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This is to certify that the
thesis entitled

THE CHARACTERIZATION OF AUTOMOBILE BODY
FILLERS

presented by

SARA CHRISTINE MCNORTON

has been accepted towards fulfillment
of the requirements for the

MASTER OF degree in FORENSIC SCIENCE

 

 

V" Major Profeis ?’s Signature
V 4/5 07

Date

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MSU is an Affirmative Action/Equal Opportunity Institution

 

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To AVOID FINES return on or before date due.
MAY BE RECALLED with earlier due date if requested.

 

DATE DUE 1 DATE DUE DATE DUE

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

6/01 c/CIRC/DateDuepssopJ 5

THE CHARACTERIZATION OF AUTOMOBILE BODY FILLERS
BY

Sara Christine McNorton

A THESIS

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
Department of Criminal Justice
2004

 

 

 

 

 

 

 

 

 

 

 

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ABSTRACT
THE CHARACTERIZATION OF AUTOMOBILE BODY FILLERS
By

Sara Christine McNorton

Body fillers and spot putties are sometimes encountered with paint
evidence from hit-and-run accidents in forensic casework. It is a challenge for
the forensic scientist to attempt to Classify and compare the body fillers since no
research has been published on the subject since 1986 when Walsh, et al.
compared body fillers in New Zealand.

The objective of this study was to determine if chemical and physical
differences in body fillers from various manufacturers existed and could be
identified. A Perkin-Elmer Spectrum One FTIR Spectrometer, a stereoscope and
a Hewlett Packard 5890 Series II Gas Chromatograph were used to analyze the
body filler and spot putty samples. The results of this study are of significant
value because they will provide useful data for trace evidence examiners when
examining body fillers.

Extensive research was done to obtain a complete sample of light-weight
automobile body fillers and spot putties used in the United States. After all the
samples were identified, thirty-three were Obtained. Twenty-four of the samples
were body fillers and nine were spot putties. Nine different companies were

identified as the manufacturers of these 33 samples.

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ACKNOWLEDGMENTS

I would first like to acknowledge Guy Nutter for your interest, enthusiasm
and support for this project. You have been a great source Of knowledge and
help! Thanks also to Cheryl Lozen and Guy Nutter for making my internship with
the Michigan State Police a valuable learning experience and fun too! Additional
thanks goes to Dr. Siegel, for your ongoing support, encouragement and care.

A final thanks to my family, friends and to Phil, who have provided ongoing
love and support. I appreciate you putting up with me, especially during my
trying times! I could have not done as well with my Master’s and this project
without you!

Lastly, thank you to the Midwest Association of Forensic Science (MAFS)

for generously providing the funding for this project.

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TABLE OF CONTENTS

LIST OF TABLES .................................................................................. vi
LIST OF FIGURES ............................................................................... vii
INTRODUCTION ................................................................................... 1
Purpose Of this research ................................................................. 2
Review of the Literature .................................................................. 2

Body filler and spot putty composition ................................................ 3
Introduction to the techniques .......................................................... 4
MATERIALS AND METHODS .................................................................. 6
Sample preparation ....................................................................... 6
Fourier Transform Infrared Spectroscopy ........................................... 7

Aging Study ........................................................................ 8

Hardener Study ................................................................... 8

Bench v. Microscope Study .................................................... 9

Sample Analysis .................................................................. 9

Blind Study ....................................................................... 10

VIsible Microscopy ....................................................................... 10
Pyrolysis Gas Chromatography ...................................................... 11
RESULTS .......................................................................................... 12
Fourier Transform Infrared Spectroscopy ......................................... 12

Aging Study ...................................................................... 12

Hardener Study .................................................................. 12

Bench v. Microscope Study .................................................. 20

Sample Analysis ................................................................ 20

Blind Study ....................................................................... 34

VIsibIe Microscopy ....................................................................... 35
Pyrolysis Gas Chromatography ...................................................... 36
Overall Summary ........................................................................ 42
DISCUSSION ...................................................................................... 43
CONCLUSIONS AND FUTURE RESEARCH ............................................. 45
SUGGESTED PROTOCOL .................................................................... 46
APPENDICES ..................................................................................... 48
APPENDIX A: Fourier Transform Infrared Spectra .............................. 49
APPENDIX B: Pyrolysis Gas Chromatograms ................................... 83

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LIST OF TABLES

Table 1: The body fillers and spot putties used for the analysis ........................ 7
Table 2: Results from the blind study ........................................................ 34

Table 3: The results from all 3 analysis techniques, showing the groupings for
each sample .............................................................................. 42

vi

 

 

 

 

 

