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The chloride ion diffusion method for the determination of the age of ink writing on documents

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The chloride ion diffusion method for the determination of the age of ink writing on documents

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Content THE CHLORIDE IOH DIFEDSIOH METHOD ?OR THE DBTERMIHATIOH
0? THE AGE OE I HE WRITIHG OS DOCUMEHTS
G
3*'
--------------
A fhe8iB
Presented to
the Faculty of the Department of Chemistry
University of Southern California
In Partial Fulfillment
of the Requirements for the Degree
Master of Seienee
hy
Roger A* Lovett
June 1955
UMI Number: EP41468
All rights reserved
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UMI EP41468
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This thesis, written under the direction of the
candidate's Faculty Committee and approved by
all its members, has been presented to and ac
cepted by the Council on Graduate Study and
Research in partial fulfillment of the require
ments for the degree of
Master of Soienoe
'cretary
Dean
Date...
Faculty Committee
Chairman
Aoknovle dgmente
Shis opportunity la taken to thank hoth
Dr* Paul H. M*-P. Brinton and Mr* Prank
B* (tamper t for their many valuable crit
icisms and augge8tlona*
TABLE 07 OONTEHT8
CHAPTER PAGE
I* STATEMENT AND JUSTIFICATION 07 PROBLEM . • . . 1
Definitions of terms used ......... 8
II, REVIEW 07 PREVIOUS RELATED STUDIES..... 4
III, PREPARATION OF STANDARDS............... 9
Produotion of the chloride and sulfate dif
fusion patterns ........... 13
Writer's method for chlorides ......... 14
Writer's method for sulfates ,,*•••• 15
Method given in Turkel............ . . 15
IV, CONSIDERATIONS 07 THE MIGRATION PATTERNS ... 19
Chloride patterns on standard papers • • • , 19
Paper , ............. 19
Types of pens................ . . . . 88
Blotting • ....................... . . 84
Treatment subsequent to writing... 86
Age • ,••,•••••••••••••• 86
Sulfate patterns on standard papers • • , , 41
V. SUMMARY.............................. A4
BIBLIOGRAPHY.................................. *8
APPENDIX...................................... 80
LIST OF FIGURES
FIGURE BAGS
X* Typical standard paper • . . .............. 12
2. Effect of chloride development on different
papers................................... 18
8* Effeot of age on different exposed writings . . 26
4* Effects of age on different nnexposed writings • £7
5. Effeot of treatment subsequent to writing on
different inks ............... ....... £9
6. Chloride patterns for Sanford's ink writings . •
(faoe) ............. ...... 53
7* Chloride patterns for Sanford's ink writings
(rear) • . . . . ......................... 35
8* Series of ohloride patterns for Carter's ink . . 58
9* Sulfate diffusion development.............. 42
10. Two writings on same paper.............. • • 47
CHAPTER I
STATEMENT ASP JUSTIPIOATIOH OP PROBLEM
Many law trials, both oiril and criminal, have to
do la some way with written documents* In the oiril oases
questions arise as to the true age of a document, whether
or not it has beea altered in some way since the original
writing, etc. In criminal cases someone is usually charged
with haring either falsified an entire dooument or altered
a true document* Sometimes this altering may oonoern the
typewriting, a consideration which is outside the soope of
this investigation. Many questions oaa arise concerning a
written document* A few, for example, are: 1, Is all the
writing done with the same ink, and if not, which is differ
ent? £, Is all the writing of the same age, and if not,
which is older? 2« Is the writing as old as the date indi
cates or as some person says it is?— * All these questions
and many others oan, and hare come up in connection with
actual trials* Experts are usually called upon to giro
their opinions in answer to such questions, and hare done
so with more or less justification* As a basis for their
answers, these experts hare dereloped different methods for
the testing of ink writing to determine age, type of ink,
eto* Some of these methods are purely physical, such as
z
the comparison of the color of an ink at one date and the
color at a later date# Others depend upon chemical reac
tions#
It is the purpose of this investigation to deter
mine, if possible, the limits of error of the prinoipal
ohemioal method for age determination, and then to compare
its efficiency with other methods#
Chloride pattern; or pattern# A deposit of silver
on paper, formed as a result of ohemioal reactions which
precipitate visible metallic silver in the place previous
ly oooupied by the chloride of the original ink stroke.
Sulfate diffusion pattern# Same as above, only
lead sulfide is deposited on paper which previously con
tained sulfates from the ink#
Inner space# Conditions found in chloride patterns
after certain ages# the gradually clearing space occupied
originally by the ink line itself#
Inter space# Space between written strokes of
letters#
Exposed or unexposed# Referring to papers means the
DEFINITIONS OF TERMS USED
inner
sntice
3
subjecting of the papers to the effeots of atmospheric
and climatic conditions.
CHAPTER II
REVIEW 07 PREVIOUS RELATED STUDIES
Those ohiefly responsible for the development and
application of the ohloride and sulfate diffusion patterns
of ink strokes to the determination of the age of ink writ*
ing are Dr. Hugo Rall9 Dr. Walter Hees«v and the late Dr.
Otto Megger.1 Their studies and findings on this subject
have been published in several articles•
The basis for this method is the fact that inks
contain sulfates and chlorides in varying amounts When
one writes with ink on a paper* the liquid penetrates into
the fibers and dries naturally or is blotted.3 The ohlor-
ides of the ink then migrate away from the original ink line
by dissolving in the water layer which surrounds the eellu-
n
lose of the paper. Due to this solution in the water layer*
the chlorides are free to migrate away from the original ink
^Hesger, Otto; Heess, Walter; and Rail* Hfeigo* "Die
ChemiBohe Identifigierung und Alterbestimmung von Tinten-
sohrift." In Tdrkel's* Beitr&ge sur Krimlnallstische Symp*
tomalogie und Teohnik. 1931. p 97.
^Mezger* Rail, and Heess, geitsohrift fur angewandte
Chemie. 44, 645-51, (1931). "Jfeuere Tlntenuntersuohungen.*
0Mezger, Rail, and Heess, Arehiv fur Eriminalogie. 92,
March and April* (1933). "Ein nones Verfahren* Identitat und
Alten von Tintenschriften festzustellen."
5
stroke in all directions, finally reaching the baok side
of the paper* and then spreading out laterally. In the
same way the sulfates migrate, only more slowly.® The
considerations are based on the form of the chloride pat*
terns; that is, whether or not the pattern around the
letters has filled up the inter spaoe of the writing.*
Sinoe judgement does not depend upon the strength of the
ohloride pattern* the migration is not affeoted by the
types of ink and pen* and is almost independent of the
4
paper*
The humidity of the atmosphere affeots the moisture
layer around the fibers of the paper and therefore the mi
gration of the ohloridew. naturally, migration is more
rapid in damp conditions. In a dry* heated room the mi
gration is retarded* while in an unheated room in winter it
is accelerated* The longer the period of time after writ
ing, the less certain is the interpretation of the results.
This migration of the chlorides cannot be falsified because
