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This is to certify that the

thesis entitled

THE ANALYSIS AND COMPARISON OF ADHESIVES BY
PYROLYSIS GAS CHROMATOGRAPHY/MASS SPECTROMETRY

presented by

Kirsten Renee James

has been accepted towards fulfillment
of the requirements for

M.S. degree in WJustice

Specializing in Forensic Science

in M

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Date DJ 0/03

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6/01 c-JCIRC/DateDuepGS-p. 15

THE ANALYSIS AND COMPARISON OF ADHESIVES BY
PYROLYSIS GAS CHROMATOGRAPHY/MASS SPECTROMETRY

By

Kirsten Renee James

A THESIS
Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of
MASTER OF SCIENCE
School of Criminal Justice

2003

ABSTRACT

ANALYSIS AND COMPARISON OF ADHESIVES BY
PYROLYSIS GAS CHROMATOGRAPHY/MASS SPECTROMETRY

By
Kirsten Renée James
Pyrolysis gas chromatrography-mass spectrometry, or PyGC/MS, is a sensitive
technique used to compare complex compounds. This research evaluated PyGC/MS as a
method for characterizing adhesives. It is a technique that has not commonly been used
in forensic science to analyze various types and brands of adhesives. 48 brands were
dried overnight before analysis. A minimum sample size of lOOug was placed in a quartz
tube with both ends sealed with quartz wool. Samples were pyrolyzed to obtain
pyrograrns indicative of each sample’s chemical components. Using the general patterns
of the pyrograms the adhesives were compared and distinguished by brand and type. The
adhesives were grouped into eight classes according to their general use. These eight
classes of adhesives include: All - purpose glues, Contact Cement, Caulk, Fabric glues,

Hot melt glue sticks, Super glues, Twist & Paste Glue Sticks, and Wood glues.

Copyright by
Kirsten R. James
2003

I dedicate this work to our God for blessing me to bring it to completion.
To my husband Sonny, and our sons Robert and Lemuel for their love and support.

iv

ACKNOWLEDGEMENTS

I would like to express my deepest appreciation to Dr. Jay Siegel for teaching me,
and advising me at Michigan State University, and for hanging in there with me over the
past few years. Much thanks to Jennifer Rizk for her dedication and assistance on this
research. Sincere gratitude and thanks to Elizabeth Murray of the College of Mt. St.
Joseph for her editorial assistance and for inspiring me to pursue a career in forensic
science. Thanks to Jeff Kindig, Doug Heitkemper, Fred F ricke, Duane Satzger, Karen
Wolnik and the staff of the US. Food and Drug Administration’s Forensic Chemistry
Center (FCC) for giving me the opportunity to gain hands-on experience in the field. I
would also like to thank Thomas Wampler with Chemical Data Systems (CD8) and Ray
Huang of the Michigan State University Chemistry Department for their technical
support. Last but not least, I would like to extend a special thanks to my parents, Harold

and Emily Stewart, for their years of love, support, and encouragement.

TABLE OF CONTENTS

LIST OF TABLES ...................................................................................................... vii
LIST OF FIGURES ................................................................................................... viii
KEY TO ABBREVIATIONS ..................................................................................... ix
INTRODUCTION ....................................................................................................... 1
REVIEW OF LITERATURE ...................................................................................... 5
METHODS AND MATERIALS .............................................................................. 10
RESULTS AND DISCUSSION ............................................................................... 16
CONCLUSION ......................................................................................................... 28
APPENDICES ........................................................................................................... 30
Appendix A: Pyrograms of Adhesives ......................................................... 31
Appendix B: Three Sample Studies of Five Variables ................................. 65
REFERENCES ......................................................................................................... 81

vi

LIST OF TABLES

Table l - Adhesives Evaluated by PyGC/MS .................................................................. 11
Table 2 - Pyrolytic Parameters ......................................................................................... 15
Table 3 - Adhesive Studies .............................................................................................. 27

vii

LIST OF FIGURES

Figure 1 - Diagram of Pyroprobe pyrolyzer ...................................................................... 14
Figure 2 - Diagram of Pyrolysis - GC Instrumentation .................................................... 14
Figure 3 - Representative Pyrograms for All - purpose glues and Caulking Adhesives...17
Figure 4 - Representative Pyrograms for Contact Cements and Fabric Glues .................. 18
Figure 5 - Representative Pyrograms for Glue Gun Glue Sticks and Superglues ............. 19
Figure 6 - Representative Pyrograms for Twist & Paste Glue Sticks and Wood Glues....20

Figure 7 - Representative Pyrograms showing differences in Abundance ........................ 25

viii

KEY TO ABBREVIATIONS

CDS - Chemical Data Systems

DRIF TS - Diffuse Reflectance Infrared Fourier Transform Spectroscopy
FTIR - Fourier Transform Infrared Spectroscopy

GC - Gas Chromatograph(y)