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LIST OF FIGURES

Figure 1: FTIR Spectra Results from Aging Study ....................................... 14
Figure 2: FTIR Spectra Of the Pink Hardener Group .................................... 15
Figure 3: FTIR Spectra of the Blue Hardener Group .................................... 16
Figure 4: FTIR Spectra of the Dark Red Hardener Group .............................. 17
Figure 5: FTIR Spectra Of Bondo with 4 Hardeners ...................................... 18
Figure 6: FTIR Spectra Of Bondo with 3 Hardeners ...................................... 19
Figure 7: FTIR Bench v. Scope Comparison Spectra ................................... 21
Figure 8: FTIR Representative Spectra from Group 1 .................................. 22
Figure 9: FTIR Representative Spectra from Group 2 .................................. 23
Figure 10: FTIR Representative Spectra from Group 3 ................................. 24
Figure 11: FTIR Representative Spectra from Group 4 ................................. 25
Figure 12: FTIR Representative Spectra from Group 5 ................................. 26
Figure 13: FTIR Representative Spectra from Group 6 ................................. 27
Figure 14: FTIR Representative Spectra from Group 7 ................................. 28
Figure 15: FT IR Representative Spectra from Group 8 ................................. 29
Figure 16: FTIR Representative Spectra from Group 9 ................................. 30
Figure 17: FTIR Representative Spectra from Group 10 ............................... 31
Figure 18: FTIR Representative Spectra from Group 11 ............................... 32
Figure 19: FTIR Representative Spectra from Group 12 ............................... 33
Figure 20: pyGC Representative Chromatograph from Group 1A ................... 37
Figure 21: pyGC Representative Chromatograph from Group 18 ................... 38
Figure 22: pyGC Representative Chromatograph from Group 2 ...................... 39

vii

Figure 23:
Figure 24:

Figure 25:

Figure 26:

Figure 27:
Figure 28:
Figure 29:
Figure 30:
Figure 31:
Figure 32:
Figure 33:
Figure 34:
Figure 35:

Figure 36:

Figure 37:

Figure 38:
Figure 39:
Figure 40:
Figure 41:

Figure 42:

Figure 43:
Figure 44:
Figure 45:

pyGC Representative Chromatograph from Group 3 ..................... 40
pyGC Representative Chromatograph from Group 4 ..................... 41
FTIR Spectra Of U.S.C. Quality Light-weight Feather-rite ................ 50
FTIR Spectra of U.S.C. Premiere Light-weight ............................. 51
FTIR Spectra Of U.S.C. Basecoat/CIearcoat Extra ......................... 52
FTIR Spectra of U.S.C. Light-weight Kromate Light ....................... 53
FTIR Spectra of 3M Light-weight ............................................... 54
FTIR Spectra of Marson Body Light ........................................... 55
FTIR Spectra of Bondo ............................................................ 56
FTIR Spectra of Marson White Fill ............................................. 57
FTIR Spectra of Marson Platinum Premium Light-weight ................ 58
FTIR Spectra of Marson Golden Extra ........................................ 59
FTIR Spectra of Evercoat Rage Gold ......................................... 60
FTIR Spectra Of Evercoat Light-weight ....................................... 61
FT IR Spectra of Evercoat Chrome-a-Lite .................................... 62
FT IR Spectra of Evercoat Rage ................................................ 63
FTIR Spectra of Evercoat Z-Grip .............................................. 64
FT IR Spectra Of Evercoat Tack Free ......................................... 65
FT IR Spectra of DuPont Final Fil .............................................. 66
FT IR Spectra of Dynatron Ultimate Premium Light-weight ............. 67
FT IR Spectra of Dynatron Ultragrip ........................................... 68
FTIR Spectra Of U.S.C. Easywhite Lite ....................................... 69
FTIR Spectra of U.S.C. Blue Ice ............................................... 70

viii

Figure 46:
Figure 47:
Figure 48:
Figure 49:
Figure 50:
Figure 51:
Figure 52:
Figure 53:
Figure 54:
Figure 55:
Figure 56:
Figure 57:
Figure 58:
Figure 59:
Figure 60:
Figure 61:
Figure 62:
Figure 63:
Figure 64:
Figure 65:
Figure 66:
Figure 67:

FTIR Spectra Of 3M Premium Body Filler Gold QBA ..................... 71
FTIR Spectra Of 3M Zebra Tack Free Light-weight ........................ 72
FTIR Spectra of 3M Premium Light-weight .................................. 73
FTIR Spectra of PPG Red Oxide ............................................... 74
FT IR Spectra Of Evercoat Ever-Glaze and Spot Putty .................... 75
FTIR Spectra of Bondo Glazing & Spot Putty ............................... 76
FTIR Spectra of Nitrostan Red Spot & Glayze Putty ...................... 77
FTIR Spectra Of Dynatron Glazing & Spot Putty ............................ 78
FT IR Spectra Of 3M Acryl Green Spot Putty ................................. 79
FT IR Spectra Of Marson Spot & Glazing Putty .............................. 80
FTIR Spectra Of Nitrostan Green Spot Putty ................................ 81
FT IR Spectra of Nitrostan Grey Spot Putty .................................. 82
pyGC Chromatograph of U.S.C. Quality Light-weight Feather-rite....84
pyGC Chromatograph of U.S.C. Premiere Light-weight .................. 85
pyGC Chromatograph of U.S.C. Basecoathlearcoat Extra ............. 86
pyGC Chromatograph of U.S.C. Light-weight Kromate Light ........... 87
pyGC Chromatograph of 3M Light-weight .................................... 88
pyGC Chromatograph of Marson Body Light ................................ 89
pyGC Chromatograph Of Bondo ................................................ 90
pyGC Chromatograph of Marson White F "I .................................. 91
pyGC Chromatograph of Marson Platinum Premium Light-weight....92
pyGC Chromatograph of Marson Golden Extra ............................ 93

ix

Figure 68: pyGC Chromatograph of Evercoat Rage Gold ............................. 94

