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I i at ” (LY) llllllllHllllllllll’llllllllllllllllllllll 02050 9950 E?’fii jx" ‘7 H t afif‘ A ; rd ‘ at "5...! £‘a'-‘vll!i fignk ‘23 l UETSZ‘E sty: I This is to certify that the thesis entitled DIFFERENTIATION OF SMOKELESS POWDERS USING FOURIER TRANSFORM INFRARED SPECTROPHOTOMETRY AND MORPHOLOGY presented by Melissa Dawn Felton has been accepted towards fulfillment of the requirements for M.S. degree in Criminal Justice or p essor Date ”/3 Q/q? 0-7639 MS U is an Affirmative Action/Equal Opportunin Institution PLACE IN REI'URN BOX to remove this checkout from your record. TO AVOID HNB return on or before date due. MAY BE RECALLED with earlier due date if requested. DATE DUE DATE DUE DATE DUE 11m mm.pe5-p.14 - DIFFERENTIATION OF SMOKELESS POWDERS USING FOURIER TRANSFORM INFRARED SPECTROPHOTOMETRY AND MORPHOLOGY BY Melissa Dawn Felton A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE School of Criminal Justice 1999 ”O- h- 1.1-; . C. a “H V“ a.“ D“- ‘v ABSTRACT DIFFERENTIATION OF SMOKELESS POWDERS USING FOURIER TRANSFORM INFRARED SPECTROPHOTOMETRY AND MORPHOLOGY BY Melissa Dawn Felton In this study, a combination of Fourier transform infrared spectrophotometry (FTIR) and morphology was used to differentiate between brands of smokeless powders. FTIR spectra and morphological characteristics such as shape, color, perforation, and size were obtained for each of 50 smokeless powders. In addition, a digital micrograph of each powder was taken using a scanning electron microscope. After analyzing all of the powders, the FTIR spectra, morphological data, and micrographs were compiled to create a reference manual. Three of the 50 smokeless powders examined were randomly selected by Christopher Bommarito, a forensic scientist with the Michigan State Police, and reanalyzed. Based on the results of these analyses, each of the three questioned powders was identified correctly. Because these questioned powders were randomly selected from the powders in the reference manual, the results are consistent within this database only. Therefore, the reference manual can be used for identification purposes as long as the questioned powder is one of the smokeless powders in the database. ACKNOWLEDGMENTS My sincere thanks to my professor and advisor, Dr. Jay A. Siegel, for his commitment and dedication to expanding my knowledge of forensic science. His expertise, encouragement, and support helped make this research project a reality. I would also like to express my gratitude to Christopher Bommarito, a forensic scientist with the Michigan State Police, who suggested the project and provided the materials and instrumentation necessary to carry out the project. Without his guidance, this research would not have been possible. iii bk. :4 1 air! Revie 1. J. Pa “3 A: C“ . 7., n. ‘Y“\ y ‘ ‘5' ‘ e I TABLE OF CONTENTS List of Tables .............................................................................................. v List of Figures ............................................................................................ vi List of Abbreviations .............................................................................. viii Introduction ................................................................................................... 1 Review of the Literature ...................................................................... 11 Materials and Methods ............................................................................. 15 Results and Discussion .......................................................................... 22 Conclusion ....................................................................................................... 57 References ....................................................................................................... 62 Appendix A.—— Organic compounds that may be found in smokeless powders ................................................ 66 Appendix B —— Reference manual of smokeless powders ........ 67 Appendix C —— Distinguishing peaks present in the FTIR spectra of each of the SO smokeless powders analyzed .......................................................... 118 iv Table Table Table Table Table Table Table Table LIST OF TABLES Alphabetical list of smokeless powders analyzed. Particle size data for Hercules Bullseye. Morphological characteristics. Smokeless powders grouped according to shape. Morphological characteristics of questioned smokeless powders. Powders with similar morphology to Questioned Smokeless Powder #1. Powder with similar morphology to Questioned Smokeless Powder #2. Powders with similar morphology to Questioned Smokeless Powder #3. ...,q 0. wk. 1 g; Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure Figure 10 ll 12 l3 14 15 16 17 18 19 20 LIST OF FIGURES Five basic shapes of smokeless powders. Perforated and non—perforated powders. Basic components of a Michelson interferometer. Analytical scheme used for identifying smokeless powders. Ball powders. Cylinder powders (A). Cylinder powders (B). Cylinder powders (C). Cylinder powders (D). -— Cylinder powders (E). —— Cylinder powders (F). —— Disk powders (A). —— Disk powders (B). —— Disk powders (C). —— Disk powders (D). —— Disk powders (E). —— Flake powders. —— Flat Ball powders (A). —— Flat Ball powders (B). —— Flat Ball powders (C). Vi Figure Figure Figure Figure Figure Figure Figure Figure 21 22 23 24 25 26 27 28 Flat Ball powders (D). FTIR spectrum of Questioned Smokeless Powder #1. FTIR spectrum of Questioned Smokeless Powder #2. FTIR spectrum of Questioned Smokeless Powder #3. Comparison of spectra similar to Questioned Smokeless Powder #1. Micrograph comparison of Hodgdon H-4831 and H-57O to Questioned Smokeless Powder #1. Comparison of spectra similar to Questioned Smokeless Powder #2. Comparison of spectra similar to Questioned Smokeless Powder #3. vii PH," F R -‘é‘ "F G“ ~ - L 58:. fi“? but — .9 v ...D non.“ "W 1!“. ‘- v.“ h-«Y _ A.u‘ fix ,\ b‘Wi‘ L.‘ \ '1‘? m“ 7‘ \ "f ‘2.:‘ LIST OF ABBREVIATIONS FTIR —— Fourier transform infrared spectrophotometry GC —— gas chromatography GC—MS —— gas chromatography—mass spectrometry GTN —— glycerol trinitrate HPLC —— high performance liquid chromatography IR —— infrared KBr —— potassium bromide MCT —— mercury cadmium telluride NC —— nitrocellulose NG —— nitroglycerin PMR —— proton magnetic resonance SEM —— scanning electron microscope UV/TEA —— ultraviolet/thermal energy analyzer viii - ”:4 TaCJL‘ Lt u are [Di . - cas 8. Au Ad ”Us l I de: ~lo Ident. DOW EXD ”Ry-q. c . Uta.i“( ‘d con; INTRODUCTION Smokeless powders are propellants formulated and manufactured for use in firearms [7]. Specifically, they are used by firearms enthusiasts in reloading cartridge casings and shotgun shells. For this reason, smokeless powders are readily available for purchase at sporting goods stores. Aside from their legitimate use in firearms, smokeless powders are sometimes used in the production of pipe bombs and other improvised explosive devices. Following an explosion, unburned particles of the smokeless powder may remain. Since forensic scientists occasionally encounter such particles, a method capable of differentiating between manufacturers of smokeless powders is desirable. For instance, if a single brand of smokeless powder was used and the brand could be identified, then investigative efforts could be focused on suspects with that particular brand in their possession. Even if the brand could not be identified, the smokeless powder found at the crime scene could still be compared to smokeless powder(s) found in a suspect’s possession. In this study, FTIR spectra and morphological characteristics such as shape, color, perforation, and size were obtained for a variety of smokeless powders. In addition, a digital micrograph of each powder was taken using a scanning electron microscope. The spectra, KETHr b;..