placing the paper over water causes the outlines of the
pattern to vanish completely* as is not the ease with nat
ural age. Complete wetting destroys both the ohloride and
sulfate patterns.*
*Zeitschrift fur angewandte Chemie. loo, oit.
®Arohiv fur Kriminalosie. loo, oit.
6
The development of the imer space is regarded as
being due to an equilibrium set up between the ink salts on
the paper and the free acid* which tends to force the chlor-
ides away from the original writing. The width of the in
ner space on a ohloride pattern is an Indication of the
migration of the sulfates. Whenever this inner space has
noticeably increased in width over the original ink line*
an old ink is present. Dr. Mesger et give reasons for
the migration of the chlorides of inks* depending on their
type* i.e., whether lron-gallt blue dye* or logwood.6
The conversion of the chlorides of the ink into a
visible substance requires a special proeess. Mitchell is
given credit for suggesting the use of silver nitrate and
sulfurie acid for detecting chlorides in peno11 writing.7
Mesger* Ball* and Heess have developed a technique whereby
the paper containing the writing is treated with a solution
of silver nitrate9 nitric acid* and potassium nitrite to
destroy the dye and fix the ohloride as silver chloride.6
The excess silver nitrate is washed off* and the silver
chloride remaining in place of the ohlorldes is then re
duced to black metallic silver by alkaline formaldehyde.
This procedure was developed because of the very
^Zeltsohrlft fur angewandte Chemie* loo, oit.
^Mitchell* Documents and Their Scientific Examination.
Griffin and Co.* London.
minute amount of substance on the paper ae ink, approxi
mately one-twentieth mg. for a line 1 cm. in length.8
The eulfate of an ink is converted into lead sulfate by
placing the paper in a bath of lead nitrate, nitric aoid,
and potassium nitrite, which also destroys the coloring
matter. She lead sulfate formed is then converted to lead
sulfide with hydrogen sulfide or sodium sulfide. Thus
brown lead sulfide is formed on the area originally covered
by the sulfate of the ink.
There is very little printed matter on this subject
by our American investigators. One article by Cornish is
all the writer could find on the subject. It is very in
teresting to note the two extreme views held by the two
opposed experts in the court oase referred to in the arti-
9
ole. The article la very brief and has for its argument
against the value of the ohloride test the faot that the
chlorides of different inks migrate at different speeds.
B. 23. Cornish states: ”22. 0. Heinrich claimed that
by this test (ohloride diffusion) he oould tell the age of
ink writing within 10 day periods, and that he oould obtain
differentiation within three days, although the originator
^Zeltsohrift fur angewandte Chemie. loo, oit.
^Cornish, Bobert B*; Finn, John, Jr.; and llolaughlin,
William, Ind. Bng. Chem. Hews Bd., 18, 315, (1934). "Age of
Inks as Determined by the Chloride Test".
of the test made no suoh startling claims for it."10
Cornish, et al*» say later in their article: "It
would seem from these tests that the age of an unknown ink
subject to undetermined conditions, cannot be determined by
this test."10
10Cornish# at £l., loo, oit.
CHAPTER III
PREPARATION OP STANDARDS
For a work of this kind, which has for its purpose
the determination of the validity of a test or tests, the
proper controls and standards are of the utmost importance*
As has heen explained, the number of variations of writing
is infinite* Thus, strictly speaking, there ean be no two
identioal writings; even continuous writing made with the
same pen and ink by the same person varies in some degree*
In preparation for the making of these standards,
some time was spent in observing the main oharaoteristies of
ordinary ink writing* As a result, a number of pens, papers,
and inks wezeohosen, which, when combined in various ways,
including the factors of blotting and subsequent treatment,
would give a comprehensive cross section of writing as it
is done today* Briefly, the following items were chosen:
3 types of pen points, 5 types of paper, and 6 different
inks* (For a separate and more complete description of
these items see appendix*)
After all the materials had been collected, there
remained the still more complicated and tedious procedure
of combining the various items to form the standards* As
a result of the previous considerations, five important
10
conditions were found necessary to be taken into consider*
ation: the paper, the pen, the ink, the blotting of the
ink, and the conditions subsequent to the writing.
She system of keeping a record of these considera
tions on the paper is based on the Dewey Decimal system,
in which each variable is given a number, combinations of
these numbers giving the specific conditions of the writing.
See appendix for table.
In considering the pens, it will be noticed that
two extremes have been ohosen: (1) new, or perfectly clean
pens, and (£) old, corroded pens. This was necessary to
include the effects on writing of pens such as are found
in some banks and post offices, where the pen becomes very
much corroded, and the ink changes, due to evaporation and
its solvent action on the iron of the pen. The first time
the standards were written, the pens and inks were all new
and fresh, but after this the old pens were used only with
old ink and allowed to rust in air, being dipped in ink
from time to time to aid this ageing prooess. A new pen
wag not used each time for the writing with a clean pen,
but the same point was washed carefully and dried between
each writing. The fountain pen point was used only with
clean ink; it also was washed and dried between each writ
ing. The old and new inks were from the same bottle, the
old ink being left open part of the time and used only
11
with the old pens*
In making the writings on the paper, a form was de
vised whereby the blotted and nnblotted lines were adjas-
cent, and aU of the writings on any one sheet were Iden
tical except in the faotor of age. Also, one straight line
was drawn across the length of the paper, separating the
writings of different dates, Shis line was Intended to
facilitate the measnraments that were to be made before and
after the production of the chloride pattern. She date
of the writing was placed at the left side, and the index
number indicating the conditions was placed at the top.
She letters B and U indicate which line was blotted and
which was unblotted. In blotting the ink, the following
system was used; the writing was blotted every 4 inches
while writing, which gives 3 sections of writing in which
the degree of penetration into the paper varies only slight
ly. She blotting material used was Whatmans Ho. 1 filter
paper.
Shis form was ohosen to facilitate the clipping of
a strip and inch or two wide from the right end for devel
oping. In this way writings of various ages may be obtain
ed for study. Shus on the photograph of one of these
sheets, we have known waitings which were clipped at var
ious times and developed by the ohloride method, giving
patterns for the following ages: 3 dQys, 7, 17, 89, 55,
Photograph of a standard pap or showing blotted and
unhlotted writing and continuous line (above writing)*
The three dart strips have been developed for ohlor~
ide pattern at date on bottom of strip* White strip
of undeveloped writing is left between developed
strips for comparison*