Figure 69: pyGC Chromatograph of Evercoat Light-weight ............................ 95
Figure 70: pyGC Chromatograph of Evercoat Chrome-a-Lite ......................... 96
Figure 71: pyGC Chromatograph of Evercoat Rage .................................... 97
Figure 72: pyGC Chromatograph of Evercoat Z-Grip ................................... 98
Figure 73: pyGC Chromatograph of Evercoat Tack Free .............................. 99
Figure 74: pyGC Chromatograph Of DuPont Final Fil ............................... 100

Figure 75: pyGC Chromatograph of Dynatron Ultimate Premium Light-weight.101

Figure 76: pyGC Chromatograph of Dynatron Ultragrip .............................. 102
Figure 77: pyGC Chromatograph of U.S.C. Easywhite Lite .......................... 103
Figure 78: pyGC Chromatograph of U.S.C. Blue Ice .................................. 104

Figure 79: pyGC Chromatograph of 3M Premium Body Filler Gold QBA ......... 105

Figure 80: pyGC Chromatograph of 3M Zebra Tack Free Light-weight ........... 106
Figure 81: pyGC Chromatograph of 3M Premium Light-weight ..................... 107
Figure 82: pyGC Chromatograph of PPG Red Oxide ................................. 108

Figure 83: pyGC Chromatograph of Evercoat Ever-Glaze and Spot Putty ....... 109
Figure 84: pyGC Chromatograph of Bondo Glazing & Spot Putty .................. 110
Figure 85: pyGC Chromatograph of Nitrostan Red Spot & Glayze Putty ......... 111

Figure 86: pyGC Chromatograph of Dynatron Glazing 8. Spot Putty .............. 112
Figure 87: pyGC Chromatograph of 3M Acryl Green Spot Putty ................... 113
Figure 88: pyGC Chromatograph of Marson Spot & Glazing Putty ................ 114
Figure 89: pyGC Chromatograph of Nitrostan Green Spot Putty ................... 115
Figure 90: pyGC Chromatograph of Nitrostan Grey Spot Putty .................. 116

 

 

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INTRODUCTION

Interest in the field of forensic science is becoming more popular and
scientists are constantly looking for new types of evidence to characterize from
scenes Of crimes. Since criminals are becoming more aware of the presence
and use of fingerprints and DNA as individual evidence, they are becoming more
conscientious about not leaving that type of evidence behind. Thus, trace
evidence is becoming more and more important as it is this evidence that is left
behind that may seem insignificant to the criminal, but may eventually lead to
circumstantial proof that she or he could have committed the crime in question.

Automobile body fillers have been used extensively in repair shops and by
individuals to aid in fixing minor body damage that may have occurred as a result
of an accident. Since the bond between the filler and the metal pieces of the car
is relatively weak, pieces of filler are usually removed along with adhering paint
Chips in traffic accidents (Home et.al, 1980).

Through multiple conversations with body repair shop mechanics, it was
determined that the light-weight brands of body fillers are used most commonly
due to their prevalent use in repairing damage to the metal in automobiles. Other
degrees Of fillers are commercially available (heavy-weight), but were not studied
here due to the fact that they are mostly used to repair damaged plastic parts. In
addition, a new trend was learned from the body repair shops, which is to replace
a damaged part with a plastic one, rather than fixing the damage to the metal
with automobile body filler. This information is relevant to the trace evidence

examiner as the prevalence of automobile body filler encountered in casework

will be less, however, if it is encountered, it could be considered as unique
evidence.
W

The purpose Of this project was to propose an analysis scheme for
analyzing an unknown body filler or spot putty sample. Since this type of
evidence is considered Class evidence, the best way to Classify it into the
smallest group as possible is to use an analysis scheme comprising multiple
analysis tools, since an individualization will never be possible. The idea for this
project originated from examining cases involving automotive paint with body
filler attached to it. In the past 15 years with advances in technology, product
compositions have changed greatly. Since no studies have been done in the
United States on attempting to characterize body fillers and spot putties, the
author wanted to start a new study which incorporated as many different body
fillers and spot putties that currently existed on the market today.
Review of the Literature

An extensive search of the literature for recent articles that have
attempted to characterize vehicle body fillers was done and only 3 articles dating
back to 1980’s were found. First of all, Cleverley in New Zealand proved that by
examining the color and infrared spectrum of 12 body fillers, the brand of the filler
could be identified (Cleverley, 1970).

In 1980, Home etal. studied automobile body fillers from Britain by

comparing the results Obtained through color, pyrolysis gas chromatography

(pyGC) and X-ray fluorescence analysis in order to provide a systematic scheme

 

 

 

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for their analysis. This study found that their 18 manufacturers’ samples could be
split into 5 smaller groups by examining their color variation. Analysis using
pyGC showed that they all produced different pyrograms. In addition, the use of
X-ray fluorescence gave an indication of the heavier inorganic elements, which
could be used as an additional discrimination technique (Home et.al, 1980).

