Ink Analysis

The Different Classes of Inks

The inks most commonly encountered on documents
today are writing inks and printing inks [1, 2]. Writing inks can subdivided into at least four classes the
thick (high viscosity) inks such as those used in ballpoint pens; the fluid (less viscous) inks such as those
used in rolling ball, porous plastic nib, extruded plastic tip, and felt/fiber tip pens; the gel inks; and other
inks such as erasable, dry erase, and crayon inks.
Printing inks can be divided into at least two
classes those used in impact printers such as
printing presses and typewriters and those used in
nonimpact printers such as desktop printers, photocopiers, and thermal printers. Those used in printing presses include offset, intaglio, letterpress (typographic), gravure, and flexographic inks while those
used in desktop printers include ink-jet inks and laser
jet inks (toners). The toners used in laser jet printers are also used in photocopiers. Black and white
desktop printers use black toners while color desktop printers use color toners (usually cyan, yellow,
magenta, and black, also referred to as CYMK ).

The General Composition of Inks

All inks, including those that date back hundreds of
years, consists of a colorant or mixture of colorants
in a vehicle (sometimes called a carrier, a base, or,
in printing inks, a varnish). The colorants in fluid
writing inks are dyes (dyes, as opposed to pigments,
are soluble in the vehicle). The colorants in viscous
writing inks are mostly dyes but may include some
pigments, particularly carbon black (pigments are
dispersed in the vehicle). The colorants in gel ink
writing were originally colored pigments but now are
a combination of colored pigments and dyes.
The colorants in printing inks are pigments dispersed in a vehicle except in at least the following cases: some color ink-jet printing inks contain
both dissolved dyes and dispersed pigments; some
typewriter ribbon inks contain dyes mixed with the
pigment carbon black in a thick slurry; and thermal
printers use ribbons containing thermal dye deposited
on a film (the printing process is referred to as thermal dye transfer).

The vehicle or carrier of any ink consists mostly

of a solvent or mixture of solvents and other components. For example, ballpoint pen inks contain
solvents like 2-phenoxyethanol or benzyl alcohol or a
mixture of these along with resins that thicken the ink
(resins give body to the ink and assist in making the
colorant adhere to the surface). They may also contain other components, albeit at a much lower level,
such as humectants or corrosion inhibitors. Ballpoint
pen inks consist of approximately 25% dyes, 50%
solvents, and 25% resins.
In printing ink technology, the resin is sometimes
called the binder and one of its functions is to get
the colorants to adhere to the substrate (e.g., paper).
Some binders are film-forming resins such as ethylcellulose and nitrocellulose (used in screen printing
inks) [3]. Some minor (i.e., low concentration), but
critical components of printing inks are the drying
agents.

The Reasons for Performing Ink Analysis

The forensic scientist analyzes inks for at least three
reasons:
1. to determine if two inks are the same or different
(and if they are the same, how rare or common
the ink is);
2. to determine the origin, source, or manufacturer
of an ink; and
3. to determine the date of an ink (either when
that ink was first produced or, ideally and much
more difficult, when that ink was placed on
a document).
All these determinations, except one, require the
use of reference standards. The one exception is when
inks being compared are found to be different.
Of the three determinations, the most commonly
performed is the comparison of inks; however, the
one has received the most attention due to its
difficulty is the dating of inks, particularly writing
inks. There are three progressively difficult levels of
doing this.
The first is to determine the date of the ink by
following when major changes in ink formulations
first occurred (e.g., the introduction of glycol-based
ballpoint pen inks, of copper phthalocyanine dyes
in ballpoint pen inks, of water-based inks, and
of gel inks). For this, the ink is compared with

Ink Analysis

reference standards representing historical changes in

ink production. One often consults a table of such
historical changes [1].
The second is to determine the first manufacturing
date of the ink or when certain components were
first used in ink. For this, the ink is compared with
a comprehensive collection of reference standards
(discussed below).
The third, and most challenging level, is to determine when the ink was placed on a document. One
approach to estimate the age of a single ink entry
is to compare the ink with itself before and after
inducing age (e.g., by heating). Another way is for
the questioned ink to meet a stringent, but important
requirement; namely, that it be on a document bearing
ink entries of known dates and made with the same
ink formula as that of the questioned ink. If this is
met, then one can determine the relative age of these
inks and, depending on the known dates of the other
entries, find date bounds that bracket the age of the
questioned ink. Both the estimated age of a single ink
entry and the relative age of inks entries (of the same
formula and on the same paper) are discussed below.