GC/MS - Gas Chromatography/Mass Spectrometry

GPC - Gel Permeation Chromatography

HP - Hewlett Packard

HPLC - High Performance Liquid Chromatography

IR - Infrared Spectroscopy

MS - Mass Spectrometry

PyGC - Pyrolysis Gas Chromatography

PyGC/MS - Pyrolysis Gas Chromatography/Mass Spectrometry

PyMS - Pyrolysis Mass Spectrometry

ix

INTRODUCTION

Evidentiary materials in forensic science can be found in a variety of forms.
These forms range from something as small as a fiber, a hair, or paint flake to something
as complex as ink, plastic, copier toners, and in the case of this research, adhesives.
When this evidence is brought into the lab, it is the goal of the forensic scientist to
identify these materials and to link them to their source of origin. Connecting evidence
to its origin can only be done by analyzing and comparing the unknown (questioned)
sample, which comes from the crime scene, to the known (control) sample, which is the
material suspected to be the source of origin. For example, a white powder collected at a
crime scene is thought to be cocaine (unknown sample). A small bag of white powder,
similar to that retrieved at the crime scene, was found in the possession of the person
suspected of committing the crime (possible known sample). So, the two samples of
powder are analyzed and compared. It is concluded that the sample at the crime
scene(unknown) could have in fact come from the sample obtained from the suspect
(known). Since chemical evidence rarely comes into the forensic lab as a pure substance
it is the job of the forensic scientist to break down these substances into their chemical
components. By doing so two different samples can be compared one component at a
time. This will better assist the lab personnel to better connect the evidence to its source
of origin.

There are several analytical methods used to identify and characterize various
types of physical evidence. One technique commonly used to analyze fibers, paints, and
other polymers is Pyrolysis Gas Chromatography-Mass Spectrometry, or PyGC/MS. The

intent of this research was to evaluate PyGC/MS by determining the extent to which it

can differentiate household adhesives. This was an exploratory pilot study to determine
the feasability of even using PyGC/MS to analyze adhesives. The interest of this study
lied in generating peak patterns for a variety of adhesives. Forty-eight in all were
purchased in craft and grocery stores. These samples were obtained from local stores
where most people can conveniently select from a diverse supply of adhesives each with a
particular function. Each sample was smeared on a microscope slide and dried overnight.
A small piece of sample, IOOug, was placed in a quartz tube which was then plugged with
quartz wool. Sample-filled tubes were pyrolyzed in a Pyroprobe 1000’ which was
mounted to a Chemical Data Systems (CDS) 1500 valved interface. Both pieces of
equipment were coupled‘to a Hewlett Packard 5971 Series Gas Chromatograph and Mass
Spectrometer.

Pyrolysis is the chemical breakdown of macromolecules by heat in the absence of
oxygen(l). During the pyrolysis process there are other chemical reactions going on
besides the degradation of polymers. The chemical bonds of these molecules can
depolymerize, or “unzip”; an elimination can occur in which there is the loss of a small,
neutral molecule; then there is random cleavage which makes rearrangement reactions
impossible if a polymer consists of bond energies that are similar (2). Helium which is
the carrier gas used in this research is ofien used to minimize secondary degradation
reactions (3). As the gaseous residues elute off the column via the Helium each
component of the original sample is picked up by the detector, which creates a pattern of
peaks specific to that sample. The output of the PyGC is the pyrograrn, which shows the

breakdown of the sample’s chemical fragments in the form of a peak pattern. The

pyrograms were compared to determine consistencies between samples.

What was found were peak patterns common to a specific type, or group of
adhesive. Many of the adhesives could be individualized, however, with out the run of a
blank between samples there may have been some carry over from previous adhesives
pyrolyzed. This may have contributed to the difficulty in determining some
differences/similarities between samples. So, the adhesives could be classified into eight
groups, by type, and distinguished one type from another (i.e. Super glues vs. Wood
glues). There were, however, a few exceptions within some groups that were labeled as
sub-classes for the purpose of differentiation.

Some cases and situations in which this type of evaluation could be useful include
package tampering and mail fraud. For instance, a package-tampering case may involve
the opening of a package with the motive of contaminating its contents. The suspect, in
an effort to conceal the opening of the package, reseals the package with a different
adhesive. The analysis of such a case would include: 1) collecting a sample of adhesive
from the suspect package (unknown sample); 2) adhesive from an unaltered package that
looks like the suspect package would come from the manufacturer (control); and, 3) if
possible, the adhesive the suspect used (known sample) to reseal the tampered package.
The pyrograms of the two adhesives on the tampered package should correlate to the
pyrograms of the two known adhesives found in the possession of the suspect and from
the manufacturer. Package tampering is encountered in the pharmaceutical industry when
individual boxes containing medicine are opened to get to the enclosed bottle. In the food
industry, labels can be counterfeited and placed on cans that did not come fiom the

manufacturer, or on expired products. These labels are applied to the surface of cans

using a different adhesive from the manufacturer’s adhesive. The postal service can also

use this analytical technique in the event letters and packages have been opened illegally,

then rescaled.

LITERATURE REVIEW

Throughout history people have made adhesives from a variety of materials
including beeswax, egg yolks, tree sap, protein from animal hides, hooves, and blood (4).
Now, most adhesives are made from polymers and other synthetic materials. To
determine the composition of the aforementioned materials, adhesives were analyzed by
several methods. For this research PyGC/MS was the method of focus.

Even throughout the literature it was common to see PyGC and PyMS being used
as separate analytical techniques. Although GC/MS was discussed in some of the papers
it was rare to come across the coupling of PyGC and MS. PyGC is an analytical method
that can distinguish materials belonging to the same group, or class. Combine the
sensitivity of the PyGC and its ability to specify components in a substance with the MS’s
“fingerprinting” ability and speed of processing data, the result is a powerful forensic
analytical technique called Pyrolysis Gas Chromatography - Mass Spectrometry
(PyGC/MS).