13
69, 81, 107, 181, 185, 161, 166# A email strip of the
paper was left between the developed stripe for reference
purposes#
As has been explained, two identioal sets were made
for eaoh set of conditions# Then one of these sets was
fcept filed in the darfc# These papers were placed together
immediately after writing and drying, and then placed under
about 3 pounds of dead weight to simulate conditions such
as are to be found in recording volumes, etc#, The other
set was allowed to dry and then was exposed to light and
air to effeot the conditions which exist when papers are
left open on desfc tops, etc#
PRODUCTION 07 THE CHLORIDE AID SULFATE DIFFUSION PATTERNS
As has been stated before, the ohlorides are con
verted directly on the paper into metallic silver# This
is best and most easily accomplished by cutting out the
paper which contains the writing and bathing this entire
section#1 This method has a very great objection: American
courts do not permit doouments in evidence to be defaoed
in this manner# But as this investigation was made to de
termine the errors of the method, it was thought best to
follow the original plan as suggested by the authors#
^Archive fur Nrimlnalogle. loo# oit.
14
It mast be stated here that the procedure for do*
▼eloping the ohloride and sulfate pattern is purely empir
ical, --that is, it is of Talus because it works, any other
method giving the same results being equally valuable. In
faet, the writer had to develop hie own methods before the
article containing the detailed procedure as given by the
authors was found. It is satisfying to note that the two
procedures differed only slightly, and then.only in minor
details. These two methods of treatment were compared, and
probably because he was more familiar with it, the writer
obtained better results with his own. The writer's own
method was used for developing all the ohloride and sul
fate strips used for subsequent examination.
Writer's method for ohlorides. Handle the paper as
little as possible to prevent contamination with the ohlor*
ides from perspiration. Cut the strip from the original
sheet and plaee in the following bath;
1 $ HgS04 1 % HfOg
1 $ HN03 1 $ AgHGg
(by volume of the (by weight)
concentrated aeid.)
The strip is left in this bath for a maximum time of 1
hour. I*es8 time can be used with thin papers and some dyes,
but one hour was ohosen for all the strips developed.
The strip is then plaoed in a bath of distilled
15
water, slightly acidified with nitric acid. It Is washed
for about 1 hoar, changing the water once or twice, fol
lowing this, the strip is placed in a reducing hath of
alkaline formaldehyde of the following mixture:
16 ml. formalin (40$)
10 ml. HaOH (68)
76 ml. H O
100 ml.
Writer's method for sulfates. The strip is out as
before and placed in the following hath:
£ $ HJfQg l#Fb(H03)2
(hy volume of the £ $ HQ©
concentrated acid.)
(hy weight)
It is allowed to remain in this hath for about 1 hour and
then plaeed in a wash hath for 3 or 4 minutes, (lead sul
fate is fairly soluble.) The strip is then placed in a
hath of water saturated with I^S, containing a little 101
or HlOg to prevent iron sulfide ffom forming.
Mreotlons for producing these patterns as given
in Turkol.g for chlorides: Silver nitrate (1$) is added
to a 10$ solution of lalOg until a precipitate of silver
nitrite is obtained, and then made acid with 10$ nitric
dfttrkcl. et al.. on. cit.
acid until the precipitate dissolves again. The piece of
paper is placed in this solution. The chlorides of the ink
will he changed over into insoluble silver ohloride. The
ink body dissolves, and the dye is destroyed by the nltrio
aoid. In about one-fourth hour the ink is destroyed, where**
upon the action is stopped. lext the excess silver nitrate
Is completely washed off the paper with VfL nltrio acid, for
which 5 minutes is sufficient, sprayed with Vf> nitric aoid,
and reduced to silver by a mixture of 1 part formalin
with 10 part8 of BjJ sodium hydroxide. When finished, the
paper is washed many times with distilled water, and dried.
Instead of formalin solution, one can use sodium sulfite,
or alkaline sodium hydrosulfite. The color, however, will
not be so strong. Also a reaction takes place in daylight
which reduces some silver nitrate to metallic silver,
lot sulfates: The piece of paper is treated with a
4# solution of lead nitrate which contains about 4jt free
perohlorlo aoid and a little drop of potassium permanganate.
The sulfate of the ink is changed by this into lead sulfate,
and the dye stuff is destroyed. In a short time the oxi
dation is complete. After about E minutes longer, so that
the iron is completely dissolved, the excess lead nitrate
is then washed off. Because of the considerable solubility
of lead sulfate in water, distilled water which has been
saturated with precipitated lead sulfate is used. Bor
17
the reduction and dissolving of the changed KhOg, a orystal
of hy&rasine dichloride, not sulfate, is placed in the hath.
The paper is then rinsed with distilled water, and the
lead sulfate is changed into dark brown lead sulfide hy a
solution of 8§$ sodium sulfide and 2% sodium hydroxide.
After washing with water the paper is dried.
fignre 2
figure showiag effeot of ohloride development on
different papers* (See append!* for desoription.)
All writing identioal exoept for paper# notice
the relative amounts of diffusion and the forma*
tlon of inner spaoe on the different papers# es
pecially Index 4461.