~ morphological data, and micrographs were then compiled to create a reference manual. Although analytical techniques such as morphology, pyrolysis gas chromatography, proton magnetic resonance, gas chromatography, gas chromatography-mass spectrometry, high performance liquid chromatography, and infrared spectrophotometry have been used to differentiate between brands of smokeless powders, no studies have combined FTIR with morphology. Furthermore, none of the previous studies on the differentiation of smokeless powders compiled the results into a reference manual. For these reasons, research on the differentiation of smokeless powders by FTIR and morphology would benefit the forensic science community. Specifically, this research method would provide forensic scientists with yet another technique to use. Depending on the instrumentation available at a particular laboratory, this method might be more readily available than other methods. In addition, the reference manual allows the forensic scientist to compare a questioned sample’s FTIR spectrum and morphological characteristics to known samples in order to determine the brand of smokeless powder. Without this reference material for comparison, identification would not be possible. Smokeless Powders Smokeless powders, the safest and most powerful of the low explosives, are grouped into three general categories including single, double, and triple—base [14]. Single and double—base smokeless powders are used in rifle and pistol cartridges, respectively [4, 10]. Triple—base powders are used in rockets and military ordinance [1]. For these reasons, single and double-base powders are encountered in the forensic science laboratory more often than triple—base powders. The main constituent of single—base powders is nitrocellulose (NC) [1, 6, 12]. In addition to NC, double- base powders also contain nitroglycerin (NC) [14, 18]. The NO present in smokeless powders is known as glycerol trinitrate (GTN), whereas the NC in dynamite is a mixture of GTN and ethylene glycol dinitrate [4]. Triple-base powders are composed of NC, NC, and nitroguanidine [3]. In order to enhance the performance and/or add stability to the powder, the primary ingredients are usually combined with a variety of additional organic compounds [1, 4]. Specifically, these additives act as stabilizers, plasticizers, and flash inhibitors. Stabilizers are added to prolong the storage life of the smokeless powders [1, 6]. Common stabilizers used are diphenylamine, ethyl centralite, and methyl centralite [4, 6-7]. Plasticizers, which are used to provide strengthened flexibility, include dibutyl phthalate, diethyl phthalate, dime: .iash some a su- .nese smokr Cate< “ . v R, sq Ma. e x .3. 3 ‘ dimethyl phthalate, and triacetin [10]. Dinitrotoluene and potassium sulfate are commonly found in smokeless powders as flash inhibitors, also known as burning modifiers [7, 10]. According to Meng and Caddy, graphite is also found in some propellants [10]. Used as a coating, the graphite prevents the accumulation of static electricity and acts as a surface lubricant to improve the flow properties of the powders. Besides these commonly encountered additives, other organic compounds may be found in smokeless powders. A list of 23 such compounds was compiled by the FBI Laboratory [8]. These components are listed in Appendix A. In addition to the different chemical compositions of smokeless powders, propellants can also be divided into categories based on physical characteristics [20]. In particular, physical characteristics such as size, shape, color, and perforation, or lack thereof, differ for various powders [5, 11]. By varying size, shape, and perforation, the burning rate of the smokeless powders can be adjusted. Based on shape, smokeless powders can be divided into five basic categories including ball, cylinder, disk, flake, and flat ball [11]. An example of each shape is displayed in Figure 1. Color ranges from gray to black with some smokeless powders having central colored spots as well. For example, red and green central spots are present on Hercules Red Dot and Green Dot powders, respectively [20]. Perforation, or lack thereof, can further distinguish Disk powder. Figure l —— Five basic shapes of smokeless powders. Flat ball powder. Figure 1 (cont’d). theSi smoke a; 9‘ . , -. “lO‘I‘C—‘C between different brands of disk and cylinder powders [3]. Figure 2 illustrates the difference between a perforated and non-perforated disk powder. Due to the variety of chemical and physical characteristics present in propellants today, analysis of these characteristics can be used to differentiate between smokeless powders. Fourier Transform Infrared Spectrophotometry Fourier transform infrared spectrophotometry (FTIR) is an analytical technique used to measure the absorption of infrared (IR) light by a chemical substance [18]. Radiation in this region corresponds to the vibrational frequencies of molecules and includes the wavenumbers from 4000 to 690 cmd, where cnflis the inverse of wavelength [15]. The relatively high cutoff at 690 cm'1 is due to the detector used in this research, a narrow—band mercury cadmium telluride (MCT) detector. Instead of a diffraction grating, which is used in dispersive instruments, FTIR instruments utilize a Michelson interferometer. As seen in Figure 3, the basic components of a Michelson interferometer are an IR source, a beam splitter, a fixed and a moving mirror, and a detector [15]. A collimated beam from the IR source is directed into the interferometer where it strikes the beam splitter. This beam is then split into two collimated beams, with one beam travelling to a fixed mirror and the other beam travelling Perforated disk powder. Non-perforated disk powder. Figure 2 —— Perforated and non—perforated disk powders. fixed mirror I ‘fi beamsplitter detector 7 ‘ moving mirror sample source Figure 3 —— Basic components of a Michelson interferometer. O l" V trar ARI 8 nc I I. 3.» n..- “M. 1 ‘ ~\~ r i\ vI .O X are x~c INC a.“ AIL v I an.“ .‘ I -‘iI I~u I t IIS Ifiq A~I v I v I ~ I to a moving mirror. The two beams reflect off of the two mirrors and recombine at the beam splitter. The resulting beam then passes through the sample and on to the MCT detector. The signal from the detector is then processed by the computer and an FTIR spectrum, a plot of percentage transmittance versus wavenumber, results. In addition to these basic components, some instruments also have an IR microscope attached in order to analyze extremely small samples. The sample to be analyzed is placed on a potassium bromide (KBr) window, which does not absorb in the mid-IR region [15]. The microscope is then used to View the sample and direct the IR beam through the specific area of the substance to be analyzed [2]. Using the FTIR instrument’s data system, multiple spectral scans of the background are collected and averaged [17]. By averaging the scans, the signal to noise ratio is increased. Once the composite spectrum for the background is obtained, multiple scans of the background plus sample are collected and averaged. The Fourier transform function then subtracts the background’s average transmittance, resulting in the transmittance spectrum of the sample [15]. Transmittance is the preferred method of sampling since spectra obtained using reflectance usually suffer poor reproducibility [2]. 