PyGC/MS is the degradation of non - volatile polymers into smaller more volatile
fragments (5), Gas Chromatography (GC) performs the separation of those same
fragments, and the identification of those fragments is determined by the Mass
Spectrometer. PyGC/MS is such a sensitive analytical technique that it requires only a
small amount of sample (1 - 100 ug) (6). It practically eliminates tedious and time
consuming sample preparation because it is responsive to both soluble and insoluble
samples. This analytical technique employs a pyrolyzer interfaced to a GC that’s coupled

to a Mass Spectrometer (MS). At an extremely high temperature the pyrolyzer breaks

down non ~volatile polymeric substances into smaller, volatile molecules (7). This
mixture of smaller molecules flows through the GC, via a capillary column, where its
components are separated into fragments. The MS detects each fi'agrnent and sends a
signal to the computer as each molecule elutes off the GC column. The computer records
these signals as peaks. So, every peak represents a different molecule. The set of peaks
creates a pattern that acts as a blueprint for the substance that was originally analyzed (8).
These blueprints, or output, are called pyrograms.

The field of applications of PyGC/MS is extremely wide and diverse. This
method has been used to determine the composition of something as diverse as the natural
resins used as adhesives in art materials (9) to something as complex as polymer blends
found in food wraps, coated freezer paper, and the clear film on cigarette packages (10).
It is frequently applied to industrial processes involving large scale pyrolysis such as
municipal solid waste processing and scrap automotive tire recycling (11). One study
(12) used PyGC/MS to examine the pyrolysis of energetic materials which consist of
hazardous waste containing explosives and propellants. The goal of the aforementioned
study was to compare pyrolytic products of incomplete combustion to incineration by -
products in order to determine if the two techniques have similar outcomes. If so,
PyGC/MS would be an acceptable means to dispose of the energetic materials without
causing environmental pollution that open incineration causes.

Before PyGC/MS was implemented as an analytical tool for adhesives there were
a few other techniques used to characterize these materials such as Infrared Spectroscopy
(IR), Pyrolysis Gas Chromatography (PyGC), and Gas Chromatography - Mass

Spectrometry (GC - MS). All of these analytical methods have their benefits and

disadvantages. However, PyGC/MS possesses a combination of some of the better
benefits of many of these analytical techniques. The GC - MS oflen used for drug
analysis by most forensic laboratories, can easily be adapted for pyrolysis by mounting an
interface to the GC injector (13).

When examining the advantages of polymer identification using PyGC over IR,
the qualitative application of PyGC is actually “fingerprinting” for the comparison of
pyrograms to those of a reference library, usually accomplished using GC and retention
time data or MS spectral identification (14). Unlike the Fourier Transform Infrared
Spectral Library of Commercial adhesives created by Jeff Kindig (15) and Steve
Borowski (16), the goal of this research was not to create an adhesive library for PyGC -
MS, but to compare the results of pyrolyzed adhesives. The lack of standard pyrolytic
and chromatographic parameters amongst forensic labs has kept the creation of pyrogram
libraries from reaching its potential (17). These libraries would be helpful in identifying
and characterizing adhesives and other physical evidence. A new combined technique
which respectively analyzes adhesive samples via Diffuse Reflectance Infrared Fourier
Transform Spectroscopy (DRIFTS) and PyGC is becoming a highly discriminating
scheme of analysis (18). An actual forensic case employing this technique confirmed the
similarity between the adhesive on the flaps of yellow envelopes that held counterfeit
American bank notes, to yellow envelopes in the suspect’s possession. Infrared
Spectroscopy (IR) also has its limitations when it comes to identifying complex materials.

IR can identify the presence of functional groups, but it is difficult to characterize
insoluble samples using IR (19).

Both PyGC and IR are commonly used to analyze polymers. Between the two,

PyGC was found to be much more efficient in analyzing materials. PyGC has the ability
to analyze insoluble materials whereas, IR cannot analyze such materials without
additional sample preparation (20). By breaking down samples, the pyrolyzates would be
swept into the GC eventually resulting in pyrograms that provide the analytical
information. PyGC cannot only specify functional groups but it can also identify specific
compounds. Adhesives on tapes used to bind materials together have been analyzed by
PyGC. The adhesive on polyvinyl chloride (PVC) tapes (21), used to tape detonation
devices to bombs, has been successfully compared before and afier explosions. Afler an
explosion, small fragments of tape could be linked to the original roll. For reasons such
as this, PyGC is an excellent technique for analyzing minute samples. PyGC has also
been used to analyze cooking fat from the stomach of a murder victim. Gum from the
skin of a murder victim and suspect have been linked (22). This diverse evidence
indicates types of polymeric substances that PyGC can successfully analyze. Though
PyGC is a highly effective analytical method, it has a few limitations such as the slow
separation of a sample, a variation in column/instrument conditions makes it difficult to
replicate retention time data and process pyrograms, inter - laboratory standardization is
almost impossible due to multiple stationary phases, and variation in PyGC data make
computer treatment difficult.

Although PyMS predates PyGC, forensic science laboratories use PyGC for
economic reasons (23). PyMS is not prone to the same limitation as PyGC, but it may be
difiicult to determine the composition of a pyrolyzate, and the instrumentation is
expensive. PyMS is considered a rapid, sensitive analytical method. Like the PyGC,

PyMS breaks down the sample, but doesn’t perform a separation of the pyrolyzate prior to

entering the mass spectrometer. Here the pyrolyzates are ionized and mass spectral scans
are made. With the aid of data processing software spectra are integrated and mass
pyrograms are plotted (24).