CHAPTER 17
CONSIDERATIONS OP THE MIGRATION PATTERNS
When each portion of the standard writings reaehed &
predetermined age, it was out, and the strips were developed
acoording to the methods already given. These strips were
then fastened to their original sheet, and were ready for
comparison and examination. The results of these examinations
and comparisons are host divided into sections, each treating
of one speolflo subject. Later a summary will he given, com*
prising the outstanding and signifleant findings.
I. CHLORIDE PATTERNS 01 STANDARD PAPERS
1. PAPER
IOQ# rag hond paper. The process of developing the
ohloride diffusion pattern had less effect on this paper
than on any of the others. The clear parts of the devel
oped strips are in general slightly darkened, due either
to a traoe of chlorides left in the paper, or to sunlight
developing some of the silver nitrate on the paper while
in the first hath. Because of the purity, the diffusion
of the chlorides is most easily seen on this paper, and it
was chosen as the paper from which most of the conclusions
were drawn. After development, darker areas were found
£0
In places on the strips due to handling* because the chlor
ides in the perspiration are left on the paper and are
developed* Care was taken to reduce this effect to a min
imum* Ho appreciable differenoe in darkening appears to
exist between the exposed and unexposed sets* She inner
spaees of the writings on the unexposed set are lighter for
the same date than those on the exposed set*
Z&& rag paper. She developed stripe of this paper
are darkened considerably (see figure £)• She strips from
the unexposed section are all a shade lighter than those
on the exposed section* She sulfate development leaves a
light brown stain showing the presence of sulfate in the
paper* Shis darkness tends to reduce the contrast between
the diffusion pattern and the paper* Also* when the amount
of diffusion of the inks on this paper was compared with
the respective writings on the 100$ rag paper* it was found
to be less in every ease* Shis may be due to a covering-up
effect of the ohhlorides in this paper* obscuring the out
ermost diffusion* She inner space of the strokes on this
paper is not as light as that for the same age on the 100$
rag paper* but the inner space on the unexposed strips of
this paper is lighter in each case than on the exposed*
lumber 1 sulfite paper* Shis paper shows the max
imum amount of darkening upon development* As before* the
81
unexposed set was slightly lighter than the exposed set,
and the inner space was lighter in the nnexposed set* The
limits of diffusion of the chlorides on this paper were
very hard to determine* as can readily he seen in Figure
8. Beyond a certain age, this darkness of the paper so
covers up the weakening chloride pattern that the writing
is no longer risible* Shis may he shown diagramatioally
as follows:
S *
This curve indicate8 in a general way how
the intensity of the ohloride pattern is
inversely proportional to the age* while
the Intensity of the ohlorides present in
the paper remains constant*
Vellum note paper. The ohloride developed strips
of this paper are darkened considerably. The set left
unexposed was lighter than the exposed set9 showing a
greater difference than other papers* Also the white
ness of the inner spaoe was peculiar in this paper* being
whiter than the paper surrounding the writing* The strips
developed for the sulfate reaction were a light brown.
Chemical naner* This paper shows about the same
zz
darkening as does the Humber X sulfite paper* The unex-
posed strips are lighter than the exposed ones, and the
inner spaoe is also whiter when unexposed*
*. TO®6 OF PEHS
There were really five different pen points used9
although two were different conditions of the other two
points* Thus, the largest difference existed between the
so-called stub (index 100), the hall (Index 200), and the
fountain pen point (index 200). (See appendix for explan*
ation of index numbers*) Unless otherwise stated, the
comparisons were made on the 10Q% rag papers*
As was to be expected* the ink writing with the
100 pen is broader than that with the 200 pen* The width
of the line made with the 100 pen varies from !£ to Z times
that of the 200 line, depending upon the ink used and the
pressure applied on the pen when making the stroke* It
was also observed that, with few exceptions, the intensity
of the image left by the 100 pen was greater than that
left by the 200 pen* That is, the image was darker, due
to more Ag on writings of the same age with the different
pens* This is probably due to the 100 pen's allowing more
ink to flow through its nibs for unit distance traveled*
The fountain pen point is a little broader than the 200
point, and because of its construction, gives a thinner
zz
ana ©ora even distribution of the ink while writing*
Therefore the difference between tha blotted and unblottad
original ink stroke is lass with this point because of
this construction* Also the chloride pattern of writing
with this point is less intense than the pattern of writing
with the more flexible steel pens*
the development of the inner space does not see©
to be due to any one specific variable, so it will be
treated here for want of a better place* The width of the
inner space of the lines made by these points seems to be
dependant upon the same factors as the original ink lines*
Thus* the broader the pen point and the ©ore pressure
applied in writing* the broader the ink line and the re*
sultant inner space* In the examinations of the standard
writings, it was found that the width of the inner space
on the oldest was no greater than the original writing*
In fact* the inner space was exactly the same sise as the
original ink line* as ©ay be clearly seen on any of the
photographs showing the inner space* It must be remem
bered here that the oldest of these writings is only five
and one-half months* and that this inner space may increase
in width with age* According to Hessger* Heess* and Ball,
the width of the inner space is dependent upon the amount
of migration of the sulfate, which, according to their
findings* is not noticeable until the ink is at least two
u
years old* Examination showed that there was no perceptible
difference in the width of either the ink lines or the ohlor*
ide patterns of the writings made with the same pen* but with
different inks* The time of appearance and relative white
ness of this inner spaoe for an ink stroke, is dependent
upon several factors, especially the kind of paper, the
type of ink, and the conditions after writing*
3. BLOTTING
The blotting of an ink writing has a very great
effeet on its chloride pattern, which is quite clearly
shown by Figure 3. As has been mentioned in the descrip*
tion of the preparation of the standard papers, a line
was written for four inches and then blotted with filter
paper* This gives an extreme type of blotting, but it
is reproduoeable. The inner space of the ohloride pattern
of the blotted ink writing is a shade whiter than the re*
speotive unblotted writing* The inks strong in chloride,
such as Carter's black and Sheaffer's blue black, show
some diffusion of the chloride pattern in their blotted
writing, but inks weak in chloride content, such as
Barker's washable and permanent blue, show only a very
faint chloride pattern for the blotted writing* The dif*
ferenoe in intensity between the chloride pattern of the
of the blotted stroke of one pen as compared with another
Figure S
Photograph showing difference between writings
identioal exoept for the ink. Shis eet wae ex
posed. Observe that Index 1241 has disappeared
almost completely. Also* observe the differenoe
in pattern between the blotted and unblotted
lines. The inner spaoe formation of 1231 is pe
culiar. Ages are at left; the original strip of
writing is on right of developed strip.