10 me the (T :3 Q) rt '1 (I) U) (D DJ REVIEW OF THE LITERATURE A variety of analytical techniques have been used in an attempt to differentiate between manufacturers of smokeless powders. Specifically, past studies utilized methods including morphology, pyrolysis gas chromatography, proton magnetic resonance (PMR), gas chromatography (GC), gas chromatography—mass spectrometry (GC—MS), high performance liquid chromatography (HPLC), and infrared spectrophotometry to differentiate between brands of smokeless powders. Although several studies used a combination of these methods to analyze smokeless powders, no studies were found that combined FTIR with morphology, as is being done in this research. Physical characteristics alone were used to analyze l2 smokeless powders [20]. Although only a small number of samples were examined, particle size and shape positively identified each of the smokeless powders. Because such characteristics differed for the brands of propellants examined, morphology was sufficient for identification purposes. Pyrolysis gas chromatography was used by Newlon and Booker in an effort to differentiate between smokeless powders [13]. Of the 40 different smokeless powders analyzed, each chromatogram could be distinguished from the others. In particular, significant detail such as the 11 presence of peaks or the variation in relative peak areas of two or more peaks characterized each individual powder. In 1989, Keto attempted to distinguish between smokeless powders using pyrolysis capillary gas chromatography [7]. Unlike Newlon and Booker’s previous study, this research utilized statistical analysis to determine if pyrolysis gas chromatography is a reliable method for identification purposes. Following the analysis of four smokeless powders from each of three manufacturers, variations in relative peak areas between the different brands were seen. However, statistical analysis of the peak areas revealed that these differences were not significant. For this reason, Keto concluded that this technique has limited value for identifying the source of powder. Meyers and Meyers achieved discrimination between smokeless powders through a combination of proton magnetic resonance and gas chromatography [11]. Although the use of PMR alone permitted discrimination between powders from different manufacturers, GC analysis also permitted discrimination between powders within a single manufacturer. Therefore, a combination of the two techniques provided the best method for differentiating between smokeless powders. Capillary column gas chromatography-mass spectrometry enabled Martz and Lasswell to compare and identify smokeless powders [9]. Approximately 100 smokeless powder extracts were resolved into their organic components and identified by their mass spectra. By merging the spectra of the major 12 p8 ak: pOWG i Beca: peaks found in each extract, a composite spectrum for each powder was generated and used to build a spectral library. Because each of the spectra differed, identification of a smokeless powder could be accomplished by comparing a questioned powder’s spectrum to those in the library through a computer search. A direct comparison of the spectra and physical properties of the smokeless powders could then confirm the computer’s identification. Bender analyzed 17 smokeless powder extracts using high performance liquid chromatography with ultraviolet/thermal energy analyzer (UV/TEA) detection [3]. Using this technique, seven major components of smokeless powders were separated and identified. Bender concluded that the relative quantities of these major components and the presence or absence of minor components could be used to discriminate between the powders. For this reason, HPLC with UV/TEA detection proved to be a valuable method for identifying brands of smokeless powders. Infrared spectrophotometry followed by gas chromatography—mass spectrometry was capable of detecting all of the main constituents of single particles of smokeless powders [6]. The preliminary IR examination was used to identify nitrocellulose. Following this analysis, GC—MS was used to identify the additional components of the particles such as nitroglycerin as well as stabilizers, plasticizers, and burning modifiers. By combining these two 13 techniques, individual particles of smokeless powders were positively identified. In 1992, Andrasko used GC and HPLC to compare smokeless powder flakes recovered from around bullet holes on clothing to those from a particular cartridge or ammunition box found in a suspect’s possession [1]. After analyzing more than 20 propellant samples from various manufacturers, Andrasko concluded that both GC and HPLC analyses could distinguish between smokeless powders from different manufacturers. Because different powders showed qualitative differences in composition, single flakes were sufficient for distinguishing between different manufacturers. 14 MATERIALS AND METHODS Approximately 4 to 6 particles of smokeless powder were placed in a small piece of filter paper. About 8 to 10 drops of acetone were then added to the powder. Due to the high solubility of smokeless powders in acetone, this solvent successfully extracts the organic components from the particles [4, l6, 19]. The resulting liquid extract was collected on a microscope slide and allowed to evaporate to dryness. Following evaporation, the residue was scraped off with a scalpel and placed on the surface of a KBr window. The residue was then analyzed using FTIR with a microscope attachment. The above procedure was used to analyze 50 smokeless powders that were obtained from the Michigan State Police Forensic Laboratory in East Lansing, Michigan. An alphabetical list of the powders analyzed is given in Table l. The laboratory’s FTIR instrument, a Perkin-Elmer Spectrum 1000 with AutoImage Microscope System (Version 3.1) was used to analyze all 50 powders. Prior to each day’s analyses, liquid nitrogen was added to cool the MCT detector. As previously noted, the lower wavenumber limit for the MCT detector was 690 cmfl. Thirty minutes after the addition of liquid nitrogen, the energy levels of the instrument were monitored. The microscope’s stage was then initialized and the aperture was calibrated. 15 Table 1 ——.Alphabetical list of smokeless powders analyzed. A A A A Alcan Alcan Alcan Alcan Dupont Dupont Dupont Dupont Dupont Dupont Dupont Dupont Dupont Dupont Dupont Dupont Dupont L-5 L-7 L—8 L—120 #5 Pistol #6 Pistol 700x 800x Hi—Skor IMR—3031 IMR—4064 IMR-4l98 IMR—4227 IMR—4759 PB SR—4756 SR—7625 Hercules Hercules Hercules Hercules Hercules Hercules Hercules Hercules 2400 Blue Dot Bullseye Green Dot Herco Hi-Vel—2 Red Dot RL-ll Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon Hodgdon H-llO H-322 H-335 H-375 H-380 H-4l98 H—450 H-4831 H—4895 H-57O H-870 HS—5 HS-7 X-58 Norma N—200 Norma N-201 Norma N—204 Norma N—205 Winchester Winchester Winchester Winchester Winchester Winchester Winchester 296 450-LS 473—AA SOO-HS 571 760 785 16 fl, :3 (D It”) bask; then pp“? ‘ *- V“ at“ d] F‘— ..e pg Once calibration was completed, the smokeless powder residue was located in the field of view and the aperture was adjusted. By adjusting the aperture, the exact area of the sample to be analyzed was isolated [2]. After the area of the sample to be analyzed was selected, the transmittance mode was used to collect 32 scans of the background followed by 32 scans of the background plus the