Over the past 20 years, adhesives have been one of the least common forensic
samples analyzed by PyGC, PyMS and more recently, PyGC - MS (25). Adhesives are
often referred to as glues or resins. However, In this study the terms “glue” and
“adhesives” were used interchangeably. An adhesive is a substance capable of bonding
surfaces together (26). The ability of an adhesive to bond relies primarily on its
molecular weight or the size of its molecules. So, the higher the molecular weight,
the stronger the bond (27). Adhesives belong to a family of materials called polymers.
Polymers are composed of repeating chemical units called monomers that are linked
together in a couple of formations. The chemical makeup of adhesives has been
characterized by a variety of techniques which include nuclear magnetic resonance, IR
methods, gel permeation chromatography (GPC), and High Performance Liquid
Chromatography (HPLC) (28). One study used PyGC and IR to classify adhesives. A
few samples from each class of adhesive were analyzed by PyGC, then reference spectra

of each adhesive were obtained from IR to confirm the results (29).

METHODS AND MATERIALS
Sampling Technique

Forty-eight household adhesives (Refer to Tablel) were chosen for evaluation by
Pyrolysis Gas Chromatography - Mass Spectrometry (PyGC/MS). They were chosen
based on them being easily accessible by the public in grocery and crafi stores. Each
adhesive was smeared, as evenly as possible using a wooden applicator, on opposing ends
of a microscope slide. The adhesives were then allowed to dry overnight. The dried
adhesive was cut or scraped, with a straightedge razor from the surface of the microscope
slide. A capillary tube was used to push the sample to the center of a quartz tube, then
both ends of the tube were sealed with quartz wool. Gloves were worn throughout the
sample preparation to prevent the contamination of the quartz tubes, quartz wool and
samples, with oils from the hands.

The initial sampling began by filling quartz tubes full of adhesives for insertion
into the PyGC/MS. Over half of the adhesives were sampled in this manner. By
weighing the estimated amount of sample used to fill the quartz tubes, it was determined
that the first set of samples weighed between llOOug and lZOOug. After sampling
initially with these amounts of adhesive per pyrolysis run some broad peaks were noticed
on the pyrograms that were not characteristic of the adhesives. This was because too
much adhesive was being deposited on the column. It was determined that only a small
amount of sample was needed for each run on this particular instrument. As a result, the
Gas Chromatograph’s (GC) capillary column had to be changed. Once the column had
been replaced normal peak patterns and retention times were restored. To determine the

best sample size a test was conducted to compare sample sizes of 100 pg, 500 ug, and

10

Table 1 Adhesives Evaluated by PyGC/MS

 

 

[ BRAND NAME 1 COLOR L TYPES I SUBCLASS ]
Modge Podge Waterbase Sealant white All-Purpose (AP)"
Ross All-Purpose White Glue white AP"
Rose Art Washable School Glue white AP"
Tacky Glue white AP"I
Elmer’s Glue-All X06Dl white AP AP-l
Elmer’s Glue-All white AP AP-l
Elmer’s Glue-All 32 1C] white AP AP-l
Elmer’s Green Glue green AP‘
Contact Cement clear Contact Cement (CC)‘
Elmer’s Neoprene Based Contact Cement clear CC“
Duro Safe Contact Cement clear CC“
Duro Safe Contact Cement 61Cl429A clear CC‘
Elmer’s Silicone Acrylic Latex almond Caulk (CK) C-l
Squeeze N Caulk
Elmer’s Silicone Acrylic Latex clear CK C-l
Squeeze N Caulk
Elmer’s Squeeze N Caulk 3271 l almond CK C-2
Elmer’s Squeeze N Caulk C0861 dries white CK C-2
Dow Corning Adhesive white CK C-3
Silicone Sealer T-HC white CK C-3
Bathtub Sealer white CK C-3
Adhesive Caulk white CK C-4
Kwik Seal white CK C-4
ALEX Plus white CK C-4
Titebond Polyurethane Glue 7K5 131 white CK”
Weldbond white CK“
Flexible Stretchable Fabric Glue white Fabric (F )"
No Sew Fabric Glue white F "
OK to Wash-1t Permanent Fabric Bond white F“
Stanley Dualmelt Glue Sticks clear Glue Gun Glue Sticks (GS)
Greystone Craft & Hobby Low Temp
Glue Sticks 5154 clear GS
Fingerprint Developer clear Super Glue (SG)"
Locktite Quicktite clear SG"
Quick Setting Apoxy Adhesive Super Glue clear SG"
High Performance Future Glue clear SG“
(Superglue Corp)
Meijer Super Glue Gel clear SG $0-1
Instant Krazy Glue All-Purpose clear SG $0-1
Super Glue for Leather & Wood C13A clear SG 56.]
Elmer’s Wonder Bond Super Glue clear SG 30-1

‘Samples distinguishable from other samples within the same class of adhesives

ll

Table l (cont’d) Adhesives Evaluated by PyGC/MS

 

 

[ BRAND NAME 1 COLOR ] TYPES J SUBCLASSJ
AVSG clear SG SG-2
Surebonder clear SG SG-2
Elmer’s Washable glue stick (Dries clear) blue Twist & Paste Glue Sticks (TP)“
Elmer’s Washable School Glue Stick blue TP'
(Dries clear)
Elmer’s All-Purpose Glue Stick white TP‘
(Dries clear)
Scotch Glue Stick white TP"
Avery Permanent Glue Stick white TP‘
Franklin Wood Glue exp. Dec. 95" almond Wood glue (W)‘
Franklin Wood Glue exp, Sept. 92" almond W"
Liquid Nails for Woodwork W“
Carpenter’s Wood Glue W“

A For the purpose of comparing the consistency of batches, dates printed on the package were used in place
of batch numbers not printed on the label.