Is Blight hut noticeable, and follows the same variations
as those given in the oonsideration of the anblotted sam
ples.
4. fEmmSKf SUBSEQ0EH5? TO IRIXIM
The effects of this treatment either have been, or
will he described under the various different subjeots*
Briefly, the keeping of a paper in a dark plaoe oauses its
ohloride developed strip to be lighter* the inner spaoe
to appear sooner and beeome whiter, and to slow down the
migration of the chlorides, due to the fact that the paper
in contact with the writing absorbs some of the chlorides,
leaving less on the original paper* Comparison of Figures
3 and 4 will show these effacts better than can be ex
plained in words.
5. AGE
This is the most important consideration, the effect
of age on the migration of the chlorides of an ink* It
was mainly with this determination in view that the work
was undertaken* As in previous considerations of these
standards, most of the conclusions as to the effect of
age on ohloride patterns will be made from the results
found on the 100j( rag paper, unless otherwise stated* For
the purpose of this determination, the writings were made
Figure 4
Photograph same as Figure 3, except that the set
was unerposed* Sotice greater whiteness of ioner
space and lacfc of diffusion* as compared with Fig*
ure 3. The "ghost” pattern on some strips is the
result of chlorides from another paper penetrating
into this sheet. (See text for more complete de~
soription.)

at various intervals, and strips out off and developed in
such a manner that there were twelve different writings
varying in age from 3 to 165 days at the time of develop
ment. It will be remembered that these writings are, ex
cept in one variable, as nearly identical in original writ
ing and subsequent conditions as was possible to make them.
Thus, if age has played a part in the diffusion of the
ohloride pattern, these writings oan be used to observe the
effect. The following is a detailed aooount of the results
as they were observed when the oldest developed standard
was 165 days old. They will be oonsidered according to
the ink. Figure 5 shows the diffusion patterns of the
different inks for four different ages. Figure 4 is the
same as Figure 3, except that it is for the unexposed set.
Sheaffer's Ink. Shis ink contains a considerable
amount of ohloride, as is shown by its very hlaek pattern.
The unblotted three day writing is clear out, although
about one and one-half times the width of the original ink
stroke. It shows no filling up of the inter spaoe. The
7 day writing is still dark, and shows no clearing of the
inner spaoe and only a slight filling is of the inter
spaoe. At 17 days the writing has begun to lose its def
inite outline, and the inter spaoes are filling in, while
the inner spaoe is becoming faintly visible. As the age
Figure 5
Photographs (z Z.5) of standard writings to show
offset of treatment anhaeqaent to writing* All
in same row are identical except for ink. The
writings are all the same age-**125 days* The top
row has been exposed* bottom row has not been ex
posed* but kept filed. Hotice difference in dif
fusion between the two rows* especially for 1141
and 114B.
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30
increases, the inner space becomes increasingly clear and
the interspace becomes filled. At 120 days the inner space
has become relatively clear.
In the oldest writing the chloride has completely
filled in between the letters, but the outer region of
this chloride diffusion still outlines the original writ-
The blotted writing pattern is very faint and does
not show an inner spaoe until 69 days old. There is some
diffusion of the chlorides as shown on some of the older
patterns, but due to its faintness, does not lend itself
to even roughly quantitative considerations.
The unexposed set shows that due probably to the
double cause of the chlorides being absorbed from the
freshly written stroke onto another sheet, and to being
kept in an enclosed place, the ohloride diffusion is great
ly lessened, although still showing a gradual progression
with age. See Figure 4.
There is no apparent difference in the diffusion
patterns of this ink as made with different steel pens.
Writing made with the fountain pen point has the important
difference that since the amount of ink left by this point
31
is less than with the steel point, the ohloride pattern is
less intense* Beoause of this* the amount of diffusion
appears to he less, even though it may not he aotually so*
It is possible to definitely observe, however, that the
inner spaoe olears more rapidly in writing made with this
point.
The time of inner spaoe appearanoe, and final white-
ness, varies so greatly with the type of paper and the oon~
dltions after writing that no useful generalization may he
drawn for any of these inks on paper other than 100# rag*
Sanford's ink* Shis ink does not contain as large
a quantity of ohloride as does Sheaffer’s ink* This is
shown by its less intense ohloride pattern* Beoause of
this lesser amount of ohlorldes, the diffusion pattern is
rather faint, beooming so faint for writings over 150 days
old that its outline can not be easily determined* The
migration takes plaoe at a slower rate than is the oase
with Sheaffer’s ink, as is shown by comparison of the
two inks in Figure 5*
This ink is peculiar in the bshavior of its inner
spaoe; writing only three days old exhibits this clearing
to a very marked degree* If the theory of Mezger, Eeese,
and Ball is oorreot this is due to the sulfates whioh this
ink oontains in a considerable amount*
0 2
She blotted writing of this ink shows* as do the
other inks* a very weak ohloride pattern* As the age of
the ink increases* the visible dlfferenoe between the
ohloride patterns of the blotted and unblotted writing be*
comes less* due to the fading of the pattern of the unblotted.
No diffusion is noted for the blotted ink until it is 125
days old. These conditions may be clearly seen in the
series of photographs in Figure 6.
On the unexposed set there is praotleally no dif
fusion of the dhlorides until the writing is 125 days old.
The Inner spaoe is extremely white and the blotted writing
is very faint.
The steel pens have only a slight effect on the pat
terns* but the fountain pen causes the same characteristic
lessening of oontrast between the blotted and unblotted
writings.
As has been described before* the ohlorldes of an
ink gradually soak through the paper. This is shown on
the strips developed for the ohloride pattern. The rear
of the strips developed for this ink have been photograph
ed and are shown in Figure 7. Notice the fading of the
pattern in the period covered.
Parker's washable blue ink. According to the re
sults obtained with the chloride pattern* Parker's washable
figure $
Photographs (x 2.5) of ohloride diffusion patterns
of Sanford's ink for different ages (1131). Notioe
progression of diffusion and characteristic whiten*
ing of inner space, also the extreme difference in
the patterns of the blotted and unblotted writing.
figure 7
Photographs of rear of above writing. Hoties the
lag in migration due to time necessary for the
chlorides to penetrate the paper. Ages in middle
are the same for both figures*