Lastly, Walsh eta]. looked at 37 different formulations of body filler
available in New Zealand from 12 different manufacturers and surveyed them
using SEM-EDAX, visible microspectrophotometry, infrared spectrometry (IR)
and density. Nearly all of the samples of the different formulations could be
discriminated using this analysis scheme. This study found that SEM-EDAX was
the most powerful, single analysis tool. Density and visible
microspectrophotometry showed good discrimination with IR having the least
discriminatory ability (Walsh et al, 1986).
Body Filler and Sm: Pm Comgition

The majority of body fillers that were used in this study were comprised of
5 main components; polyester resin, talc, styrene, titanium dioxide and
glass/silica bubbles. The polyester resin is a proprietary formulation determined
by the manufacturer. It comprises the majority of the filler. Talc is used primarily
as filler, which aids in the sanding down process. Upon addition of the hardener
(comprised mainly of benzoyl peroxide), cross-linkage occurs between the
styrene and polyester resin, producing a 3-dimensional polymer. Titanium
dioxide is present in order to increase the opacity of the hardener and to give an

indication of the uniformity achieved when the hardener and filler are being mixed

(Home etal, 1980). Finally, Iighteners may be added which serve to decrease
the density of the final product. Examples Of these low weight, high volume
Iighteners are quartz, silica and glass bubbles (Walsh et al, 1986).

The spot putties that were examined were comprised of a variety of
different components. However, there were two main components that were
seen in all of the spot putties; talc and xylene. The purpose of the talc, as
mentioned above, is used as a filler to aid in the sanding process. Xylene is
used as a solvent to help keep the spot putty in its liquid-like form inside of the
tube until it is ready to be used.

Introduction to the Techng' ues

Three different analysis techniques were chosen based on their
usefulness for analyzing body filler and spot putty samples. These techniques
Chosen are also commonly used in crime laboratories.

Fourier Transform Infrared Spectroscopy (FTIR) is employed in the
analysis of small paint samples, textile fibers, particulate explosive material and
low dosage drugs by identifying the class of compounds present within a
specimen. By exposing the sample to light in the infrared region (4000-500cm"),
the interaction of the light with the bonds between the atoms in a specimen can
be measured. The bonds in the sample attain a higher state of vibrational energy
by absorbing this radiation. The absorbances are detected by an infrared
spectrophotometer, which produces a spectrum showing the intensity of the
absorption of the infrared light at each wavelength. One limitation of FTIR is that

is has a limit of detection of 5%. This means that substances that are present in

the specimen of less than 5% of its total weight may not be detected, if this
substance is not totally miscible in the rest of the specimen mixture. Since
automobile body fillers and spot putties contain several organic components,
FTIR was chosen because it can distinguish between the organic components in
each of the samples (Saferstein, 1993 & Kirkbride, 2000).

VIsible microscopy was also chosen for this study because it is a simple,
non-destructive technique, which yields discriminating results for many trace
evidence samples. All forensic science laboratories have stereoscopes, making
it very useful as part of the protocol in the body filler and spot putty analysis.

Pyrolysis Gas Chromatography is useful for analyzing substances that do
not have sufficient vapour pressure at the normal operating temperature of the
gas Chromatograph (300°C) such as hairs, fibres, paints and adhesives. Due to
their polymeric nature, automobile body fillers and spot putties are prime
candidates for analysis by pyGC. In pyGC analysis, the sample is heated under
controlled conditions to temperatures around 1000°C, causing the sample to
break apart into its smaller, constituent molecules. These molecules elute from
the column at Characteristic times and amounts. PyGC was chosen for this
research project due to its sensitivity in detecting small changes in polymer
composition, which may differ between samples from different manufacturers
(Cirimele, 2000).

MATERIALS 8 METHODS
Sample pgparation

A standard protocol was used for the preparation of the body filler and
spot putty samples for all of the studies that were performed on all of the
instruments. Manufacturer’s instructions were followed in preparation for the 24
body filler samples, which were the same for all of the samples; 2% hardener by
weight added to every sample of body filler.

The can containing the body filler was opened and the filler was stirred.
Approximately 1.009 of body filler was weighed out along with approximately
0.029 of red hardener (see results from hardener study). The filler and hardener
were mixed together and spread as a thin layer onto a microscope slide. The
slide was placed in a fume hood and allowed to dry for at least 30 minutes.

For the 9 spot putty samples, a small amount of the spot putty was placed
on a wooden stick and spread onto a microscope slide in a thin layer. The
prepared slide was then placed in a fume hood and allowed to dry for at least 30

minutes at room temperature.

Table 1: The body fillers and spot putties used for the analysis

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

BODY FILLER # MANUFACTURER PRODUCT NAME
1 U.S.C. QUALITY LIGHT-WEIGHT FEATHER-RITE
2 U.S.C. PREMIERE LIGHT-WEIGHT
3 U.S.C. BASECOAT/CLEARCOAT EXTRA
4 U.S.C. LIGHTWEIGHT KROMATE LIGHT
5 3M LIGHT-WEIGHT
6 MARSON BODY LIGHT
7 BONDO BODY FILLER
8 MARSON WHITE FILL
9 MARSON PLATINUM PREMIUM LIGHT—WEIGHT
10 MARSON GOLDEN EXTRA
11 EVERCOAT RAGE GOLD
12 EVERCOAT LIGHT-WEIGHT
13 EVERCOAT CHROME-A—LITE
14 EVERCOAT RAGE
15 EVERCOAT Z-GRIP
16 EVERCOAT TACK FREE
23 DUPONT FINAL FIL
24 DYNATRON ULTIMATE PREMIUM LIGHT-WEIGHT
25 DYNATRON ULTRAGRIP
26 U.S.C. EASYWHITE LITE
27 U.S.C. BLUE ICE
28 3M PREMIUM BODY FILLER GOLD QBA
32 3M ZEBRA TACK FREE LIGHT-WEIGHT
33 3M PREMIUM LIGHT-WEIGHT
SPOT PUTTY # MANUFACTURER PRODUCT NAME
17 PPG RED OXIDE
18 EVERCOAT EVER-GLAZE AND SPOT PUTTY
19 BONDO GLAZING & SPOT PUTTY
20 NITROSTAN RED SPOT 8. GLAYZE PUTTY
21 DYNATRON GLAZING 8: SPOT PUTTY
22 3M ACRYL GREEN SPOT PUTTY
29 MARSON SPOT & GLAZING PUTTY
30 NITROSTAN GREEN SPOT PUTTY
31 NITROSTAN GREY SPOT PUTTY