smokeless powder residue. The computer then ratioed the spectra in order to obtain a spectrum of the smokeless powder. Following analysis, each of the spectra was saved to the hard drive. The FTIR spectra were then compiled into a spectral library of smokeless powders. A digital micrograph of one particle of each smokeless powder was then taken using a LEO 435VP scanning electron microscope (SEM). After each image was captured, it was annotated with the particle’s size. This was done using the software’s measurement tools. Once annotated, the images were saved to the hard drive. Besides measuring one particle of each smokeless powder using the SEM’s measurement tools, ten individual particles of a randomly selected powder (Hercules Bullseye) were also measured (Table 2). In addition, the standard deviation of the particle size data was calculated. The purpose of such measurements was to determine whether the size of a smokeless powder varies considerably within a batch. In addition to the size characteristics, other morphological characteristics for each smokeless powder were 17 The p the s C -rom ":7 H 'U Table 2 —— Particle size data for Hercules Bullseye. PARTICLE SIZE 838 829 830 848 834 824 844 826 815 852 1 2 3 4 5 6 7 8 9 H O The population standard deviation is calculated by taking the square root of the mean of the squares of the deviations from the arithmetic mean of the distribution. n Edi-W 0:402 = i=1 = L22 = 10.964 um N 10 p 2 population mean (834 um) N = number of samples (10) 1'8 p Q'Wyd E dis~“ those Possi] DOWde: ident] noted and the observations recorded. Specifically, the shape (ball, cylinder, disk, flake, or flat ball), color, and perforation, or lack thereof, were recorded. A complete list of all of the morphological characteristics is given in Table 3. Using a series of cutting and pasting techniques, the micrograph and FTIR spectrum of each powder were printed along with the corresponding morphological characteristics. The data were then compiled to create a reference manual (Appendix B). Once the reference manual was created, three of the 50 smokeless powders were randomly selected and reanalyzed. The actual results of the three powders, which were randomly selected by Christopher Bommarito, a forensic scientist with the Michigan State Police, were not revealed until the powders had been examined and identified. The powders were analyzed using FTIR and morphology, as discussed previously. The results were then compared to those in the reference manual in an effort to identify the possible manufacturer(s) of the questioned smokeless powders. A diagram of the analytical scheme used for identifying smokeless powders is shown in Figure 4. l9 Table 3 — Morphological characteristics. NAME SHAPE COLOR. PERFORATED SIZE Alcan AL—5 Flake Black No 507 pm Alcan AL—7 Flake Black 1%) 611 flm Alcan AL-8 Flake Gray No 1.3 mm Alcan AL-120 Disk Black Yes 820 pm Dupont #5 Pistol Disk Gray No 920 um Dupont #6 Pistol Flake Black No 1.1 mm Dupont 700x Disk Black Yes 1.5 mm Dupont 800x Disk Black No 1.8 mm Dupont Hi—Skor Disk Gray Yes 849 um Dupont IMR-3031 Cylinder Gray Yes 2.0 mm Dupont IMR—4064 Cylinder Gray Yes 2.1 mm Dupont IMR—4198 Cylinder Gray Yes 2.2 mm Dupont IMR-4227 Cylinder Black Yes 570 um Dupont IMR-4759 Cylinder Gray Yes 1.4 mm Dupont PB Disk Black Yes 805 pm Dupont SR-4756 Disk Gray' No 1.1 mm Dupont SR-7625 Disk Black bk) 729 um Hercules 2400 Disk Gray No 741 pm Hercules Blue Dot Disk Black No 1 3 mm Hercules Bullseye Disk Gray N0 838 um Hercules Green Dot Disk Black Yes 1.3 mm Hercules Herco Disk Black bk) 1.6 mm Hercules Hi-Vel-2 Cylinder Gray Yes 2.3 mm Hercules Red Dot Disk Black Pk) 1.6 mm Hercules RL—ll Cylinder Gray Yes 1.2 mm Hodgdon H—llO Flat Ball Black No 566 um Hodgdon H-322 Cylinder Black Yes 810 pm Hodgdon H—335 Flat Ball Gray No 653IEm Hodgdon H-375 Flat Ball Gray No 5854pm Hodgdon H-38O Ball Black No 636 pm Hodgdon H—4198 Cylinder Gray Yes 2.2 mm Hodgdon H-450 Flat Ball Gray No 929 pm Hodgdon H—483l Cylinder Gray Yes 2.1 mm Hodgdon H-4895 Cylinder Gray Yes 1.2 mm Hodgdon H-57O Cylinder Gray Yes 2.1 mm Hodgdon H—870 Ball Black No 721 um Hodgdon HS-S Flat Ball Gray No 529 um Hodgdon HS—7 Flat Ball Gray No 917 “m Hodgdon X—58 Flat Ball Gray No 1.2 mm Norma N—200 Cylinder Gray bk) 1.0 mm Norma N-201 Cylinder Gray No 1.1 mm Norma N—204 Cylinder Gray No 1.4 mm Norma N-205 Cylinder Gray No 1.5 mm Winchester 296 Flat Ball Black bk) 573 flm Winchester 450-LS Flat Ball Gray’ No 934 pm Winchester 473—AA Flat Ball Gray No 594 pm Winchester BOO-HS Flat Ball Gray No 724 um Winchester 571 Flat Ball Gray 1%) 899 Hm Winchester 760 Flat Ball Black No 809 um Winchester 785 Flat Ball Gray 1%) 959 “m 20 questioned smokeless powder ball? cylinder? disk? flake? flat ball? . - . \ [Visual examination] 2' shape? —————€> gray? color?L-———*€> black? _————€> not certain? (include both) perforated? yes? no? \/ use SEM to obtain micrograph and <}——— determine size of particle(s) l eliminate smokeless powders with morphological characteristics (shape, color, perforation, and size) different than those of the questioned powder extract organic components with acetone] I analyze by FTIR l compare FTIR spectrum of questioned powder to spectra of smokeless powders that were not eliminated l eliminate smokeless powders with FTIR spectra different than those of the questioned powder I powders not eliminated? 1? __ report identification —— > 1?—— compare micrographs 1 report identification] Figure 4 —— Analytical scheme for identifying smokeless powders. 21 i . cate Spec axial LLE var r: a é a I RESULTS AND DISCUSSION Because the shape of a smokeless powder is easy to discern and because the shape falls into one of five groups, this morphological characteristic was used initially to categorize the 50 smokeless powders. Based on shape, the 50 smokeless powders were divided into five groups —— ball, cylinder, disk, flake, and flat ball (Table 4). Specifically, there were 2 ball powders, 16 cylinder powders, 14 disk powders, 4 flake powders, and 14 flat ball powders. Each of the FTIR spectra within the groups was then analyzed and categorized. All 50 FTIR spectra displayed peaks at 1650, 1380, 1280, 1065, 835, and 750 cmd. For this reason, these peaks were not used to differentiate between the smokeless powders. It is important to note that variations in wavenumbers (cmd) may occur due to error margins for the peaks. Specifically, peaks may vary by as many as six wavenumbers. Ball Powders Both of the ball powders shared peaks at 1718, 1456, 1125, and 1001 cm‘1 (Figure 5). Hodgdon H—870 had additional peaks at 1024 and 915 cmd, whereas Hodgdon H—380 did not. 22 Table . I. I I .. I ‘ fl.» at; .I.. "n. a "Iv; n\,~ pg a...» III:IIIIIIEIIIIIII:I SIS _ Table 4 —— Smokeless powders grouped according to shape. SHAPE NAME Ball Hodgdon H—38O Hodgdon H-87O Cylinder Dupont IMR-303l Dupont IMR-4064 Dupont IMR-4198 Dupont IMR-4227 Dupont IMR—4759 Hercule s Hi—Vel—2 Hercule s RL—ll Hodgdon H—322 Hodgdon H-4l98 Hodgdon H-4831 Hodgdon H-4895 Hodgdon H-570 Norma N -200 Norma N —201 Norma N -204 Norma N -205 Disk Alcan A L-120 Dupont #5 Pistol Dupont 7OOX Dupont 800X Dupont Hi-Skor Dupont PB Dupont SR-4756 Dupont SR-7625 Hercule s 2400 Hercule 5 Blue Dot Hercule s Bullseye Hercule s Green Dot Hercule s Herco Hercule 5 Red Dot Flake Alcan AL—5 Alcan AL—7 Alcan AL-8 Dupont #6 Pistol Flat Ball Hodgdon H-110 Hodgdon H-335 Hodgdon H—375 Hodgdon H—450 Hodgdon HS- 5 Hodgdon HS— 7 Hodgdon X—58 Winchester 296 Winchester 450-LS Winchester 473-AA Winchester SOC-HS Winchester 571 Winchester 760 Winchester 785 23 6.50309 Sam .I m 0.53m odaw 83 82 Sam Sen ode?V nu_— ~oo— one- 1 m—a as: 838: 82 fix. ”—5— nu—_ ome— 83. .688: . 