1100 pg. After testing, the sample size was reduced to 100 ug in an effort to lessen the
amount of pyrolyzates, or residual adhesive components, which had been congesting the
gas chromatograph’s capillary column. 100 ug was the maximum useful sample size, not
the optimum sample size. Any sample size from 100 ug or less could have been used to
achieve similar results.

The 100 pg sample size was found to be equivalent to a 2mm x 2mm square area
Of dried adhesive. This measurement was determined by measuring pieces of paper, of
various sizes, with a ruler. The pieces were then weighed to determine what area of
sample weighed 100ug. After weighing the 2mm x 2mm piece of paper, a piece of
adhesive the same size was weighed to determine if its weight for that particular area was
comparable to that of the paper. The weight and area Of the adhesive were comparable to

that of the paper. The pre-measured square of paper was then used as a template to size

12

the remaining samples. After sizing a few samples with the piece of paper, the
approximate size of each sample was estimated without the template.
Instrumentation

Pyrograms of the adhesives were Obtained using PyGC/MS. For the analysis of
the adhesives, each sample-filled quartz tube was loaded into the platinum coil of the
pyroprobe, then inserted into the interface of the Gas Chromatograph-Mass Spectrometer,
or GC-MS. An “Adhesive Method” was developed, based on parameters from literature,
to program the pyrolysis unit and GC-MS for a sample run time of 36 minutes, along with
the following temperature settings. The PYROPROBE 1000" was programmed to
pyrolyze samples at 700°C for 10 seconds. The pyroprobe (Figure l), with quartz tube
inserted, was screwed into a Chemical Data Systems (CDS) 1500 valved interface
mounted on top of a Hewlett Packard (HP) 5890 Series II Gas Chromatograph (Figure 2)
coupled to an HP 5971 Series Mass spectrometer. The temperature Of the interface was
set to 275°C (Refer to Table 2).

The gas chromatograph was fitted with a 30m Alltech EC-S capillary column.
The column, 32 um in diameter, contained SE-54 stationary phase with a film thickness
of 1.0 urn. Helium was used as a carrier gas at a flow of 1 ml/mn. For all adhesives

analyzed, the GC-MS was employed with a split injection ratio of 50:1.

13

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Figure 1: Diagram of a CDS Pyroprobe. (From Yinon, Jehuda, (editor), Forensic Applications of
Mass Spectrometry, Forensic A lications of 01 sis - Mass S ectrome Munson, Thomas,

Boca Raton, FL., CRC Press, Inc. I995.)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Probe
(Ribbon Or
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Figure 2: Diagram of CBS-120 Pyrolysis - GC Instrumentation. (From Voorhees, Kent J., (editor),
Analytical Pyrolysis Techniques and Applications, ' ' A li ations
WM. Smith, Charles 6., London, Butterworth & C0,, I984.

14

Table 2 Pyrolytic Parameters

 

 

PYROLYSIS CONDITIONS
Interface Oven: 275°C
Pyrolysis Temperature: 700°C
Pyrolysis Interval: 10 seconds

 

CHROMATOGRAPHIC CONDITIONS

Column: 30m x 32 um EC - 5 Capillary
(Alltech)

Injector Temp.: 27 5°C

Split Ratio: 50:1

Carrier Gas: He

Carrier Flow Rate: lml/min.

Oven Program: 50°C for 1.00 min,

then 10.0°C/min to 250°C

 

MASS SPECTROMETER SCAN PARAMETERS

Mass Range: 50 to 550 Scans/sec. 1.2

15

RESULTS AND DISCUSSION

After running samples through the PyGC/MS each run was given a filename and
saved on a computer disc. A pyrogram was Obtained as the data for each adhesive. All
pyrograms were assessed visibly by comparing the overall peak patterns, retention times,
and abundance. The pyrograms were examined by overlaying at least two, but no more
than three, pyrograms at a time on a light table often used for tracing pictures or viewing
negatives. The pyrograms of samples within the same family of adhesive were compared
one to another first (i.e. Glue sticks vs. Glue sticks). Then the pyrograms of one type, or
family, of adhesives were compared to those in the other types of adhesives (i.e.
Woodglue vs. Fabric glue). This was done to ultimately conclude if adhesives could be
differentiated using PyGC/MS.

The 48 adhesives analyzed could not all be individually characterized so they
were grouped in classes according to their useful purpose; and into subclasses based on
their being comparable to adhesives within their class. There were eight general classes
in which the pyrolyzed adhesives could be grouped (Refer to Appendix A for all
pyrograms). The groups include: Caulking glues, Contact Cement, Fabric glues, Hot
Melt glue sticks, Super Glue (Cyanoacrylate), Twist and Paste Glue Sticks, All - Purpose
glue, and Wood glue. The adhesives were grouped according to their general purpose.

A representative pyrogram for each of these types of adhesives can be found in Figures

3 - 6. Within the classes there were some adhesives that were not easily distinguished, so
subclasses were created for those particular adhesives. In addition to the comparison
between samples in the same class, and the evaluation to differentiate between the classes

of adhesives, there were a few other points of interest taken into consideration during

16

 

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17

 

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19

 

 

 

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20

 

 

the comparison. These points of interest include adhesives of the same type and brand
sampled from different batches and color, the affect sample size has on the data, and a
“repeatability” study that examined the affects of drying time on a sample.
Fabric Glues

All three of the fabric glues share some common peaks, but all of them had
distinct pyrograms. Although the Flexible Stretchable Fabric Glue and the NO Sew
Fabric Glue share a similar peak pattern up to five minutes into the run, they can still be
distinguished from one another.
Twist & Paste Glue Sticks