The Need for Reference Standards

On the basis of the discussion above, not much can
be done (other than to say that two inks are different) without the use of reference standards. For
writing inks, dried samples of different formulae can
usually be distinguished by a set of established analytical procedures [4, 5]. Samples of different batches
of the same writing ink are normally indistinguishable
by this set of procedures. This is because the manufacturing of writing ink requires strict adherence to
its formula (recipe); any deviation can cause the ink
to fail in its performance (e.g., in the way the pen
writes). Writing ink formulas are also meant to be
stable over the average lifetime of their use, particularly if they are in a container such as a cartridge.
However, such inks tend to age (fade, decompose,
etc.) after they are placed on paper, exposed to the
elements. Andrasko and Kunicki [6] also observed
that some aging (ink drying and dye decomposition)
occurs near the tip of a ballpoint pen. For nonwriting inks, particularly for ink-jet inks, thermal printing
inks, and toners, the same approach of collecting different formulations is normally taken for building
reference collections.

There are two types of reference standards:

requested standards and acquired standards.
Requested standards are those that are obtained
from ink manufacturers through formal requests and
acquired standards are those obtained from pens, ink
samples, etc., acquired, for example, from stationery
stores, businesses with promotional pens, or personal
collections of pens or pen writings. When requesting samples of different ink formulas from the ink
industry, one always asks about the existence of formula variations via component substitution and, if
any exist, requests to see these samples if differences
can be found at the forensic laboratory level (using
the established set of analytical procedures).
The forensic laboratory of the United States Secret
Service has the largest collection of reference samples
of writing ink formulas in the world. It is known as
the International Ink Library. Yearly, this laboratory
solicits samples of new, improved, or changed ink
formulas from the ink industry in the United States
and most of those abroad. As of 2007, the collection
consisted of over 8500 inks. It consists of four
parts: the company files which contain manufacturing
information such as the first date of production of
inks; the ink samples which may be in bulk, in
cartridges, or in writing; the scribble sheets which
contain the dried ink on paper; and the thin-layer
chromatograms (TLCs) which separate their dye
content.
It is critical that this collection be maintained up
to date in order to make forensically significant statements about what a match between a questioned ink
and a standard reference ink means [4, 5]. If a questioned sample, for example, is matched to a reference
standard, then one cannot eliminate the possibility
that the questioned sample is the same as the reference standard. By a match between A and B is meant
that their analytical profiles (determined using a given
set of analytical procedures) are indistinguishable.

Features That Do Not Tend to Change

with Age
Ink formulas in closed systems (e.g., cartridges) tend
to be stable over the lifetime of the inks use. Once
they are exposed to air and allowed to dry, certain features change with age (covered below), but
others such as their elemental profiles, optical properties, and certain colorants are more resistant. The

Ink Analysis
dried inks on the scribble sheets are sufficiently stable
to be used for comparisons (their stability is nevertheless periodically checked). The established set of
analytical procedures used to distinguish these inks
[4, 5] provides the analytical profile of these inks.
These profiles consist of three parts: the physical,
the optical, and the chemical features of the inks.
The physical features include the type of ink (i.e.,
one determines whether the ink comes from a ballpoint pen or a nonballpoint pen), a feature readily
determined by observing the appearance of a written line under magnification. The optical features
include the inks color, near infrared absorbance, near
infrared luminescence, and ultraviolet fluorescence.
The chemical features include the inks thin-layer
chromatogram viewed under visible light, ultraviolet
radiation, laser illumination (with filtered viewing),
and in the near infrared luminescence mode.
There are two levels of TLC examinations: the
library search level (level 1) and the higher resolution level (level 2). The first involves TLC plates that
are highly reproducible (due to their low sensitivity
to changes in ambient or developing chamber conditions), but, as a trade of, have low resolution. These
are used for developing the fourth part of library (the
TLCs) and for searching the library for matches via
plate-to-plate comparisons. The second involves TLC
plates that are highly discriminating (high resolution),
but are also sensitive to external changes. These are
used to further discriminate inks that were indistinguishable at the library search level; this is done via
within-plate comparisons.
To address the comparison, sourcing, and dating
of an ink using a collection of reference standards,
one first obtains a (level 1) analytical profile of the
ink (this requires removing inks for TLC examination). This profile is compared with those from inks in
the collection. All those that match (i.e., are indistinguishable) are further sorted by removing additional
sample from the questioned ink and from the scribble sheets corresponding to the matching standards
and performing the level 2 examination in a single plate. If a single match is found, the questioned
ink is said to bear the same characteristics (at the
given level of examination) as the matching standard and, therefore, cannot be eliminated as being that
ink. The match approaches an identity as the collection becomes more complete and the set of analytical
procedures become more discriminating. If there is

information from the manufacturer of a unique component (that no other ink has), then the match is an
identity. The unique tagging of inks assists in this
endeavor [1].