24 DIOIT‘. v. :J .64 1; O. ..I I. :1 a 9 ‘ *JI Cylinder Powders Twelve of the sixteen cylinder powders displayed a peak at 1718 cm"1 (Figures 6—9). Of these powders, three spectra had an additional peak at 1603 ch (Figure 6). Dupont IMR- 4064 and IMR-4198 exhibited similar spectra and shared prominent peaks at 1531, 1348, 1204, 915, 791, and 732 cm“. Norma N-204 also had peaks in these regions. However, the peaks at 915, 791, and 732 cm"1 were not as prominent as those in Dupont IMR-4064 and IMR-4198. Three cylinder powders shared a peak at 1544 cm’1 and displayed similar spectral characteristics (Figure 7). The remaining six powders with a peak at 1718 cm"1 can be seen in Figures 8 and 9. Three of these powders had prominent peaks at 1593 and 1495 cm‘1 (Figure 8), whereas the other three powders did not (Figure 9). Only four of the cylinder powders lacked a peak at 1718 cm’1 (Figures 10 and 11). Of these four powders, Hodgdon H— 4831 and H-570 exhibited similar spectra with peaks at 1603 and 1204 cm'1 (Figure 10). In addition, these powders displayed the same prominent peaks as those in Dupont IMR- 4064 and IMR—4198 (Figure 6). These peaks were not present in Dupont IMR—4759 and Hodgdon H—4895 (Figure 11). However, the spectra were similar to one another. Disk Powders All of the disk powders shared peaks at 1456, 1158, and 1119 cm'1 (Figures 12—16). In addition, five powders had an 25 . A5 mumpsom noocaaxo it w wusmfim Tao edgy A5¢_ A5m_ ISEN OQXU c693. rm? :2 82 3: u .2. as 32 an“ _ .. 3. 2a 2.2 :2 82 . :K 32 v3-2 «:52 3: .. Eon . no _ v.5): an Ex. 2a. f 9.2 82 r «2. “a xx. as. Kb «83.2 .895 26 QQN-Z .2552 .Amv muoc3om Moonwaxo II b wuzmwm ~05 6.8% coo— 82 ocom 80m $68? 38— as. ncN-Z 5.502 as. as. .. PIX. _¢N-Z Sup—OZ 3a. . a:— F e 86.2 «5.82 27 I. -75 -I: 3.22: N 669v .AU. mumpsom M23516 I m 9“sz 7:8. 82 82 88 8cm ‘ sees. a: «W. . . . 2: . 8:1: 8&8: . a: . a: . 2: . I. «9.: 2-12 8398: a: a: 263: 8386: . Ex. 28 li\.rl.lll\ ..l 1 Remix: .535 N . R: 9.30on Moonwaxu I: m 0.5.54.5 750 3.8 82 82 88 88 982. a: . New: .688: . s 22 Pk. r savazzeoeso . 32 .. , - .mem-m2_.8e=o . 29 .3: 30638 “06:33 I 3 3236 odae cog can ~ occm 8cm . odccv «as new. InmflxQ) nee. . .9» j . “Ia sea. . . i s 2.9: 8&8: «VMI Inn. . bx. «ms nee. . . SI. n3 1 sea. 5...: 888: 3O $.80 coc— oa: . .Leo SON .Imv muoczom umccfiaxu II Ha ousmwm 8am odoov 8%.: .688: EX. 82.5): 2695 31 .Idv muoczom Xmfin II NH musmflm odmw 82 82 Sea 83 ochV 2: an: on: n:— mvfl «an. “on 35 8.38: . EI’F 3635 683 r m_s_ . .FIA a___ an“. My; :syasna . enII eme— e_s_ x8388 . e___ new. . anII env— m_e_ I86: 2 seed I 323 . av mumvzom v1.5.5 I ma mhsmwm 780 cdaw c2: 82 8am 8am $.83. ex. :2 2: . an: en: E r 6335 88.5 _mm— Ex. 2.: . a___ wav- en__ e~e_ w—h_ xees I895 II 33 48 306on 0.63 l 3.. 393m @600 83 . 82 86" San $.89. 2 2 :2 .. an: on: .954: anon—5Q FIX. wnn _ on: 8712 58? 34 I 41131 ‘I 1' 993:5 .3393: .2: 30633 xmeo I ma 053m ~05 0.009 80— Sm— och 009m 6.25? 54.3 2: an: em: 8: . + can 2: .. 32 on: “a .8 Be 8:68: a: on: . fix. 88: 8308: I steam 838...: 35 . :5 9.50on 0.9.5 I ma muzmflm 7:6 25— can — accm cccm adccv 2 = no: cOVN 315.8: .. FIX. ONO— o— : em: 5: .. «Ch— :005 8155: 36 2 . Y . l r «li‘ 3‘ k (V I r d qd bl' — a l «a X I: e In I” a X A. .h u e 8 UL ”H“ . l a 1P“ E .J... Cu h: DI PC nUI a: peak: tZESe A CC ~ C“): extra peak at 1718 cm"1 (Figure 12). Dupont #5 Pistol, 800x, PB, and SR-7625 also displayed a peak at 1538 cm4, whereas Hercules Blue Dot did not. Furthermore, Dupont SR—7625 had a prominent peak occurring at 1345 cmd, which was not seen in the other spectra. Both Dupont 700x and SR—4756 showed a doublet at 1718 and peaks at 1531 and 1348 cm"1 (Figure 13). SR-4756 also had an extra peak at 732 cmd, whereas Dupont 700x had an extra peak at 1426 cm”. Seven disk powders lacked a peak at 1718 cm"1 (Figures 14—16). Of these powders, Alcan AL—120 and Dupont Hi-Skor shared peaks at 1538 and 1204 cm'1 (Figure 14). Hercules Bullseye and Herco also had a peak at 1204 cm'1 but lacked a peak at 1538 cm'1 (Figure 15). In addition, these two spectra displayed similar spectral characteristics with peaks at 1426, 945, and 896 cmd. Hercules Red Dot also had these peaks present but lacked peaks at 1538 and 1204 cm”1 (Figure 15). Hercules Green Dot and 2400 lacked prominent peaks at 1538, 1426, 1204, 945, and 896 cmd(Figure 16). However, these two spectra did share a prominent peak at 1020 cm"1 that was absent from the spectra in Figure 15. Flake Powders All four flake powders shared peaks at 1456, 1119, and 1020 cm'1 (Figure 17). Dupont #6 Pistol had a doublet occurring at 1731 and an extra peak at 896 cmd. Alcan AL—5, 37 I32: Sq IIIIEIIQ m .mumczom mmem II ea musmwm TED cdac 25— can _ coca 25m $62? . em: a:_ p . r 6:; «KI a as: :82 r r ea: 82 - ii I.-._< =82 . 2 Z on: 82 m:_ . 82 2: wags :32 . ea» ems. - Ins. . .88.. 3 I890 fix. 38 , ll . I. S .C 7; I S e a e w 9 L .1 h .1 r O ,3 an a C F p D. 1 KO ~L “ I .D V“ ‘ g r. ‘ 94.. 9 I: P AL-7, and AL—8 had a peak present at 1718 cmd. Alcan AL—5 also displayed a peak at 1590 cmd, which was not present in the other flake powders. Flat Ball Powders Ten of the fourteen flat ball powders had a peak present at 1718 cm'1 (Figures 18-20). In addition, these ten powders also displayed a peak at 1456 cmd. Three flat ball powders displayed prominent peaks at 1597 and 1119 cm’1 (Figure 18). Of these powders, Winchester 760 had an additional peak at 1534 cmd. Seven flat ball powders also had a peak present at 1119 but lacked a prominent peak at 1597 cm'1 (Figures 19 and 20). All of these spectra also had a peak at either 1161 or 1158 cm'1 that was absent from the spectra in Figure 18. Hodgdon HS-5 had peaks at both 1426 and 1191 cm‘ (Figure 20). None of the other flat ball powders showed the presence of both of these peaks. The four remaining flat ball powders displayed similar spectra and lacked a prominent peak at 1718 ch (Figure 21). A clearer representation of the FTIR spectra results (Figures 5—21) is given in Appendix C. Validation of Reference Manual The morphological characteristics (shape, color, perforation, and size) and FTIR spectra for the three 39 g n Is: 8366: .2: amazon 33 ”I62 I 3 0.33m 98¢ coo— 83 SON 82.. Q89. an: 82 8a 682653 fix. 2: 1 n: 88:53 “In: seem—6: 40 .Im. 6906300 damn spam I: ma magmas mun—0 0.000 000— 002 000m 000m 0.000? a... .a__ saw. . . as. . m=-00m 580053 a:_ . an: en: . as. r ex. a:_ eazsasaaz ”SI . cm: 0:.— 83. 833: . 41 0 n v. >:.....E...::§ N .on muoozom Hana umam :1 on musmflm 75 0.0% 80— 002 000m 000m 0.003. a: G: 8: a: a: a: . 2: . 3: 838: a: a: on: 1 . = u - 2: n: x 8 B: E. a: on: a: 2: a: 27: 833: fl 3: 2: Km g3? 42 00n— .on mumcsom damn umam I: am musmflm 000m 0.009g mwxgsggam mqénv §8Ao£3 Ex. «2?th 23 r cam 83055? 43 randomly selected smokeless powders can be found in Table 5 and Figures 22—24, respectively. According to the data shown previously in Table 2, the particle size of a smokeless powder does not vary considerably within a batch. For this reason, size is a useful morphological characteristic for differentiating between smokeless powders. Based on morphological characteristics alone, a number of smokeless powders in the reference manual were eliminated as the possible brands of the questioned powders. Specifically, only seven of the fifty powders had similar shape, color, perforation, and size characteristics as Questioned Smokeless Powder #1 (Table 6). Only one of the fifty powders shared similar morphology to Questioned Smokeless Powder #2 (Table 7). Furthermore, three powders shared similar morphology to Questioned Smokeless Powder #3 (Table 8). Using the FTIR spectra, the possible brands of the questioned powders were narrowed further. Of the seven powders sharing similar morphological characteristics to Questioned Smokeless Powder #1, two of the powders (Hodgdon H—483l and Hodgdon H-570) shared similar spectral characteristics (Figure 25). Because more than one powder shared similar spectral characteristics to the unknown, a micrograph comparison was conducted (Figure 26). Based on this comparison, Hodgdon H-483l could not be eliminated as a possible source for this unknown powder. 