There were five adhesives analyzed. Three of which were distinguishable. Two
of the samples were of the same type and brand, but different colors. Their peaks were
grouped at intervals about every 1.5 min. - 2.0 min. Despite the difference in color their
pyrograms almost matched peak for peak. SO, the color didn’t play much Of a factor in
differentiating the brands.
All - Purpose Glue

The all - purpose glues, in general, have been used for basic crafis and school
projects. However, they can be used for adhering a variety of things. Out Of eight
samples analyzed three were indistinguishable. The remainder were distinguishable.
Hot Melt Glue Sticks

There were only two types Of Glue Sticks pyrolyzed. These particular glue sticks
are used in hot glue guns for crafts. Aside from a couple of extra peaks on one pyrogram
there was little difference between the two samples. One of the samples was pyrolyzed

in a quartz tube, then in a glass tube of similar dimensions. This was done to determine if

21

glass tubes could be used in place of quartz tubes when pyrolyzing samples. There was
no significant difference between the glass and the quart tubes. The decision was made to
continue pyrolyzing samples in quartz tubes since quartz tube had been the primary
vessels for holding samples during pyrolysis.

Caulking Adhesives

This class of adhesives is often used to “fill joints, gaps, and cavities between two
or more similar or dissimilar substrates” (27). Caulking adhesives could be grouped into
four subclasses (See Table 1) because some of the samples were not easily distinguished
within this particular class of adhesives. A total of 12 samples were analyzed. Since only
two of the 12 could be differentiated by brand they weren’t placed in subclasses.

Super Glues ( C yanoacrylates)

Out of the 10 glues, eight possessed broad “humps” characteristic only to the
cyanoacrylates. Upon request, Thomas Wampler of Chemical Data Systems (CDS), ran a
couple of cyanoacrylates by PyGC/Ms and found similar results (28). It was not
completely certain what caused the peak broadening in the pyrograms of the super glues.
It was presumed that these “humps” are homogeneous and not a mixture of unresolved
peaks.

Wood Glues

These glues are used to bind wooden substrates together, Often in carpentry or
when performing simple repairs on wooden structures. Contact cements are viscous,
tacky glues Often used in making crafis. The pyrograms within each of these classes of

adhesive were distinguishable one from another.

22

 

Color & Batch Number Study

The purpose of this study was to conclude if there were any distinctions in
samples that were offered in more than one color. The other goal of this study was to
note the consistency of samples taken from different batches of the same brand of
adhesive. The lot number, or batch number, was recorded for each sample. If one was
not present then the date on the package was used. A total of 10 adhesives from four
classes were examined in this study (Refer to Table 3 & Appendix B). Samples taken
from different batches did not pose much difference in their pyrograms. Around the '
twenty rrrinute retention mark there appears to be some contamination. There were some
minor distinctions in color, also. The Elmer’s Squeeze & Caulk Almond and White
caulking glues also showed some differences in there pyograms.
Sample Size Study

Three different brands of adhesives were examined at varied approximate weights
(Refer to Table 3). After each sample was dried they were run consecutively on the
PyGC/MS. Elmer’s All - Purpose glue stick was dried for five days and pyrolyzed at
weights Of 100 ug, 500 ug, and 1100 ug. At 1100 ug the sample managed to hold its peak
definition. However, the best peak resolution of this sample was seen at 500 ug. Rose Art
washable school glue was dried for 24 hours and pyrolyzed at weights of 100 ug, 1100
ug, and 1900 ug. The peak resolution for this sample was best at 100 ug. Although the
baseline for the 100 ug and 1900 ug samples shifted, the peaks stilll correspond between
runs. The Modge Podge water based sealer was also dried for 24 hours and pyrolyzed at
100 ug and 1100 ug. The baseline again was distorted in these two pyrograms for some

unknown reason, and the peaks only correspond up to about 22.00 minutes. The

23

distortion in the baseline could be due to too much sample being applied to the column at
once. As the literature stated, a sufficient amount of sample would consist of 100 ug, or
less. Overall, this study shows that with an increase in sample weight the abrmdance, or
constituents’ concentration, may have increased, but it is possible to maintain some peak
definition (Figure 7). However, it’s best to use the minimum sample weight that gives
the best resolution and prevent damaging the column, which can attribute to distortion in
the pyrograms.
Repeatability and Drying Time Study

This study took into account the affects of drying time and how well consecutive
runs of a sample were repeated with similar results. According to literature (32),
“Repeatability” is the precision in one lab, by one analyst, and on one instrument.
“Reproducibility” on the other hand refers to precision between different labs, different
analysts, and different instruments. It is for this inconsistency with instrumentation and
parameters that forensic labs lack standardization. So, for clarification the term
“Repeatability” was used since it best described the repetitive results of this section.

Three aliquots Of the sample were dried overnight and three aliquots were dried
for 11 days. (Refer to Table 3) After the samples were dried they were run consecutively
on the PyGC/MS. Aside from one peak visible at 20.00 min. for the second and third
runs Of the 24 hour sample the extension of drying time didn’t improve the definition of
the sample’s peaks. However, the resolution, or the separation of each sample’s
constituent parts increased with each successive run from the retention range of 13.00
min. to 21.00 min.

To improve the overall resolution and consistency of pyrogram patterns it would

24

 

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Figure 7: (Top) Pyrogram of a sample with a greater weight and abundance.
(Bottom) Pyrogarn of a sample with a smaller weight and abundance.