36
blue ink contains a smaller amount of chloride than do
Sanford*s blue-black and the Permanent blue of the seme
make* This ink exhibits the peculiarity that the chlor
ide pattern disappears before it diffuses to any extent*
This can be seen in Figure 3* The inner space becomes
visible in a little over 107 days* At this time the ohlor-
ides have diffused, but they are so weak that their bound
ary is extremely indistict*
The blotted writing with this ink gives a pattern
for ages up to 70 days* but wilting older than this date
gives no pattern that is recognisable as having been due
to ink writing* The type of pen point has little effect,
except for the fountain pen; with this pen there is little
difference between the blotted and unblotted patterns after
1 month*
On the unexposed set of writing* the chloride pat
terns are much stronger and persist for a longer period of
time* An explanation for this may be that this ink dries
very rapidly and completely, so that it does not penetrate
into the paper with which it is in contact* The pattern
of the blotted writing is still visible after 165 days, al
though rather faded. A little diffusion is noted for the
unblotted writing, but it is so confused with the chlorides
from other inks appearing in the same area that no deductions
can be made*
36
Parker’s permanent bine Quink, this ink oontains a
considerable amount of chlorides, coming between Sheaffer's
and Sanford’s in intensity of pattern* It exhibits the
property of inner spaoe clearing more than washable blue and
Sheaffer's ink, but less than Sanford’s* The inner spaoe is
visible at 3 days, but not clear until about 17 days* The
chlorides diffuse fairly rapidly and do not fade to the ex-
tent of the washable blue* On sheet Ho* 1161 a line was
found whioh was laoking in ink; showing, in the resulting
chloride pattern, whioh is very faint and scarcely diffused,
the effect of the amount of ink on the appearance of the
pattern*
The pattern of the blotted line for this sheet is
faint, although more definite than with the washable blue*
It has not disappeared entirely, even in the oldest writing*
The chloride pattern of writing made with the fountain pen
point differs only slightly in the blotted and unblotted
seotions in ages over 30 days* Otherwise the type of pen
has little effeot.
The unexposed section of this ink shows the same
characteristics as that of other inks, mainly that the
inner spaoe becomes whiter, and the chloride pattern remains
for a longer period of time, especially noticeable on the
blotted writing*
Carter’s permanent black ink* Garter’s ink contained
37
the maximum amount of chloride of any of the inks examined*
It is on the 1X61 paper that the most characteristic and
representative changes take flace with increasing age.
These writings of different ages have been photographed
after enlarging, and the series is given in Figure 8. Con
sidering first the unblotted exposed set we find that the
chloride pattern of the first writing (3 days) is solid
black and clearly defined. At seven days there is slight
if any diffusion but the inner space is becoming visible*
At 17 days diffusion has begun which has filled in between
the dosed lines and the inner spaoe is becoming more clear.
At 89 days the diffusion has not increased a great deal,
but the inner spaoe has cleared considerably. With the
writing 55 days old the inner space is almost clear and
the inter space has begun to fill in. The succeeding dates
Show a continuous and gradual lightening of the inner space
as may be seen by referring to the photographs*
As the ink ages on the paper, there is observed in
the ohloride pattern on the reverse side of these developed
strips practically the same changes as have been recounted
for the front. With thiok. heavily sised papers, the time
of appearance of the ohloride pattern is retarded, and then
the consecutive changes are delayed an amount equivalent to
the retardation* There seems to be no advantage in a con
sideration of the backside of a chloride pattern, except
figure a
Photograph (x £»5) of the series of standard writ
ings for Carter's ink (Index 1161), showing Bigra-
tion of ehlorldes at the different ages* They are
all from the exposed set and are identical as far
as possible* The white strip at the left in eaeh
photograph is the original writing*
39
perhaps in the determination of a very fresh writing on
very thick paper before the chlorides have penetrated through
the paper.
The above consideration has been for the unblotted
writings. The chloride pattern of the blotted writing is
extremely different. The most apparent difference is the
lack of intensity. This may be clearly observed in the
photographs. Considering the three day writing, the pattern
is very weak and the inner space is visible. It Is to be
remembered in considering these writings that the blotting
conditions were extreme, so that actual conditions would
vary between the two conditions of blotting and not blotting
as shown on the above mentioned photographs. There is
found, however, a diffusion of the chlorides, scarce as they
are. whioh first becomes noticeable at 81 days. At the
subsequent ages we find more diffusion patterns whioh seem
to show a continuous filling in of the inter spaces, but
whioh are really too faint to be definite. This is another
hasard to the exact determination of the date of a writing.
There seems to be little or no difference between
the chloride patterns of the writings made with the two
conditions of the steel stub pen. With the dean ball pen,
a less intense pattern is noticed and also a slight retard**
ation of the diffusion as can be seen by examining the
inter spaces of the writings of the same ages on sheets
40
1X61 and 1361. The patterns of the used hall pen are seem
ingly more intense than those for the clean point. This
may he explained hy the fact that an old corroded pen can
hold more of a head of ink and so allow more Ink to flow
onto the paper. The fountain pen here again leaves its
characteristic effect of a less Intense patternf and little
difference between the unblotted and blotted writings after
a short time.
On the unexposed set we find that as usual the chlor
ide patterns are less intense for the same age on the ex
posed set, although this ink is still considerably darker
than other inks on the unexposed sheets. Also, it is very
easy to see that the diffusion precedes at a definitely
slower rate than it does on the exposed sheet, as is shown
by the filling in of the inter spaoes. Also, as has been
stated for other unexposed sheets, the inner spaoe is
definitely lighter on this set. There is no visible dif
ference in this set between the two conditions of the stub
pen. The ball pen leaves suoh a relatively small amount
of ink that there is no apparent diffusion of the unblotted
writing until an age of 70 days is reached. The difference
between the blotted and unblotted writing is more pronoun
ced than it is with other inks. The fountain pen again
leaves its characteristic effects, which are the same as
on the exposed set.
41
XI* SULFATB PATTEEtBS OH STAHDARD PAPERS
Waterman18 blue-black ink is a typical sulfate ink;
i.e., it contains practically all sulfates and only very
little, if any chloride, as is shown by the chloride and
sulfate diffusion patterns* The standard writings were
used for this part of the investigation in the same way
as for the chlorides. The strips were cut off and devel-
oped according to the method given previously.
The effects of the different variables are given
below.
In developing the sulfate pattern* the paper is
bathed in a solution containing lead nitrate or acetate.
If there is any sulfate in the paper, it will be changed
into lead acetate and then to lead sulfide as well as the
sulfates of the ink. As was explained in another chapter,
the darkening of the paper depends a great deal on the
amount of washing. The 100# rag paper has no sulfates.
Although some of the strips are darkened in color due to
the above explanation, the other papers all show a slight
tanning in color. There is no visible difference between
the sulfate darkening on exposed and unexposed sets of
papers.
The types of pen points seem to have no more effect
on the sulfate pattern of an ink than it has on the original
Figure 9
Photograph (x 2*5) of sulfate development of
Watermanls ink. Writing is 185 days old. Notice
lack of diffusion, and the laok of effect of oon~
ditions, such as blotting, exposure, etc.

