J. Forens. Sci. Soc. (1976), 16, 69.

The Mechanism of the Restoration of

Obliterated Serial Numbers by Acid Etching
J. I. THORNTON
Department of Biomedical and Environmental Health Sciences, School of Public Health,
University of California, Berkeley, California, 94720, U.S.A.
and
P. J. CASHMAN
Department of Criminal Justice Administration, California State University at Sacramento,
Sacramento, Calfornia, 95819, U.S.A.
The mechanisms involved in the restoration of obliterated punch marks is discussed in
relation to the chemistry and physics of steel.
Introduction
A review of the forensic literature reveals a paucity of information pertaining
to the mechanism by which obliterated serial numbcrs or other markings are
visualized by acid etching. Although a number of papers describe the efficacyof
various etching reagents (Forbes, 1939; Law, 1944; Nickolls, 1956; Mathews,
1972), few attempts have been made to explain the restoration phenomenon
in terms of the chemistry and physics involved.
O n the other hand, there is at least one article (Paholke, 1969) which con-
tains an erroneous explanation of the restoration process. I t is the purpose of
the present work to clarify certain points in the matter of the restoration of
obliterated marks by means of acid etching.
I n the article referred to previously (Paholke, 1969), it was asserted that the
obliterated serial number is visualized because the metal nearest the number is
"work-hardened" or "cold-worked" and is not as susceptible to the action of
the etching solution. According to this explanation, the etching treatment
therefore results in an escarpment of harder metal in the vicinity of the obli-
terated mark projecting bcyond the background of the unaffected metal. The
number, presumably, is visualized by means of shadow and relief effects.
Unfortunately, this explanation is not in consonance with the chemistry or
physics of the etching of metals. Perhaps our intuition would suggest to us that
the cold-worked (and therefore harder) metal would be less susceptible to the
action of the acid. I n reality, however, the opposite occurs. The phenomenon
of relief does play a r81e in the visualization of a restored number, but in a
subtlc fashion and not as a projection of structure from the background.
The Effects of P u n c h M a r k i n g Metal
When a serial number is punched into metal, a plastic deformation occurs.
(The term plastic is used here in the engineering sense to indicate a permanent
deformation). The impression remains even though the force causing it has been
removed. I n this way, the metal is permanently strained in the area which has
been compressed. This strained area extends for a considerable distance
below the surface of the punched mark. I n pure zinc the affected area may be up
to 20 times the depth of the impression (Kehl, 1943), while in steel the affected
area may be approximately 6 times as deep as the stamped mark. When plastic
deformation occurs a t a temperature below the recrystallization temperature
of a metal, the metal is said to be "cold-worked".
The cold-working process increases the hardness of the metal, its tensile
strength, and its yield point. I t decreases the malleability and ductility of the
metal. Besides these mechanical properties, the position of the metal in the
elcctromotive series is raised, which results in a lowering of resistance to chemical
oxidation in general, and to the actions of acids in particular. The practical
significance of this phenomenon is that the areas of an obliterated mark which
have been affected by the stamping process will be removed (oxidized) by the
etching solution more rapidly than the surrounding metal. I t is not apparent
from the forensic literature that this is fully appreciated, or that its implications
are fully recognized.
Evcry metal or alloy contains irregularities in the atomic structure. The more
common irregularities consist of dislocations, which are a misalignment of
atomic planes, and point defects, which are "holes", or areas in which an atom
is missing. These irregularities are associated with a certain free energy. When
the crystal lattice of a metal is disturbed by a cold-working process such as the
stamping of serial numbers, an increase of internal free energy occurs. This
results in an increase in the electron density in the interstitial space of the
lattice of the deformed metal. The increase in the electron density implies a
certain weakening of the chemical bonds, with a resultant proclivity toward
oxidation (Gubkin, 1960).
In reality, unworked metal contains an enormous number of dislocations,
perhaps as many as 1012 per cubic inch of metal. The process of stamping a
serial number, however, creates a much greater number of these dislocations,
perhaps as much as a millionfold increase (Bunshah, 1968), and increases the
degree of entanglemcnt of dislocations. Along with the increase in the number
of dislocations there is a commensurate increase in free energy. The disruption
of the crystal lattice also results in the formation of somewhat smaller and
chaotically arranged crystals. The atomic bonds are disrupted and reformed,
often in a different manner than before the original forming process. The
process, then, results in what metallurgists call a "change in grain." The
material is still steel, for instance, but a somewhat different sort of steel. Etching
simply enables us to visualize the difference in grain.
Etching of Steel
Steel is a mixture of a number of elements. I t always contains iron and carbon.
Nickel, manganese, chromium, cobalt, vanadium, and molybdenum may be
purposefully included to alter the properties of the steel, while sulfur and
phosphorus are invariably present as impurities. These components are bound
a t the atomic level by specific chemical bonds, which are differentially affected
by chemical reagents. Strong acids, such as hydrochloric or sulfuric, will
rapidly attack the manganese sulphide, leaving voids in the lattice occupied
by the manganese. Copper salts, which are common to many etching reagents
for steel, are reduced to metallic copper by areas of the metal rich in iron or
deficient in phosphorus. The chemical reactions involved follow classical
oxidation-reduction phenomena (Bloor, 1962).
Anodic reaction: FeO-, Fe++ 2e- +
Cathodic reaction: Cu++ + CuO + 2e-
The etching solution does not act in a uniform manner on different faces of
the crystals, or on different areas of the grain. Acid will initially attack the grain
boundaries to a greater extent because they represent regions of higher energy
than the interior of the grains. Upon further etching the grains themselves are
attacked, the rate being dependent in part on the orientation of the grains. An
unworked sample of steel will show a regularity of grain after etching. The sur-
face will appear only slightly and uniformly pitted from the removal of man-
ganese, sulfur and phosphorous. (An exception is steel in the cast form, where
the presence of dendrites is apparent).
The structural detail in the areas affected by the stamping process is revealed
by selective removal of portions of the surface downward, resulting from the
differing rates of solubility of the various constituents of the metal, and the
orientation of the faces of the crystals.
Visualization After Etching
The principal mechanism by which the mark is visualized, however, is
specular reflection. Consider a surface as depicted in Figure 1. A sample of
otherwise homogeneous steel contains a cold-worked area resulting from the

Figure I . Light striking a metal surface after acid etching. The cold-worked area resulting
from the stamping of the serial number is much more disrupted than the surrounding metal,
the etching solution having acted in a differential manner upon the faces of the different
crystals, and having attacked the grain boundaries to a greater extent than the other portions
of the grain. The light striking this area is reflected differently, resulting in a visual image
of the affected area. (In reality many more reflections would be involved due to the fact
that in general practice the light would be polychromatic, and would not be collimated as in
this diagram).

stamping of a serial number. (It is assumed that the serial number has been
ground off previously). The etching has resulted in the selective removal of
certain components of the steel from different faces of the crystals, causing an
irregular surface. The unaffected metal is acted upon by the etching solution,
certainly, but to a lesser extent and in a much more uniform manner. Light
incident on this surface follows the classical laws of physical optics (Crawford,
1965), and will therefore be differentially reflected by the surface. This differ-
ence in reflectivity will delineate those areas of discontinuity, i.e., will show the
grain boundaries separating the affected metal from that which is not affected
I t is this difference in specular reflectivity which is responsible for the image
received by the eye and perceived by the brain, and which permits the restora-
tion of the obliterated number.

References
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