractive index (anatase 2.52, rutile 2.76). Anatase is
photochemically active but provides clear white color therefore its main application is interior
paints. Photochemically inert rutile is used for protection of paints from degradation by light.
Titanium oxide is the most widely used pigment.
– Zinc Oxide (ZnO) is a white synthetic inorganic pigment having refractive index 2.01.
– Zinc Yellow is Zinc Chromate (ZnCrO4).
– Chrome Oxide Green is olive-green inorganic pigment with a high level of opacity. Chrome Oxide
Green is the most stable green pigment.
– Phthalocyanine Green imparts green-blue color. It is used as the pigment for decorative
applications. The pigment is resistant to heat, solvents and alkalis.
– Phthalocyanine Blues are widely spread pigments. They provides a wide spectrum of color: from
reddish-blue to yellowish-green. The pigments are non-toxic and resistant to solvents, chemicals
and elevated temperatures.
– Ultramarine Blue is natural pigment made of the semiprecious mineral lapislazuri. The pigment is
resistant to fading. It is stable at elevated temperatures.
– Vermilion is a natural orangish red pigment consisting of toxic mercuric sulfide (HgS).
– Pigment Brown 6 is red inorganic pigment based on Iron(III) oxide (Fe2O3).
– Red 170 is a synthetic organic pigment widely used in automotive industry.
– Dioxazine Violet is organic synthetic pigment.It is non-toxic and has high tinting strength.
– Carbon Black is the pigment obtained from organic materials (wood, bones) by charring (thermal
decomposition in a limited amount of Oxygen). large quantities of Carbon Black are used for
coloring and reinforcing automobile tires.
– Iron (II) Oxide (FeO) is inorganic black pigment.
 Additives for Paints
• Additives are small amounts of substances modifying
the paint properties.

1. Driers accelerate the paints drying (hardening) by catalyzing the oxidation of

the binder.
2. Plasticisers increase the paints flexibility.
3. Fungicides, Biocides and Insecticides prevent growth and attack of fungi,
bacteria and insects.
4. Flow control agents improve flow properties.
5. Defoamers prevent formation of air bubbles entrapped in the coatings.
6. Emulsifiers are wetting agents increasing the colloidal stability of the paints in
liquid state.
7. UV stabilizers provide stability of the paints under ultra-violet light.
8. Adhesion promoters improve the adhesion of the coating to the substrate.
9. Corrosion inhibitors reduce the corrosion rate of the substrate.
10. Texturizers impart textures to the coatings.
 Automobile Paints
• Automobiles are painted
with at least 4 layers of
paint formulations.

1) Electrocoat primer
2) Primer surfacer
3) Base Coat
4) Clearcoat

• The composition of each

manufacturer’s paint
layers are
characteristics.
 Electrocoat Primer
– Epoxy-based resins electroplated onto body to
prevent corrosion

– Uniform in appearance

– Color ranges from black to gray

 Primer surfacer
– Originally intended for corrosion control

– Before basecoat

– It smoothes out or hides imperfections or seams

– Color pigments used to prime for color

• Ex. Gray used for pastels
• Red oxide used under dark colors
 Base coat
– This is actually the color of the car

– Integrity depends on its ability to resist weather,

UV radiation, and acid rain

– Acrylic based polymer comprises binder

– Heavy metals like lead and chrome no longer used

in favor now is organic based pigments
 Clearcoat
– Unpigmented coat to improve gloss, durability,
and appearance

– Most acrylic based

– Polyurethane clearcoats becoming popular

• Offers etch resistance and great appearance
 Microscopic Examination of Paint
• Stereoscopic microscope best
– Color
– Surface texture
– Color layer sequence
– 10x-125x magnification
– Not inverted or reversed like regular microscope
– 3d object can be placed in view
– Large objects
 Pyrolysis

• The decomposition of organic matter by heat

• Solids such as hairs, trace fibers, and paints

cannot be dissolved in solvent for normal
GC/MS run.

• Materials like these can be heated or pyrolyzed

into gas at temperatures of 500-750 degree
celcius
Ink Analysis
 Ink
• Ink is a type of colored liquid which is used to produce colored surface
in different fields like a painting image, text or any kind of design.

• Ink is composed of solvents, pigments, dye, resins, lubricants,

solubilizer, surfactant, particular matter, fluoresces and other materials.

• Each component has its own importance to make it more useful.

• However, the Ink formulas vary, but commonly involve four

components:
1. Colorants
2. Vehicles (binders)
3. Additives
4. Carrier substances
 Older vs Modern Inks
• The earliest black writing inks, developed before 2500BC, were
suspensions of carbon, usually lampblack, in water stabilized with a
natural gum or materials like egg albumen.

– The pigment may or may not be colored, and the solvent may be aqueous or
organic.

• Modern ink formulations are rather more complex.