 

 

Fourier Transform Infrared Smoscopy
The Perkin-Elmer Spotlight Fourier Transform Infrared Spectrophotometer

(FTIR) was used for a number of preliminary studies as well as to compare the

Chemical compositions Of all Of the body fillers and spot putties.

Aging Study- F TIR Microscope

The purpose of this study was to determine if the chemical composition of
the body fillers and spot putties Changed over specific time intervals. The results
of this study are used to determine how long a sample would produce reliable
results, after it had been prepared.

In order to perform this study, one type of body filler was chosen; Bondo.
The Bondo sample was prepared according to manufacturers’ directions (as
mentioned above). After specific time increments had passed, a small amount of
the body filler was scraped off the slide, flattened and placed onto the FT IR salt
plate, for analysis. This method was conducted on samples at the following
intervals:

30 minutes (estimated drying time as suggested by the manufacturer)

60 minutes

24 hours

5 weeks
The spectra were analyzed to compare peaks and determine if any of the spectra
Changed over time. The sample of Bondo was stored at room temperature, on
an analysis bench in between the time intervals.
Hardener Study- F TIR Microscope

The purpose of this study was to determine if differences existed between
the different colors and manufacturers of the various hardeners used in body filler
preparation. All 19 hardeners were prepared by putting a small amount on a

wooden stick and spreading a thin layer onto a microscope slide. The hardeners

were allowed to dry by placing them in the fume hood at room temperature for 24
hours. To prepare the hardener for analysis, a small amount was scraped off the
slide, flattened and placed on the FT IR salt plate. Three different locations were
scanned on each hardener sample and the spectra Obtained were compared.

Comparing the spectra from all of the hardeners and determining
similarities and differences, separated the hardeners into 7 groups. Next, one
hardener from each group was mixed with Bondo body filler (as per procedures
mentioned above), and allowed to dry in the fume hood. Once dry, a small
amount was scraped off, flattened, placed on the salt plate and analyzed with the
FTIR microscope.
F TIR Bench Spectra v. F TIR Microscope Spectra

All 33 samples (prepared as mentioned above) were initially run using the
FTIR microscope. The spectra were examined and were found to be too
concentrated. The peaks were too broad and not well resolved. It was then
decided that the 33 samples would be run again on the FTIR, but this time using
the main bench and having the samples prepared as potassium bromide (KBr)
pellets. The spectra Obtained from both analysis techniques were compared.
Sample Analysis— F TIR Bench

Each Of the 33 body filler and spot putty samples were made into KBr
pellets and run on the FTIR bench. The samples were prepared for analysis as
follows: a square of size 0.5 cm x 0.5 cm was cut out of the sample from the
microscope slide and placed into a mortar. Three scoops Of KBr was added and

ground in with the sample using a pestle. A small amount was placed into a

press and a pellet was made. The pellet was placed into the FTIR holder and
placed into the instrument. Five scans of each sample were done from 4000cm'1
to 450m".

The spectra from the 33 samples analyzed on the FTIR bench were
collected, compiled and put into a database so a library could be created. Future
samples could then be run and compared against these standards, producing a
list Of either exact matches or similar body fillers and spot putties.

Blind Study- F TIR Bench

A blind study was conducted in order to evaluate the protocol used in this
research for accuracy in comparing and attempting to distinguish and
characterize the 33 body filler and spot putty samples. A Forensic Scientist at
the Michigan State Police Crime Laboratory prepared thirteen samples. The
unknown samples were chosen at random, so the author was unaware of what
was being tested. Once the author received the samples, the same protocol was
followed as for the sample analysis in order to Obtain reliable spectra of each of
the unknowns. Once a sample had been analyzed on the FTIR bench, it was
searched against the spectra library and the results were recorded in terms Of
their percent match to the sample in question.

Visible Microscopy

Each sample was selected and examined on the microscope slide on

which it had been prepared using a Leica MZ7 stereoscope under 20X

magnification. The color that was observed by the author was recorded for each

Of the 33 samples.

10

is Gas Chromat ra h
A Hewlett Packard 5890 Series II Gas Chromatograph was used for

comparing the organic components of each of the 33 body filler and spot putty
samples. A method was created on the pyrolysis gas Chromatograph, which
resembled that of what is used to analyze paint samples. Each of the samples
was run twice through this method. The samples were prepared by scraping Off
a small amount from the microscope slide and placing it in a glass tube. In order
to make sure that the pyGC was free Of contamination, blank runs were
performed after every 8 samples and the method was designed to have long
holds at the final temperature before the next sample was run. The spectra
obtained were compared by checking for reproducibility and similarities and/or

differences amongst the samples.