Features That Tend to Change with Age

Once ink is exposed to the elements, then, like paints,
they begin to dry [7, 8]. This drying process primarily
involves the evaporation of solvents, but it can also
involve the oxidation of resins, the penetration of the
ink into the paper, and possibly other interactions
of the ink with the papers chemistry and physics.
Overtime, there could also be natural degradation of
ink dyes or degradation induced by heat or light.
Aginsky [9] found that inks that contain high boiling solvents and a binder such as a resin (even at
low levels) have the property that their solvents do
not readily evaporate. In essence, as such an ink dries
via solvent evaporation, it thickens and its solvents
evaporate more slowly. Thus, solvent evaporation
along with ink setting is the major aging process in
ballpoint pen inks that is currently extensively studied. This drying process affects several measurable
features (aging parameters) such as how much ink
solvent remains in the ink, how much ink solvent is
extractable into organic solvents of varying strength,
and how fast and to what extent the ink dyes are
extractable into weak extracting solvents. The section
below summarizes some of these and those due to dye
degradation. It should be noted that these can be used
for determining the relative age of inks (where several
inks of the same formula and on the same document
are compared for their age) and the estimated age
of a single ink entry; the latter usually involves the
accelerated aging approach (where two samples of
the same ink, one of which is heated, are compared).
To be useful (e.g., for comparing inks of different
age), these measurements must have no dependence
on the amount of ink sampled. One way of achieving
this mass invariance is to take ratios of measurements
(e.g., measurements of the same sample at different
wavelengths, retention times, temperatures, etc.) each
of which depends linearly on the same amount
sampled [2]. Furthermore, to determine if two inks
are of the same or different age, one needs to
make multiple measurements, average these, and
use statistical methods such as significance tests to
determine if there are significant differences between
the two means (averages) or not [1, 2].

Ink Analysis

Sketch of Some Ink Aging Parameters

Aging Process: Solvent Evaporation plus Ink
Setting
Extraction of ink volatile components into a
solvent

Vehicle-to-dye and vehicle-to-vehicle ratios [10].

Percent extraction of solvents into a slow extracting solvent (compute difference between an
unheated and heated ink specimen, each followed
by a fast extracting solvent and the results are
ratioed in such a way that a percent extraction
into the slow extracting solvent is obtained) [9,
10]. Comment: This mass invariant method is the
one most studied and used by Aginsky. To estimate the age of an ink, he implored the induced
aging approach using heat.
Amount of solvents extracted into a fast extracting solvent (compute percentage of solvent loss
when comparing an equally sampled unheated
and heated sample) [912]. Comment: Gaudreau
and Brazeau [12] modified this Aginsky method
by removing the ink sample from the cuvette
before sampling the extract (i.e., the cuvette is
free of the sample). This method is not mass
invariant so equi-sampling is imperative.

Direct measurement of ink volatile components

Thermal desorption of ink solvents (using solid
phase microextraction SPME) [13, 14]. Comment: Andrasko [14] used a SPME holder as his
thermal desorption device and used it to characterize inks. This simple device can also be used to
make mass invariant measurements for example,
by measuring the same sample at two different
temperatures and taking a ratio of these.
Extraction of ink (or of individual dyes) into a
weak solvent: [1, 2, 7, 8, 1517]
Rate of extraction
Extent of extraction
Time to extract X% (e.g., 90%) of ink (or a dye)
Comment: The changes that this approach measures cease after three to four years while those
of the mentioned above cease after one to two
years.

Extraction of nonvolatile and noncolored vehicle

components
Solvent extraction [10]
Thermal desorption using SPME [18]. Comments:
Bugler et al. [18] characterized inks via their resin
(which volatilize at high temperature) and solvent
components; however, it can also be used to
make mass invariant measurements (see comment
above regarding the use of SPME by Andrasko
[14]).
Surface reflectance vs. subsurface reflectance
using polarizing light microscopy [11]
Comment: This surface vs. subsurface reflectance
phenomenon is based on the ink drying (solvent
evaporation).
Discoloration of ink when exposed to gaseous
organic bases [10]
Comment: In this reversible phenomenon, as the
ink ages (solvent evaporates) the ink becomes
more resistant to discoloration.
Ratio of infrared peaks [19]
Comment: The changing infrared peaks involve
the OH, CH, and CO groups and are believed
to be from the evaporating solvent. For the ink
studied, the ratio of these changes seems to cease
after 10 to 20 years.

Aging Process: Dye Decomposition

Follow the demethylation process
Crystal Violet Methyl Violet Tetramethyl
Para Rosaniline others. Comment: Using high
performance liquid chromatography (HPLC),
Andrasko [20, 21] observed dye degradation for
inks exposed to light, but also for inks stored
in the dark (albeit the rate is slower). Using
desorption ionization mass spectrometry (MS)
Grim et al. [2224] explored similar changes.
Other who have applied desorption ionization MS
include Weyermann et al. [25] and Ifa et al. [26]
who basically used it to characterize inks.

References
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Cantu, A.A. (1995). A sketch of analytical methods

for document dating, part I. The static approach: determining age independent analytical profiles, International
Journal of Forensic Document Examiners 1, 4051.

Ink Analysis
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