43
ini: stroke, that 1b, shading and width.
The blotting of a writing has the effeot of reducing
the intensity of the sulfate pattern, the same as for the
ohloride pattern. As was said before, there seems to be
no difference between the sulfate pattern of a writing
which has been exposed and one which has not. At no time
was there observed any sulfate migrating from one sheet
onto another.
The principal characteristics of the sulfate pattern
are the slowness with which it migrates. The sulfates have
migrated through to the back in one month's time on the
100% and 85# rag papers so that is is visible* This is
true of both the exposed and unexposed sets. Or the Ho. 1
sulfite paper the pattern oan be seen from the back, although
it has not really penetrated entirely through the paper
even at its greates age. The sulfate pattern is not visible
from the rear of the strips of the vellum note paper. On
the ohemioal paper we find that the sulfate pattern is vis
ible, but not completely migrated through to the back.
CHASTER V
SUMMARY
We Rave seen in the foregoing the effeote of a number
of variables* Briefly* they may be summarised as follows:
1* Different types and grades of paper show differ
ent intensities of darkening after the ohloride developing
prooess* The paper affoots the diffusion pattern greatly*
With paper8 of high ohloride content* the diffusion pattern
Is greatly obscured* or entirely obliterated*
2* The width of the diffusion pattern depends upon
the same factors as the original Ink line* The intensity
of the diffusion pattern varies with the type of pen* The
Inner space development varies greatly with a number of
factors depending upon the type of Ink* the kind of paper,
and whether or not it was blotted,
3* The blotting of a fresh Ink stroke Is* next to
age* the largest single effect* Blotted writings show
only a very faint diffusion pattern, which lags e great
deal behind the migration of the chlorides from from an
unblotted writing of the same age*
4* The effect of keeping a paper pressed tightly
against another in an enclosed place is of great importance*
oausing the resultant ohloride pattern to be decidedly
45
different from the pattern of an unexposed writing#
5# As well as can be determined from these conditions 9
the chlorides of an ink migrate progressively with agef but
due to the infinite variations possible, the amount of mi
gration cannot, by itself, indicate the age of the ink*
In conclusion, it might be well to express the
writer's opinion as to the value of this method# This in
vestigation has shown that due to the great number of var
iations, it is impossible to arbitrarily determine the age
of ink writing on a written dooument# Sven when all the
conditions are known. it is still impossible, without an
identical standard writing of different ages for comparison,
whleh is again impossible#
On the other hand, a chemist, using this method, can
give some valuable information as to the relative ages of
two ink writings on the same dooument. within certain limits#
In a case of this kind, many of the variables are essential
ly constant, and the amount of diffusion of one stroke as
compared with another can be used to estimate the difference
in age if the writings are not older than a certain age
(varies for the ink and condition) and if the elapsed time
between the two writings is sufficiently great, (see Figure
10.)
fhe sulfate diffusion pattern shows promise of being
46
valuable for the determination of ages of inks older than
two or three years, because of the faet that it is so little
influenced by varying conditionsy but this investigation
has not covered a period of time sufficiently lengthy to
make any definite conclusions on this subject*
Figure 10
Photograph (x £*5) showing appearance of two writ
ings made on the same paperf with the same pen*
inks, etc., but differing in age by 16£ days, in
dicating possibility of giving valuable information
in oertain oases as to whether or not one stroke
was older than another*
agpgps
» _,yv —
BIBLIOGRAPHY