11

 

 

 

 

 

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RESULTS

Fourier Transform Infrared Sm!
Aging Study

There was no continuous trend of change in chemical composition
detected by the FTIR as the samples aged at room temperature. The spectra for
all of the samples did not differ significantly from each other (see Figure 1). This
suggests that drying time does not affect IR spectra, as the body fillers and spot
putties maintain their chemical composition over an extended period of time.
This is useful information for a forensic scientist since body filler and/or spot putty
samples may come into the crime lab for analysis after a hit-and-run accident,
and would have been on the car for an unknown period Of time. If one assumes
that body filler and spot putty samples maintain their Chemical composition over
time, one can be sure that the spectra being produced resemble that of the filler’s
original condition.
Hardener Study

Nineteen different hardeners were received along with all Of the body filler
samples. The problem that existed here was to establish how similar or different
each Of the hardeners were in order to determine the number of hardeners that
were needed to make up the body filler samples. Before running the hardeners,
they were divided into three groups according to their color (pink, blue or red), as
determined by visual examination. After running all of the hardeners on the FTIR
microscope, it was determined that the hardeners of the same color could still be

considered members of their original group. However, smaller groups could now

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be created, based on the similarities and/or differences to other members within
their color group. All of the pink hardeners could be considered one group, with
similar spectra. The blue hardeners were further sub-divided into 4 groups and
the red hardeners into 2 groups. This hardener study resulted in the creation of 7
different groups of hardeners based on their FT IR spectra (see Figures 2, 3, 4).
In order to determine how each hardener group would interact with a body
filler sample, one type Of body filler; Bondo was chosen as the test filler. As
previously mentioned, Bondo was mixed with one hardener from each of the 7
groups. It was allowed to dry at room temperature and analyzed on the FTIR
microscope. Results from this study indicated that there was no change in
Chemical composition observed when the Bondo was mixed with any of the 7
different hardeners (see Figures 5 & 6). This result was advantageous because
it allowed the author to Choose one hardener (red) to prepare all of the body filler
samples for analysis. This would ensure that the results obtained from the FTIR
analysis would only be due to the filler composition and not be affected by the
composition Of the hardener. When the hardener is mixed in with the filler,
polymerization occurs, which allows the filler and hardener to form bonds with
each other. This polymerization causes the hardener to be evenly dispersed
throughout the mixture, thus proving that the existence of the hardener has not

effect on the final FTIR spectra result.

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F TIR Bench Spectra v. F TIR Microscope Spectra

Various samples were chosen for the purpose of comparison of the
spectra obtained from the FTIR microscope and the FTIR bench analysis. Upon
examination of the spectra, it was concluded that there was no difference in peak
location or general shape between the spectra acquired from both analysis
techniques (see Figure 7). The main difference that was found, however, was
that the spectra from the FTIR bench were less concentrated, making the peaks
look sharper and more resolved. Since the spectra that were acquired from the
FTIR bench were a better representation of the chemical composition of the body
fillers and spot putties, that analysis technique was then chosen as the one to
use for the rest of the analyses.
Sample Analysis

The results from the FTIR bench analysis of the body fillers and spot
putties, resulted in the author being able to group the 24 body fillers into 6 groups
and the 9 spot putties into 6 groups; for a total of 12 individual groups comprised
of anywhere from 1 to 9 members (see Figures 8—19). The way in which each of
the samples was grouped was by examining peak shapes and locations found in
the fingerprint region. More specifically, the most pronounced differences that
were observed between the groups were from 1700cm" to 1200cm", with
smaller, but still significant differences from 7500m'1 to 500cm". This was a very
successful analysis tool as it provided straightforward criteria for separating out

the samples.

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33

Blind Study

After analyzing the 13 unknown samples using the FTIR bench, each was
searched against the library of body filler and spot putty results from the sample
analysis portion of this study. The spectra from blind samples 1, 3, 5, 6, 8, 9, 11
and 12 all matched with what they actually were, whereas blind samples 2, 4, 7,
10 and 13 when searched against the library came up with spectra that were

different to what they actually were.

Table 2: Results from the blind study

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

UNKNOWN ACTUAL PRODUCT PRODUCT FROM CHOICE # CORRECTI
# LIBRARY SEARCH AND INCORRECT
PERCENT MATCH
1 USC Premiere LW USC Premiere LW 1, 96% CORRECT
Body Filler Body Filler
2 Bondo Body Filler Zebra Tack Free LW 16, 91% INCORRECT
Body Filler
3 Bondo Glazing 8- Bondo Glazing & 1, 99% CORRECT
Spot Putty Spot Putty
4 Zebra Tack Free LW 3M Premium Gold 4, 97% INCORRECT
Body Filler QBA Body Filler
5 Nitrostan Grey Spot Nitrostan Grey/Red 1/2, 91% CORRECT
Putty Spot Putty
(indistinguishable)
6 Evercoat Ever-glaze Evercoat Ever-glaze 1, 99% CORRECT
& Spot Putty 8. Spot Putty
7 3M LW Body Filler Marson Body Light 9, 95% INCORRECT
Body Filler
8 Nitrostan Green Spot Nitrostan Green Spot 1, 98% CORRECT
Putty Putty
9 Marson Body Light Marson Body Light 1, 99% CORRECT
Body Filler Body Filler
10 Marson Golden Extra USC Easywhite Lite 3, 94% INCORRECT
Body Filler Body Filler
11 Marson Spot 8. Glaze Marson Spot & Glaze 1, 98% CORRECT
Spot Putty Spot Putty
12 3M Acryl Green Spot 3M Acryl Green Spot 1, 99% CORRECT
Putty Putty
13 DuPont Final Fil Body Dynatron Ultimate 16, 81% INCORRECT
Filler Premium LW Body
Filler