– In addition to the pigment, they contain many other ingredients in varying

levels. Collectively known as 'vehicle', these additional ingredients include pH
modifiers, humectants to retard premature drying, polymeric resins to impart
binding and allied properties, defoamer/antifoaming agents to regulate foam
efficiency, wetting agents such as surfactants to control surface properties,
biocides to inhibit the fungal and bacterial growth that lead to fouling, and
thickeners or archeology modifiers to control ink application.
 Components of Inks
– Pigments (organic and inorganic)

– Dispersants (surfactants and polymers)

– Resins or polymers improve binding

– Humectants retard premature drying

– Defoamers and antifoaming agents

– Wetting agents enhance contact with the substrate

– pH modifiers (usually amine derivatives)

– Biocides and bacteriostats

 Pigment
• A pigment is essentially any particulate solid - colored, black, white or fluorescent -
that alters the appearance of an object by the selective absorption and/or scattering of
light.

• Pigments are the chief constituent of an ink and contribute about 50% of its cost.

• It occurs as a colloidal suspension in ink and retains a crystal or particulate structure

throughout the coloring or printing process.

• Fluorescent pigments have a variety of applications, such as in security inks to prevent

forgery, in traffic light signals, poster boards and advertising.

• Most commonly used pigments in inks are-

1. Azo pigment
2. Copper phathalocyanin blue
3. Quinacridone
4. Diaryl pyrrolopyrrole
 Pigment vs Dye
• Pigment
– A pigment is a dry, powdery substance that must be mixed with a liquid
like water to leave behind black, white or color.
– The pigment is usually water insoluble, but it may remain suspended in
the liquid (much as is the case for a “colloid").
– Pigment particles tend to bond to edges within the chosen medium, a
reason why these inks tend to last longer and resist fading over time.

• Dye
– Dye-based inks tend to be cheaper and water soluble.
– Dye ink generally takes more time to dry and results can be poor if a
drop of water hit a page.
– Colors are brighter because various optical compounds are added to
dye ink to enhance the color.
– However, these compounds have a low resistance to light or to UV rays,
– Fading can be an issue if your document will be exposed to the sun.
 Classification of Inks
• Inks generally fall into three classes:

1. Aqueous

2. Paste

3. Powder
 Types
• Indian Ink-
– It consists of amorphous carbon in the form of lamp black.
– The color may vary from dark-brown to blue-black depending upon the quality of the
lampblack.

• Fountain Pen Ink –

i. Blue-black Permanent – contains iron compounds
ii. Non-staining – doesn’t contain iron salts

• Ball-point Pen Ink -

– This ink is base on polyethylene glycols of suitable viscosity. They are non-hygroscopic.

• Logwood Ink -
– It is obtained by mixing chromium salts with an aqueous extract of logwood chips.

• Iron gall ink –

– A purple-black or brown-black ink made from iron salts and tannic acids from vegetable
sources.
 Scope of Ink Analysis
– Disputed documents/writings

– Counterfeit currency

– Paintings and Reference literature

– Passports/Aadhaar etc

– Graffiti

– Tattoos

– Environmental issues
 Systemic Approach to Forensic Ink Analysis
1. Physical examination
• This includes the optical examination of ink with the help of hand
magnifier or compound microscope to determine:
– The type of ink used (ball point pen, fountain pen or fiber tip etc)
– Color of ink
– Comparison of secondary color shades, ultraviolet rays are used to compare
the degree of fluorescence.
– Infrared rays are used to differentiate dyes and pigments and especially ball
point pen inks.

2. Chemical examination
• The chemical analysis of ink can be conducted in two different ways-
– Preliminary tests: Performing chemical spot tests on the punched out
fragments of ink strokes or on the ink strokes itself.
– Confirmatory tests: Chromatographic analysis for isolation and characterizing
various dye stuff inks.
Chromatographic Analysis/TLC of Inks
• Principle of chromatography:
– Distributes of sample into two immiscible phases (stationary and mobile phases)
which is described by partition or distribution coefficient, Kd.

• Thin layer chromatography (TLC) is most commonly used methods for

separation of ink components and comparisons of various inks.

• For differentiation of two inks, their spots are marked on the same TLC plate
and if these samples show same number of spots with the same Rf values and
colors, then the two inks are identical in their dyes composition otherwise not.

Distance travelled by solute in stationary phase

R f= _____________________________________________________________

Distance travelled by solute in moving phase

 Commonly used Mobile Phases for Ink Analysis

1. Butanol: ethanol: water – 50:15:10

2. Ethyl acetate: cyclohexane: methanol: ammonia –

70:15:10:5

3. Ethyl acetate: butanol: ammonia – 50:35:5

4. Ethyl acetate: ethanol: water – 70:35:30

5. Toluene: acetate: ethanol: water – 30:60:7:2