Anonymous, Bur. Stds.. Circular 400 (1933).
Carvalho, Clairs, and Sparks, Boyden, Crime in Ink. Scribner's
Sons, Hew York, 1989.
Carvalho, D. 31,, forty Centuries of Ink. Banks Publishing Co.
Hew York, 1904.
lehner, Sigmund, Manufacture of Ink. Soott, Greenwood A Sons,
London, 1986*
Meloher, Webster A., Documentary Records. Philadelphia.
Meloher, Webster A., Questioned Ink Marks.
Mitchell, C. A., Documents and Their Scientific Bacamination.
Griffin & Co., London, T528.
Mitohell, 0. A., "Writing Inks”, (In Allen’s, Commercial
Organic Analysis. Vol. V.)
Mitohell, C. A., Analyst. 33, 80 (1908).
Mitchell, C. A., Analyst. 45, 843 (1980.)
Mitohell, C. A., "Ink", (In Pitman's, Commercial Commodities.)
Mitohell, C. A., and Mepworth, T. G., Inks. Their Composition
and Manufacture.
Osborn, A. S., Questioned Documents. 2nd Ed., Chap. ZX7.
Pines, Charles C., "The Story of Ink" American Journal of
Polios Soienoe. Vol II, Ho. 4.
Quioke, A. J., gorged. Anonymous. and Suspected Dooument s.
George Rout ledge & Sons, London, 1930.
Rupert, Prank P., Manufacture and Properties of Writing Inks.
Rupert, Frank P., "Examination of Writing Ink", Ind. Eng.
Chem.. 15, 489*93 (1983)*
Sohlittig A Heuman, Die Bisengallustinten. Dresden, Germany.
49
Ward, T. J., "The Mioroohemioal Identification of Ink in
Handwriting”, Analyst. 59, 621-2 (1954).
Waters* C. B., "Blue Dye as Bridenoe of the Age of Writing”,
Ind. Sag. Qhem.. vol. 25, Sept., 1933.
SPECIAL REFERENCES
Cornish, Robert B; Finn, John, Jr.; and MoI*enghlin, William,
Ind. Eng. Cheat. Hews Ed., IE, 5X5, (X954). ”Age of Inks
asDeiermined by the Ohloride Test."
Hezger, Otto; Heess, Walter; and Ball, Hngo, "Die Chemisohe
Identifigiemng und Alterbestimmung yon Tintensehrift."
In TorkeXvs, Beltrage znrgrimlnalistische Symptomalogle
and Teohnik. TffSITp W “ .
Ilezger, Ball, and Heess, Zeitsohrift fur axyewandte Chemie.
44, 645"»51, (1951). wHeuere TintentratersnohungenT*
Ilezger, Ball, and Heess. Arohiv fur Eklmlnalogle» 92, Hardh
and April, (1955). ''Sin nen.es' Verfabren, Klentitat and
Alton yon Tintensohrlften feszustellen.”
APMHDIX
list and description of Items used in preparation of
Standard Writings*
A. Pens
1* Semi bell steel point— "Radio Pen”, Bsterbrook Wo* 986
8* Semi stub— "Probate Pen", Bsterbrook 3lo* 313*
3* fountain pen point* medium*-Waterman’s Ideal Wo* 5*
B. Papers
1. A 100# rag paper— Agawan bond* 16#* 8£ by 13 inohes,
oookle finish*
8* A 86# rag paper— Stationers bond* 16#* 6|- by 13 inohes*
oookle finish*
3* A Wo* 1 sulfite paper— Hammermill Bond* 16#* 8%- by
13 Inohes, plain whits finish*
4* A note paper— Baton’s Bluefield Vellum, Carmen P 364*
Baton* Crane* and Pike*
5, A yellow second sheet— Standard Amber second sheets*
Bo 683^-T* Sationers Corp.* Sj- by 13.
C* Inks
1. Waterman’s Ideal Ink* blue-blaok*
8. Sheaffer's Scrip, permanent blue-blaok.
3# Sanford's* blue-blaok permanent Bo* 5*
4* Parker1 e washable blue Quink.
5. Parker’s permanent blue Quink*
6. Carter's Midnight blaek permanent*
Scheme for Decimal Index System*
A* Papers Index no*
1* 100# rag 1000
£• £5# rag £000
3* Ho* 1 sulfite 3000
4* Ho* 4 sulfite 4000
5* Chemical 5000
B* Pens
1* Clean stub (clean ink) 100
£* Busty stub (old ink) £00
3* Clean ball (clean ink) 300
4» Busty ball (old ink) 400
5* Pountain pen (clean ink) 500
C* Inks
1* Blue-black (Waterman's) 10
£• Blue-black (Sheaffer's) £0
3* Blue-black (Sanford's) 30
4* Washable blue 40
5« Permanent blue 50
6* Permanent black 60
Conditions
X. Open
2. m o d
3* Blotted
4. Unblotted
Index no*
1
£
B (on paper)
U (on paper)

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Asset Metadata

Creator Lovett, R. A (author)

Core Title The chloride ion diffusion method for the determination of the age of ink writing on documents

Degree Master of Science

Degree Program Chemistry

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag chemistry, analytical,OAI-PMH Harvest

Language English

Contributor Digitized by ProQuest (provenance)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c17-786306

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