 

 

All of the spot putties were found to match with the correct sample, while only

29% of the body fillers matched and 71% did not. With the exception of the last

34

sample, all of the samples that were considered incorrect, were within the top
10% (90% or higher match rate) of the library search results. Since the library is
attempting to choose between very similar spectra, and rank them according to
their similarity to the questioned sample, it is entirely possible that if the blind
samples were run again, the library may choose another sample within the top
10% as correct. A general practice in forensic science is to use 90% as a means
of possible inclusion. That is, all of the samples with the exception of one would
still be included as a possible match to the unknown sample. One would then
have to examine the spectra obtained from the unknown sample and compare it
visually to the standard samples that resulted in 90% or greater match from the
library search in order to determine inclusion or exclusion.
Visible Worm

A stereoscopic examination was done in order to see if the body filler and
spot putty samples could be distinguished by their color alone. Body fillers and
spot putties look very different from each other. Obvious differences are
observed in terms of texture and lustre, thus making it very easy to separate the
body fillers from the spot putties upon initial examination. After examining each
of the samples under the stereoscope, the body fillers were placed into one of
two groups (peach or gold) and the spot putties were placed into one of three
groups (red, green or grey). The author, in consultation with another forensic
scientist, categorized the samples into these color groups, so to attempt to

eliminate examiner subjectivity.

35

F_’y_r_ofiis Gas Chromatggraghy
Pyrolysis Gas Chromatography also proved to be a useful tool in helping

to place the body filler and spot putty samples into 4 groups. One unique result
was observed using the pyGC: some of the spot putties fell into the same groups
as the body fillers, which is different from the groups formed from FTIR and
microscopy analysis in that all of the body fillers fell into different groups than the
spot putties. Additionally, the first group had to be further divided into 2
subgroups because subtle differences existed in the Chromatograms. These
slight differences were not significant enough to create separate groups.

The way in which the samples were separated out into different groups
depended on the presence/absence of a peak at 2 minutes as well as the sizes
and shapes of peaks that were present around 6 minutes. Although many other
peaks were present, these peaks were chosen because they represented the
most significant differences between the pyrolysis groups as seen on the
programs. Group 1A had similar Chromatograms to group 18 except for the
presence of a really tall peak at 2 minutes (around 1 500 000 abundance),
whereas group 18 had virtually no or a very small peak (less than 500 000) for
the same time interval. Members of group 3 stood out due to the absence of any
significant peak at 2 or 6 minutes, while group 2 was characterized due to the
presence of a doublet peak between 6-8 minutes and a small peak at 2 minutes,
and group 4 showed multiple peaks at 2 minutes and a small, single peak around

6 minutes (see Figures 20-24).

36

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Table 3: The results from all 3 analysis techniques, showing the groupings for each sample

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

GROUP # FILLER # STEREOSCOPE PYGC FTIR BENCH
lndivid ual 1 Peach 2 4
2 Peach 1A 5
4 Gold 1 B 4
10 Gold 1 B 1
12 Peach 18 6
1 3 Gold 1 B 3
23 Peach 1A 2
32 Peach 1 B 3
l 3 Gold 1A 3
1 1 Gold 1A 3
28 Gold 1A 3
ll 5 Peach 1 B 4
7 Peach 1 B 4
15 Peach 1 B 4
III 6 Peach 1 B 1
8 Peach 1 B 1
16 Peach 18 1
26 Peach 1 B 1
IV 27 Peach 1A 3
33 Peach 1A 3
V 9 Peach 1A 1
14 Peach 1A 1
24 Peach 1A 1
25 Peach 1A 1
SPOT PUTTY # STEREOSCOPE PYGC FTIR BENCH
Individual 17 Red 4 7
20 Red 4 10
22 Green 3 8
30 Green 2 9
31 Grey 4 10
VI 18 Red 4 12
29 Red 4 12
VII 19 Red 1 B 1 1
21 Red 1 B 1 1

 

 

 

 

 

 

 

42

 

DISCUSSION

The purpose of this research project was to perform multiple analysis
techniques in order to attempt to characterize different types of body fillers and
spot putties. The primary goal of this study was to create a scheme by which
every sample that may be encountered in a crime laboratory could be
differentiated using 3 different analysis techniques. Upon examining the results,
it can be concluded that 13 of the 33 body filler and spot putty samples could be
individualized, while the rest of the samples, could be put into smaller groups of
2-4 samples.