44 Table 5 —— Morphological characteristics of questioned smokeless powders. NAME SHAPE COLOR PERFORATED SI ZE Questioned Cylinder Gray Yes 2.1 mm Smokeless Powder #1 Questioned Disk Black No 734 flm Smokeless Powder #2 Questioned Disk Black No 1.6 mm Smokeless Powder #3 45 ~ \ uouiom 328.05% 3020,3330 N. M. on «2. .3 .3630.“ 33.3.95 630.3350 «0 55.30QO 5.5 I. mm 933m 002 72 .72 j 30— 000m 000m 0.0009 : .838 .833.“ 38280 0.0 v 0— .m— mm .3 Ex. .mm .9. .3 Tan . mom 46 A130 a:— on: n3”— .3 “onion anode—05m omaoeummao no £3.30QO «Huh ..I mm 83mg 002 on: «an _ 0:.— 000m 0.000v N», 80300 mac—3.08m 0250350 «.0 .0— .m— .3 .0— . on . a S. a . 8 . «a . 8 . mm . em .. n.0m 47 ma 50301 3.29325 0.25:“..on \. 0: MI: .3 amazon $39.95 0233350 no 533QO «Ham II vm 83m: 0.0M0 000— 002 000m 000m 0.009. 0 can 2: on: u h a 0 .0” u on: 2 a. \ .2 Ex. ma. 80300 «8.3—oEm 0280390 r «.2 48 .I ,numfl U UEOOO % N 0.3 3 3 D H n: H n: Table 6 —— Powders with similar morphology to Questioned Smokeless Powder #1. NAME SHAPE COLOR PERFORATED S I ZE Questioned Cylinder Gray Yes 2.1 mm Smokeless Powder #1 Dupont IMR—303l Cylinder Gray Yes 2.0 mm Dupont IMR—4064 Cylinder Gray Yes 2.1 mm Dupont IMR-4198 Cylinder Gray Yes 2.2 mm Hercules Hi-Vel—2 Cylinder Gray Yes 2.3 mm Hodgdon H—4l98 Cylinder Gray Yes 2.2 mm Hodgdon H—483l Cylinder Gray Yes 2.1 mm Hodgdon H-57O Cylinder Gray Yes 2.1 mm 49 Table 7 —— Powder with similar morphology to Questioned Smokeless Powder #2. NAME SHAPE COLOR PERFORATED S I ZE Questioned Disk Black No 734 Mm Smokeless Powder #2 Dupont SR-7625 Disk Black No 729 um 50 Table 8 —— Powders with similar morphology to Questioned Smokeless Powder #3. NAME SHAPE COLOR PERFORATED S I ZE Questioned Disk Black No 1.6 mm Smokeless Powder #3 Dupont 800x Disk Black No 1.8 mm Hercules Herco Disk Black No 1.6 mm Hercules Red Dot Disk Black No 1.6 mm 51 .2“ hogan mmmamxosm 693.2695 0» “83.53 muuuomm no comaummsoo I mm whom?“ 7:8 .33 82 82 88 Son 38.. S. n8. . p .2. 82 :2 n; .2. if 4i f 29: 833: 8.: :2 . S. 82 .2. 2o 32 . Ex. :31: 8E8: , $2 :2 5 82 as «8 . 32 5 836m mac—838m Became—.0 r 52 Hodgdon H—4831. Hodgdon H—S70. Questioned Smokeless Powder #1. Figure 26 —- Micrograph comparison of Hodgdon H—483l and H-570 to Questioned Smokeless Powder #1. 53 Only Dupont SR-7625 displayed similar morphological characteristics to Questioned Smokeless Powder #2. In addition, this powder displayed similar spectral characteristics to the questioned powder (Figure 27). For this reason, Dupont SR-7625 could not be eliminated as a possible source for Questioned Smokeless Powder #2. After comparing Questioned Smokeless Powder #3 to the three powders sharing similar morphological characteristics, only Hercules Herco displayed similar spectral characteristics as those in Questioned Smokeless Powder #3 (Figure 28). Therefore, Hercules Herco could not be eliminated as a source for this unknown powder. Following the comparison of the morphology and FTIR spectra of the questioned powders to those in the reference manual, the actual unknowns used were revealed. Questioned Smokeless Powder #1 was Hodgdon H—483l, #2 was Dupont SR- 7625, and #3 was Hercules Herco. 54 ..N&w uEUHZIth .umZUAfiwv:u=aw —vmzunfifinumzwngu .Unu “unfinwéfifimu muuomflm no :OmflHmQEou II hm musmfim 75 92$ 82 82 88 88 38.. 2: m3: .unm. 22 . . r on: on: 28.5 285 «Qfl_ unfl— o_._ u on: 1 an: «.5— Q 338 mafioam 3.88:0 Ex. 55 .3 wanton numauxosm 60.3.3250 ou Mada—«m 93¢ 82 82 coon a» 2: a: an: on: n3 32 a:— can «I unnummm uo camwummsou II mm 9153 080: 8398: m; 826.— a8_oonm 12692.0 . Ex. 56 CONCLUSION As seen in this research, differentiation between smokeless powders was achieved using a combination of FTIR and morphology. Of the fifty smokeless powders analyzed, some shared similar morphological characteristics and some shared similar spectral characteristics. However, none of the powders analyzed shared both similar morphological and spectral characteristics. Since the smokeless powders analyzed in this study did not share similar morphology and FTIR spectra, identification of questioned smokeless powders could be achieved. For example, each of the three randomly selected questioned powders was identified correctly by following the analytical scheme shown earlier in Figure 4. Because these three questioned powders were randomly selected from the powders in the reference manual, the results are consistent within this database only. Therefore, the reference manual can be used for identification purposes as long as the questioned powder is one of the smokeless powders in the database. Identification of the brand of a smokeless powder will be extremely beneficial to the forensic science community. If a forensic scientist can determine the brand of smokeless powder used in an explosion, then investigative efforts could be focused on suspects with that particular brand of powder in their possession. Furthermore, suspects who do 57 not have that powder in their possession could be exonerated. Even if the brand of smokeless powder cannot be identified, comparison of the smokeless powder found at the crime scene to powder found in a suspect’s possession will still have strong probative value. Since the smokeless powders in this study did not share similar morphological and spectral characteristics, two powders displaying such similarities could have originated from a common source. While 4 to 6 particles of each smokeless powder were used in this study, identification is still possible if fewer particles are recovered from a crime scene. While conducting my research at the Michigan State Police Forensic Laboratory in East Lansing, Michigan, a case arose involving one particle of what appeared to be smokeless powder. Upon extraction of the particle's organic components with acetone, the resulting residue was analyzed using FTIR with a microscope attachment. Once the spectrum was obtained, a search of the smokeless powder spectral library was conducted. The single particle's FTIR spectrum displayed all of the same peaks as one of the smokeless powders in the library. Although the morphological characteristics of this questioned particle were not analyzed, these results still demonstrate the usefulness that FTIR has for differentiating between smokeless powders. Moreover, these results indicate 58 that brand identification can be achieved in cases where only one particle of smokeless powder is recovered. It should be noted that spectra obtained on one FTIR instrument should appear similar to spectra obtained on another FTIR instrument. Therefore, the spectra obtained on a different FTIR instrument should appear essentially the same as those displayed in the reference manual. The reason FTIR spectra obtained on one instrument are similar to spectra obtained on another instrument is because FTIR does not depend on the instrument’s settings. In order to continue advancement of the forensic sciences, future research is necessary. Specifically, additional