 

 

be best to ensure the complete elution of components and consistent sample size. This
would ensure that there are no contaminants from previous samples eluting off with
subsequent samples run. To make sure all of the adhesive components are eluting off the
column between pyrolysis runs, conduct a run with a blank tube injected into the GC -
MS. Ifany peaks appear on the pyrograms, then it will be evident that all of the sample is
not flowing off the capillary column. Performing this blank run between samples may
help preserve the life of the GC column. Too many residual components deposited on the
column could over saturate the stationary phase of the column, thus causing broadening
of peaks. If blanks were run between samples during this study, having to replace the
column could have possibly been prevented. A consistent sample size throughout the
analysis would provide an abundance set at a particular level. This would make
comparing pyrograms of different adhesives a little easier because the peak patterns
would have been about the same proportion. None the less, samples with varying
abundance can still be compared because only the concentration, not the chemical
makeup changes.

Although it was found that adhesives cannot be individualized 100% by pyrolysis,
the fact that they can be narrowed down to their particular class , or type, of adhesive still

makes it a pertinent form of analysis in forensic science.

26

Table 3 Adhesive Studies

 

REPEATABILITY AND AF F ECTS OF DRYING TIME STUDY

 

 

 

 

 

 

 

 

 

 

Adhesive I Color I Drying Time I Sample Weight+
Ross All Purpose Glue white 24 hours“ IOOug
Ross All Purpose Glue white 24 hours IOOug
Ross All Purpose Glue white 24 hours IOOug
Ross All Purpose Glue white 11 days IOOug
Ross All Purpose Glue white 11 days lOOug
Ross All Purpose Glue white 11 days IOOug
SAMPLE SIZE STUDY

Adhesive I Color I Drying Time I Sample Weight+
Elmer’s All Purpose Glue Stick white 5 days lOOug
Elmer’s All Purpose Glue Stick white 5 days SOOug
Elmer’s All Purpose Glue Stick white 5 days llOOug
Rose Art Washable School Glue white 24 hours lOOug
Rose Art Washable School Glue white 24 hours 1100ug
Rose Art Washable School Glue white 24 hours 1900ug
Modge Podge Waterbase Sealer white 24 hours lOOug
Modge Podge Waterbase Sealer white 24 hours llOOug

 

COLOR AND BATCH NUMBER STUDY

 

 

 

 

Adhesive l Batch Number‘l' 1 Color Drying Time ISarnple Weighw
Elmer’s Glue green 24 hours lOOug
Elmer’s Glue All XO6D1 white 24 hours lOOug
Elmer’s Glue All white 24 hours lOOug
Elmer’s Glue All BZlCl white 24 hours lOOug
Franklin Wood Glue exp. Dec. 95 off white 24 hours IOOug
Franklin Wood Glue exp. Sept. 92 off white 24 hours lOOug
Uhu Stic 3082 purple 24 hours lOOug
Uhu Stic 4049 white 24 hours 100ug
Elmer’s Squeeze N Caulk B2711 almond 24 hours IOOug
Elmer’s Squeeze N Caulk C0861 white 24 hours IOOug

 

I"24 hours is an approximate drying period for samples dried overnight.
'I’Batch number not always available. The brand name, color, or date were used to identify sammes.

+Samples were weighed on an analytical scale.

CONCLUSION

Py GC/MS is a practical analytical technique because it involves very little sample
preparation, this instrument can receive both soluble and insoluble materials, its
sensitivity alots for minute sample sizes ranging from 100 ug or less, and it provides a
simple and economical process to interface a pyrolyzer unit to a GC - MS. It was also
noted that PyGC/MS produces repeatable results, especially when running the same
sample consecutively.

The majority of the adhesives analyzed, as predicted, were grouped in classes
spt:cific to their type (i.e. Fabric glues with Fabric glues). About halfof the adhesives
could be differentiated from other adhesives, even within their own class (Refer to Table
l). The absence or presence of a few peaks were the minor factors separating many of
these adhesives from others in the same group. Subclasses were also created within some
of the adhesive families for those samples that were not easily difl‘erentiated, but could be
matched to other adhesives within their particular class (Refer to Table 1). There were
also some minor distinctions between samples with different colors and those taken from
various batches.

A larger sample size constitutes for a greater abundance, or concentration, for the
group of samples pyrolyzed before the GC column was changed midway through the
research. This may have made it possible for some more resolved peaks seen , for
example, in a 100 ug sample to be obscured amongst a group of peaks in an 1100 ug
sample (Figure 7). Although there was little difference in the peak patterns of samples

with a greater weight versus those at 100 ug, it would be best to keep the sample size the

28

 

same throughout.

PyGC/MS by itself isn’t 100% identifiable, but a scheme of analysis including
F TIR and PyGC/MS could categorize and individualize complex samples like adhesives.
This would be particularly effective if more adhesives were added to the library created
by J eff Kindig, against which an unknown adhesive brand and type could be confirmed.
All of the samples noted as “indistinguishable” aren’t all exactly the same, some
differences with repeated runs and blank runs may be revealed as significant. Further
research is needed with the cyanoacrylates to determine the composition of the
unidentified “humps” in the cyanoacrylate pyrograms. In the future this comparison of
pyrolyzed adhesives could be extended to classes of adhesives not run in this study, such
as spray adhesives, nail glue, adhesives used by makeup artists, adhesive on the backing

of tapes, and resins used to bind porcelain to teeth in dentistry (33).

29

APPENDICES

30

APPENDIX A

Pyrograms of Adhesives

Eight Groups Evaluated

1.