The first conclusion that can be drawn is that all of the spot putties could
be differentiated from the body fillers based on color alone. The spot putties tend
to be comprised of more vibrant, unique colours such as green and red, whereas
the body fillers tend to resemble dull colors like peach and gold. Since an
attempt was made to find a representative sample of all of the body fillers and
spot putties currently on the market, it would be likely that the samples that were
tested in this study would be similar to what a forensic scientist would encounter
during his or her casework.

When referring to Table 3, some additional conclusions can be reached
with respect to the spot putties. Five out of nine spot putties can be
individualized using visible microscopy, pyGC and FTIR together (17, 20, 22, 30,
31). The remaining 4 can be grouped into 2 groups: 18 & 29 could not be
differentiated from each other and 19 & 21 could not be differentiated from each

other.

43

Additionally, when referring to Table 3, it can be concluded that 8 out of 24
body filler samples can be individualized using the 3 analysis tools from this
study (1, 2, 4, 10, 12, 13, 23, 32). The remaining 16 samples were further
divided into 5 smaller groups: 3, 11, 28 could not be differentiated from each
other; 5, 7, 15 could not be differentiated from each other; 6, 8, 16, 26 could not
be differentiated from each other; 27, 33 could not be differentiated from each

other; and 9, 14, 24, 25 could not be differentiated from each other.

 

 

 

 

 

a!

3U

CONCLUSIONS AND SUGGESTIONS FOR FURTHER RESEARCH

The protocol that was created for characterizing body filler and spot putty
samples proved to be a straightforward, easy and a relatively quick procedure.
The combination of three different techniques helped to individualize 13 out of 33
samples, while placing the remainder of the samples into smaller groups.
However, this analysis scheme can only be successful if a crime laboratory has
access to all three of the instruments used in this study.

The analysis techniques that were used in this study primarily focussed on
the organic components of the body filler and spot putty samples. Since these
samples are largely made up of inorganic elements, it would be extremely useful
to test all of these samples using Scanning Electron Microscopy (SEM-EDX),
which would help in identifying some of the major inorganic components. The
author believes that the use of SEM-EDX would help to further individualize the
remaining samples and/or place them into even smaller groups. In addition,
these samples were run as they came from the manufacturer, straight from the
can and not taken from paint chips or an automobile. It would be interesting to
see if the results would change when a sample was taken from an automotive
shop floor or from a car itself that has been repaired and its filler painted over.
The author feels that there would not be much seen by way of changes in
chemical composition. The body filler/spot putty would be protected from
weathering and destruction by the application of paint over top of it when placed

on a car, or by being protected in the shop by storing and capping it properly.

45

SUGGESTED PROTOCOL

Before attempting to analyze this type of forensic evidence, there are a
number of factors that a scientist must keep in mind. First of all, the scientist
must decide how much weight to place on a specific type of evidence. This will
help to determine the analysis protocol the scientist will follow. Also, the scientist
must be aware of the quantity of the sample, because some tests are destructive.
Keeping all of this in mind, a protocol is suggested for the analysis and
comparison of forensic body filler and spot putty samples.

Since pyGC is a destructive test, the scientist should first attempt to
examine any known and questioned samples under the stereoscope so they
could make a good observation of the color. Next, the scientist should attempt to
scrape away as much of the sample as possible from the paint or metal it’s
attached to, keeping in mind that if the sample is being removed from adhering
paint, contamination may result from the bottom layer of paint interacting with the
top layer of sample. Thus, the scientist should attempt to obtain the best
representative sample as possible, by sampling from the middle of the body filler
or spot putty layer and not from either end. With the remaining sample, the
scientist should then try to perform FTIR by preparing the sample as a KBr pellet.
If the sample is limited, FTIR should be done before pyrolysis since it is not a
destructive test. If the sample needs to be recovered after FTIR, one could
dissolve the KBr into water, evaporate the water and recover the sample. Lastly,
pyrolysis should be performed since it is destructive and does not require a very

large amount of sample. Hopefully, if all 3 analysis techniques are available and

46

used, the scientist will get a really good idea of whether these two samples are
alike or not.

Finally, the results of all 3 of the analysis techniques should be taken into
account and given equal weight when drawing any conclusion as to whether the
questioned body filler/spot putty sample could or could not have originated from

the same source as the known body filler/spot putty sample.

47

APPENDICES

48

APPENDIX A

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REFERENCES

117

 

REFERENCES

Cleverley, B. (1970). The Identification of Motor Body Fillers. Joumal of the
Forensic Science Society, 20: 73-76.

Cirimele, V. (2000). Gas Chromatography. The Encyclopedia of Forensic
Science, Analytical Techniques: 151 -1 52.

Home, J. et al. (1980). The Characterization of Motor Vehicle Body Fillers.
Medicine, Science and Law, 20(3): 163-174.

Kirkbride, K.P. (2000). Spectroscopic Techniques. The Encyclopedia of Forensic
Science, Analytical Techniques: 179-191 .

Saferstein, R. (1993). Forensic Applications of Infrared Spectroscopy. Forensic
Science Handbook, Volume III, Englewood Cliffs, New Jersey: Regents/Prentice
Hall, page 155.

Walsh, K.A.J. et al. (1986). New Zealand Body Fillers: Discrimination Using IR
Spectroscopy. Visible Microspectrophotometry, Density and SEM-EDAX.
Forensic Science lntemational, 32: 193-204.

118

 

 

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