research on the differentiation of smokeless powders should be conducted. Although 50 of the 80 smokeless powders available at the Michigan State Police Forensic Laboratory were analyzed, additional brands of smokeless powders should be obtained and analyzed. The FTIR spectra and morphological characteristics of the powders could then be added to the reference manual. Such research should be pursued until all available smokeless powders are displayed in the reference manual. According to the Arson and Explosives Section of the Alcohol, Tobacco, and Firearms Forensic Science Laboratory in Rockville, Maryland, 134 powders are currently available in the United States. Besides extending the reference manual, the spectral library of smokeless powders should be expanded as well. 59 Although creating a spectral library was not the ultimate goal of this research, an FTIR search program was generated in the process. Because FTIR search programs allow the rapid comparison of a questioned sample’s spectrum to those in the library, such programs are extremely beneficial to the forensic science community. In addition to expanding the spectral library, another library could be created as well. Specifically, the morphological data and FTIR spectra could be compiled into a single searchable program. Such a program would provide similar results to those obtained using the reference manual but in a shorter period of time. Additional research studies could focus on using other methods to differentiate between smokeless powders. In particular, diffuse reflectance infrared Fourier transform spectrophotometry could be used in an effort to discriminate between propellants. Using this technique, the smokeless powders could either be mixed with KBr or ran neat. The spectra obtained using this method could then be compared to those obtained using FTIR to determine which technique yields more information. A final topic for future research could focus on differences in smokeless powders over time. Various smokeless powders could be analyzed using FTIR and morphology over a certain time period. The results from the different times could then be compared to determine whether 60 the FTIR spectra and/or morphology of propellants change with age. Due to the increase in violence involving homemade explosives, it is likely that smokeless powders will continue to be encountered in the forensic science laboratory. Once smokeless powders are recovered from the crime scene, the particles can be analyzed using FTIR and morphology. The results can then be compared to those in the reference manual in order to identify the brand of smokeless powder used, assuming the powder is in the database. Furthermore, the results can be compared to smokeless powders found in the possession of a suspect in order to determine whether the two powders could have originated from a common source. This piece of information could be the ultimate link to connect a suspect with an explosive device. 61 REFERENCES 62 [l] [3] [4] [5] [6] [7] [8] [9] [10] REFERENCES Andrasko, J. “Characterization of Smokeless Powder Flakes From Fired Cartridge Cases and From Discharge Patterns on Clothing.” Journal of Forensic Sciences 37 (1992): 1030—47. Bartick, E. G. & Tungol, M. W. “Infrared Microscopy and its Forensic Applications.” Forensic Science Handbook, VOlume III. Ed. R. Saferstein. Englewood Cliffs, NJ: Prentice—Hall, 1993, pp. 196—252. Bender, E. C. “Analysis of Smokeless Powders Using UV/TEA Detection.” Proceedings of the International Symposium on the Analysis and Detection of Explosives. Federal Bureau of Investigation, Washington, DC, 1984, pp. 309-20. Beveridge, A. D. “Development in the Detection and Identification of Explosive Residues.” Forensic Science Review 4 (1992): 17-49. Hoffman, C. M. & Byall, E. B. “Identification of Explosive Residues in Bomb Scene Investigations.” Journal of Forensic Sciences 19 (1974): 54-63. Kee, T. G., Holmes, D. M., Doolan, K., Hamill, J. A., & Griffin, R. M. E. “The Identification of Individual Propellant Particles.” Journal of the Forensic Science Society 30 (1990): 285-92. Keto, R. O. “Comparison of Smokeless Powders by Pyrolysis Capillary Gas Chromatography and Pattern Recognition.” Journal of Forensic Sciences 34 (1989): 74-82. Maloney, R. S. & Thornton, J. I. “Color Tests for Diphenylamine Stabilizer and Related Compounds in Smokeless Gunpowder.” Journal of Forensic Sciences 27 (1982): 318-29. Martz, R. M. & Lasswell, L. D., III. “Smokeless Powder Identification.” Proceedings of the International symposium on the Analysis and Detection of Explosives. Federal Bureau of Investigation, Washington, DC, 1984, pp. 245-54. Meng, H. & Caddy, B. “Gunshot Residue Analysis: A Review.” Journal of Forensic Sciences 42 (1997): 553— 70. 63 [ll] [12] [13] [14] [15] [17] [18] [19] [20] Meyers, R. E. & Meyers, J. A. “Instrumental Techniques Utilized in the Identification of Smokeless Powders: Proton Magnetic Resonance (PMR) and Gas Chromatography (GC).” Proceedings of the International Symposium on the Analysis and Detection of Explosives. Federal Bureau of Investigation, Washington, DC, 1984, pp. 93- 106. Midkiff, C. R. “Arson and Explosive Investigation.” Forensic Science Handbook. Ed. R. Saferstein. Englewood Cliffs, NJ: Prentice-Hall, 1982, pp. 222*66. Newlon, N. A. & Booker, J. L. “The Identification of Smokeless Powders and Their Residues by Pyrolysis Gas Chromatography.” JOurnal of Forensic Sciences 24 (1979): 87-91. Saferstein, R. Criminalistics: An Introduction to Forensic Science, 5th ed. Englewood Cliffs, NJ: Prentice-Hall, 1995. Suzuki, E. M. “Forensic Applications of Infrared Spectroscopy.” Forensic Science Handbook, Vblume III. Ed. R. Saferstein. Englewood Cliffs, NJ: Prentice-Hall, 1993, pp. 71-195. Washington, W. D. & Midkiff, C. R. “Systematic Approach to the Detection of Explosive Residues. I. Basic Techniques.” Journal of the Association of Official Analytical Chemists 55 (1972): 811—22. Washington, W. D. & Midkiff, C. R. “Explosive Residues in Bombing-Scene Investigations: New Technology Applied to Their Detection and Identification.” Forensic Science, 2nd ed. Ed. G. Davies. Washington, DC: American Chemical Society, 1986, pp. 259—78. Yinon, J. & Zitrin, S. The Analysis of Explosives. Elmsford, NY: Pergamon Press, 1981. Yinon, J. & Zitrin, S. Mbdern.Methods and.Applications in Analysis of Explosives. New York, NY: Wiley, 1993. Zack, P. J. & House, J. E. “Propellant Identification by Particle Size Measurement.” JOurnal of Forensic Sciences 23 (1978): 74-7. 64 APPENDICES 65 APPENDIX A Organic compounds that may be found in smokeless powders. cresol resorcinol carbazole diphenylamine dimethyl phthalate N-nitrosodiphenylamine dinitrocresol carbanilide nitrodiphenylamine triacetin nitrocellulose dinitrotoluene RDX (cyclonite) diethyl phthalate nitroglycerin trinitrotoluene dimethylsebacate N, N-dimethylcarbanilide (methyl centralite) 2, 4—dinitrodiphenylamine N, N—diethylcarbanilide (ethyl centralite) dibutyl phthalate PETN (pentaerythritol tetranitrate) N, N-dibutylcarbanilide (butyl centralite) 66 APPENDIX B Reference manual of smokeless powders. 67 Alcan AL-S Shape: Flake Color: Black Perforated: No Size: 607 pm 47.4 . 45. 40. 35. 30. %T 25. 20. l l .1 4000.0 3000 2000 1500 1000 690.0 68 Alcan AL-7 Shape: Flake Color: Black Perforated: No Size: 611 um 70. 65 . 60. 55. %T4i w. 35. 30.. 25. 19.5 - . . 4000.0 3000 2000 1500 1000 690.0 69 Alcan AL-8 Shape: Flake Color: Gray Perforated: No Size: 1.3 mm 44.6 40. 35. 30. 25. %T 20. 5.4 4000.0 3000 2000 1500 1000 690.0 cm-l 70 Alcan AL-120 Shape: Disk Color: Black Perforated: Yes Size: 820 um 59.8. 