2

All Purpose Glues

. Caulking Glues

Contact Cement

Fabric Glues

Hot Melt Glue Sticks

Super Glues (Cyanoacrylates)
Twist & Paste Glue Sticks

Wood Glues

3]

All Purpose Glues

32

 

 

 

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64

APPENDIX B

Three Sample Studies of Five Variables

1. Color and Batch Number

2. Repeatability and the Affects of Drying Time

 

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65

 

 

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71

 

Repeatability and Affects of Drying Time Study

72

 

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80

10

11

References

US Environmental Protection Agency, Engineering Bulletin, Molysis
Treatment Office of Emergency and Remedial Response, Washington, DC,
Office of Research and DeveIOpment, Cincinnati, Ohio, (October 1992).

 

Settle, Frank A., editor, Handbook of Instrumental Techniques for Analytical
Chemistry, Pyrolysis Measurements. Smith, Charles, UpperSaddle River, NJ
07458, Prentice Hall, Inc., 1997.

 

2".
Ibid, pg. 896.
Daryl J. Doyle, “Adhesive,” World Book OnIine Edition,
http://www.aolsvc.worldbook.aol.com/wbol/wauth/j sp/warticle.j sp,
November 16, 2002.
Wampler, Thomas P., editor, Applied Pyroysis Handbook, Analytical flrolysis: _L

An Overview. Wampler, Thomas P., New York, Marcel Dekker, Inc., 1995.

Inger Ericsson, “A New Technique (Pyrolysis) for the Anslysis of Adhesive,”
ATAS: A Total Analytical Solution, PYROLab,
Http://www.atas.co. uk/Applation_Notes/pyrola_app_notes/p 1 2. pdf,

November 16, 2002.

Inger Ericcson, “Pyrolysis: An Introduction to the Modern State of the Art,”
ATAS: A Total Analytical Solution, PYROLab,
Http://www.atas.co.uk/application__Notes/pyrola_app__notes/p12.pdf,
November 16, 2002.

Chromatography Study Guide #5,
Http://www.msu.edu/~people/chroma.html, November 16, 2002.

Stevenato, R.; Rovea, M.; Carbini, M.; F avretto, D.; Traldi, P., Curie-point
Pyrolysis/Gas Chromatography/Mass Spectrometry in the Art Field. Part 3: The
Characterization of some Non-Protenaceous Binders, Rapid Comunicatigns in

Mass Sfltromegy, February 1997, 11 (3, 15): 286 - 294.

Wampler, Thomas P.; Zawodny, Charles P., “Analysis of Polymer Packaging
Products Using Pyrolysis - Gas Chromatography - Mass Spectrometry,”
Httpz/lwww.iscpubs.com/articles/aln/n9909wam.pdf.

Moldoveanu, S. C., Molysis GC/MS, Present and Future (Recent Past and
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81

12

13

14

15

16

17

18

19

20

21

22

REFERENCES Continued

Cropek, Donald M., Pyrolysis/Gas Chromatography/Mass Spectrometry of
Energetic Materials [microfilm], US Army Corps of Engineers, Construction
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distributor, 1998.

Yinon, Jehuda, (editor), Forensic Applications of Mass Spectrometry, Forensic
ApplicatiOns of Pyrolyis - Mass Spectrometry. Munson. Thomas, Boca Raton,
FL., CRC Press, Inc. 1995. Pg. 172.

Voorhees, Kent J ., (editor), Analytical Pyrolysis Techniques and Applications,
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Kindig, Jeff P., The Development of a FTIR Spectral Library of Commercial
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Borowski, Stephen G., Development of a Comprehensive Adhesive Spectral
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Liebman, S. A.; Levy, E. J ., (editors), Pyrolysis and Gas Chromatography in
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Lennard, C. J. And Mazzella, W. D., Simple Combined Technique for the
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Voorhees, Kent 1., (editor), Analytical Pyrolysis Techniques and Applications,

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Ibid, pg. 438.

Williams, E. R. And Munson, T. 0., The Comparison of Black Polyvinylchloride
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Liebman, S. A.; Levy, E. J., (editors), Pyrolysis and Gas Chromatography in

Polymer Analysis, Forensic Aspects of Analytical Pyrolysis. Saferstein, Richard,
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82

 

23

24

25

26

27

28

29

30

31

32

33

REFERENCES Continued

Jones, C. E. Roland and Cramers, Carl A., (editors), Analytical Pyrolysis,
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Hughes, J. C., Wheals, B. B. And Whitehouse, M. J ., Pyrolysis Mass -
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Yinon, Jehuda, (editor), Forensic Applications of Mass Spectrometry, Forensic
Applications of Pyrolyis - Mass Spectrometry, Munson, Thomas, Boca Raton,
FL., CRC Press, Inc. 1995, pp. 195 - 196.

 

 

Petrie, Edward M., Handbook of Adhesives and Sealants, New York, McGraw -
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Pizzi, A. And Mittal, K. L., (editors), Handbook of Adhesive Technology,
Analysis of Adhesives, Hon, David N. S., New York, Marcel Dekker, 1994.

 

Skeist, Irving, (editor), Handbook of Adhesives, Wood Adhesion, New York, Van
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Noble, W., Wheals, B. B. And Whitehouse, J ., The Characterization of
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Skeist, Irving, (editor), Handbook of Adhesives, Sealants and Cagks,
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Wampler, Thomas, Interview, CDS Analytical, Inc., 1998.

McNair, Harold M. And Miller, James M., _B_asic Gas Chromatogmphy:
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Jones, S. E. B., Adhesion and Dentistry, Int. .1 Adhesion and Adhesives, 1995;
15(2) pg. 113.

83

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