55. 50. 45. 40. %T 35. 30. 25. 20. l 1.4 . 4000.0 3000 2000 1500 1000 690.0 71 Dupont #5 Pistol Shape: Disk Color: Gray Perforated: No Size: 920 um 32.9. 32. 30. 28. 26. 24. 22. %T 20 . 4000.0 3000 2000 l500 1000 690.0 72 Dupont #6 Pistol Shape: Flake Color: Black Perforated: No Size: 1.1 mm 5.7 4000.0 3000 2000 1500 1000 690.0 cm-l 73 Dupont 700x Shape: Disk Color: Black Perforated: Yes Size: 1.5 mm 26.0 . 24. 22. 20. 7.4 ' 4000.0 3000 2000 1500 1000 690.0 74 Dupont 800x Shape: Disk Color: Black Perforated: No Size: 1.8 mm 35.61 34. 32. 30. 28. 26. 24- %T 22. 20. 9.9 . 4000.0 3000 2000 1500 1000 690.0 75 Dupont Hi-Skor Shape: Disk Color: Gray Perforated: Yes Size: 849 um 40.2 = 30. 25 . %T 20. 6.9 4000.0 3000 2000 1500 1000 690.0 cm-l 76 Dupont IMR- 3031 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.0 mm 92.2. 85. 80. 75 ‘M %T 55“ 45. 40. 35. 30. 23.6‘ 4000.0 3000 2000 1500 1000 690.0 cm—l 77 Dupont IMR— 4064 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.1 mm 37.0. 35. 30. 25. %T 20. 4.3 ‘ I . 4000.0 3000 2000 1500 1000 690.0 78 Dupont IMR- 4198 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.2 mm 53.6. 50. 45. 40. 35. 3O . %T 25. 20. 3.9 ' 4000.0 3000 2000 1500 1000 690.0 79 Dupont IMR—4227 Shape: Cylinder Color: Black Perforated: Yes Size: 570 um 50.9. 45. 40. 35. %T 30. 25. 20. 14.0 ' 4000.0 3000 2000 1500 1000 690.0 80 Dupont IMR-4759 Shape: Cylinder Color: Gray Perforated: Yes Size: 1.4 mm 58.2 551 50. 45 . 40. 35 . %T 30. 25. 20. l 1 2 4000.0 3000 2000 1500 1000 690.0 81 Dupont PB Shape: Disk Color: Black Perforated: Yes Size: 805 um 5% 40- 351 30. %T 20. 4000.0 3000 2000 1500 1000 690.0 82 Dupont SR-4756 Shape: Disk Color: Gray Perforated: No Size: 1.1 mm 49.1. 45. 40. 35. %T 30. 25. 20. 15.1 , . 4000.0 3000 2000 1500 1000 690.0 83 30.1 %T 28. 26. 24. 22. 20. 1m 7.9 Dupont SR-7625 Shape: Disk Color: Black Perforated: No Size: 729 um 4000.0 3000 2000 1500 1000 cm-1 84 690.0 Hercules 2400 Shape: Disk Color: Gray Perforated: No Size: 741 um 58.7. 55. 50. 45. 40. %T 35. 30. 25. 20 . 17'8 I I I l I 4000.0 3000 2000 1500 1000 690.0 85 Hercules Blue Dot Shape: Disk Color: Black Perforated: No Size: 1.3 mm 32.8. 30. 28. 26. 24. 7.9 4000.0 3000 2000 [500 1000 690.0 86 Hercules Bullseye Shape: Disk Color: Gray Perforated: No Size: 838 um 39.5 . 35. 30. 25. %T 20. 2.8 4000.0 3000 2000 1500 1000 690.0 cm-l 87 Hercules Green Dot Shape: Disk Color: Black Perforated: Yes Size: 1.3 mm 39.8. 35 . 30 25 . %T 201 10. 4000.0 3000 2000 1500 1000 690.0 88 Hercules Herco Shape: Disk Color: Black Perforated: No Size: 1.6 mm 73.2. 70- 65. 60- 55- 50. 45. 40. %T 35. 2.8' 4000.0 3000 2000 1500 1000 690.0 89 Hercules Hi- Vel—2 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.3 mm 51.3. 45. 40. 35. 30. %T 25. 20. 4000.0 3000 2000 1500 1000 690.0 90 Hercules Red Dot Shape: Disk Color: Black Perforated: No Size: 1.6 mm 40.3 = 35. 30. 25. %T 20 . 52 4000.0 3000 2000 1500 1000 690.0 cm-l 91 Hercules RL—11 Shape: Cylinder Color: Gray Perforated: Yes Size: 1.2 mm 30.0. 4000.0 3000 2000 1500 1000 92 690.0 Hodgdon H-110 Shape: Flat Ball Color: Black Perforated: No Size: 566 um 37.0. 35. 30. 25. %T 20. 6 2 4000.0 3000 2000 1500 1000 690.0 93 Hodgdon H—322 Shape: Cylinder Color: Black Perforated: Yes Size: 810 [lm 33.0. 32. 30. 28. 26. 24. 22. %T 20 . 4000.0 3000 2000 1500 1000 690.0 cm-l 94 Hodgdon H-335 Shape: Flat Ball Color: Gray Perforated: No Size: 653 um 412. 45. 40. 35. 30. 96T 25. 20. 9.3 - . . 4000.0 3000 2000 95 1500 1000 6900 Hodgdon H-375 Shape: Flat Ball Color: Gray Perforated: No Size: 585 um 30.1 28. 26. 24. 5.9 . I I 4000.0 3000 2000 1500 1000 690.0 96 67.2 65. 60. 55. 50. 45- 40. %T 35. 30. 25. 20. 9.3 ' 4000.0 3000 Hodgdon H-380 Shape: Ball Color: Black Perforated: No Size: 636 um 2000 1500 1000 cm-1 97 690.0 Hodgdon H- 4198 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.2 mm %T 25. 20. 10. 8.5 4000.0 3000 2000 1500 1000 690.0 98 Hodgdon H-450 Shape: Flat Ball Color: Gray Perforated: No Size: 929 um 30. 25. 20 . %T 1.9 4000.0 3000 2000 1500 1000 690.0 99 Hodgdon H-4831 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.1 mm 48.2. 45. 40. 35. 30. %T 25. 20. 3.2- 4000.0 3000 2000 1500 1000 690.0 cm-l 100 Hodgdon H—4895 Shape: Cylinder Color: Gray Perforated: Yes Size: 1.2 mm 60. 55. 50. 45. 40. %T 35. 30. 25. 20. 15. 13.0 . 1 4000.0 3000 2000 1500 1000 101 690.0 Hodgdon H-570 Shape: Cylinder Color: Gray Perforated: Yes Size: 2.1 mm i 66.1. 60. 55. 50. 45. 40.. %T 35. 30. 25. 20. 4000.0 3000 2000 1500 1000 690.0 102 37.4. 35. 30. 25. %T 20. 4f mmo Hodgdon H-870 Shape: Ball Color: Black Perforated: No Size: 721 um 3000 2000 1500 1000 690.0 103 Hodgdon HS—5 Shape: Flat Ball Color: Gray Perforated: No Size: 529 um 46.8 451 40. 35. 30. %T 25. 20. 6.6 4000.0 3000 2000 1500 1000 690.0 104 235. 22. 20. 3.7' 40000 3000 Hodgdon HS—7 Shape: Flat Ball Color: Gray Perforated: No Size: 917 um 2000 105 1500 1000 6900 Hodgdon x-58 Shape: Flat Ball Color: Gray Perforated: No Size: 1.2 mm 29.0. 28. 26. 24. 22. 7.6 ‘ , . 4000.0 3000 2000 1500 1000 690.0 106 22.0 . 20. 4.7 Norma N—200 Shape: Cylinder Color: Gray Perforated: No Size: 1.0 mm 4000.0 3000 2000 1500 1000 690.0 107 Norma N-201 Shape: Cylinder Color: Gray Perforated: No Size: 1.1 mm 24.2: 22. 20. 2.9 4000.0 3000 2000 1500 1000 690.0 108 Norma N-204 Shape: Cylinder Color: Gray Perforated: No Size: 1.4 mm 27.3. 26. 24. 22. 20. 4000.0 3000 2000 1500 1000 690.0 109 Norma N-205 Shape: Cylinder Color: Gray Perforated: No Size: 1.5 mm 70.0 65 60. 55. 50. 45. %T 40. 35. l 8'3 . I I I ' I I 4000.0 3000 2000 1500 1000 690.0 110 Winchester 296 Shape: Flat Ball Color: Black Perforated: No Size: 573 um 47.4 45 40. 35. 30. 25. %T 20. 3.4 4 4000.0 3000 2000 1500 1000 690.0 111 Winchester 450-LS Shape: Flat Ball Color: Gray Perforated: No Size: 934 um 61.9. 60. 55. 50. 45. 40 %T 35. 30. 25. 20. 16.5 , r f . 4000.0 3000 2000 1500 1000 690.0 112 Winchester 473-AA Shape: Flat Ball Color: Gray Perforated: No Size: 594 um 43.8. %T 15.3- 4000.0 3000 2000 1500 1000 690.0 cm—l 113 Winchester SOD-HS Shape: Flat Ball Color: Gray Perforated: No Size: 724 pm 24.5 22. 20. 2.3 4000.0 3000 2000 1500 1000 690.0 114 Winchester 571 Shape: Flat Ball Color: Gray Perforated: No Size: 899 um 41.9 40 35. 30. 25. %T 20. 4000.0 3000 2000 1500 1000 690.0 115 Winchester 760 Shape: Flat Ball Color: Black Perforated: No Size: 809 um 3.1 4000.0 3000 2000 1500 1000 690.0 116 Winchester 785 Shape: Flat Ball Color: Gray Perforated: No Size: 959 um 4000.0 3000 2000 1500 1000 690.0 117 APPENDIX C Distinguishing peaks present in the FTIR spectra of each of the 50 smokeless powders analyzed. 118 NNMIm GOUOOOE bNNvaxH ucoafla HMOMImSH uGOQ:Q mmH¢Im sconce: Hauqm «magnum: NIH0>IMr mmasoumr mONIZ GEHOZ HONIZ MEHOZ OONIZ GEMOZ «ONIZ MEHOZ x. x x x made-mzH uconso x x $385 9895 30:35 osme coomnom omm-m menace: 2mm mzcz 1", I mmMmHHsm mwasuuom uomeA= access ONHIA< CMUH< omvamm unease Xoor ucomsa UOQ 03AM m0H50H0= mmwhnmm uCOQSQ mm ucoaso xoom unease acumen mu unease xmwa mmme-: conmoo: mmFVImZH uGOQnQ obm-= covmnom ammVIx cowuwom WZ¢Z 4/ I madmm 120 s-m= cocmoom ovam copmvom ooh kummnocflz map “mummsocnz Hana mbm-m coumnom pods m-q< cuoH< qu< cooa< m-q< anufla x Houmnm 6* unease wxoam oosm «unsouo: you smoke mmasouwm x woo pom mwasouwm x ovum: modsouo: .2-L IIIIIIIIII ngz macaw / 121 mme covmuom quomv kummSUCwZ ii MFfi HOUMQAMUCflS mam “0000:0043 mImm covaoo: mmmIm conmoom OHHI: downpom «pm noummnucns szOOm “mummcucfla 31 x m2<2 _ mmcmm 122 MCI-110m smTE UNIV. LIBRRRIES 1 I 111 "WI”WW1W111111111111111 9 0509950 312 302