e x 1 3:: :21 .2 I. r t :2: II. 5‘. \. 7.x. .5: 4., «r. . 1 3 . : Pint. .. $32.“: l. uh. 3.5.: .3; ~ .1 .335 i: r 9.: .1: . z :6 7: :K . ‘ i: I. .1 2. ....;L€T.. .‘2 . s :2: hi. .4 . . . Ltl’nt‘lfl 4 . . 2, . :1? 2:. .32 . 3v. « . : .r. 3.. . : : 1:...1ug z: ‘ 1.3;: T1... f5 ,5; t H“ .. PI: \11.’ :: 1?. a; ‘21)»: in. M Illllllllllllll llllllllllllllllllll'llllllllllelllll ( 3 1293 02079 9254 This is to certify that the thesis entitled DEVELOPMENT OF A COMPREHENSIVE ADHESIVE SPECTRAL LIBRARY - CYANOACRYLATE GLUES presented by Stephen G. Borowski has been accepted towards fulfillment of the requirements for Master of Science degmmin Criminal Justice with Specialization in Forensic Science 0-7639 MSU is an Affirmative Action/Equal Opportunity Institution RETURN BOX ckout from your record. r before date due. frequested. PLACE iN ove this the FiNES return on o with earlier due date i to rem T0 AVOlD MAY BE RECALLED DEVELOPMENT OF A COMPREHENSIVE ADHESIVE SPECTRAL LIBRARY - CYANOACRYLATE GLUES By Stephen G. Borowski A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE School of Criminal Justice 2000 ABSTRACT DEVELOPMENT OF A COMPREHENSIVE ADHESIVE SPECTRAL LIBRARY - CYANOACRYLATE GLUES By Stephen G. Borowski Adhesive-type evidence can appear in a variety of forensic science cases ranging from postal fraud, product tampering, and to certain cases involving homicide. In such cases, a comprehensive library composed of adhesive spectra collected by Fourier transform infrared, (FTIR) spectrophotometry would aid the forensic scientist analyzing such evidence. The purpose of this research was to focus on the individual adhesive class of cyanoacrylate glues, or "super glues." Fifty cyanoacrylate glue spectra were collected and entered into a spectral library. A test of the library was then performed to demonstrate the practicality of such a database. The test showed that, despite the similarities between cyanoacrylate glue spectra, individual samples could be identified. Copyright by Stephen G. Borowski 2000 I would like to dedicate this to my Parents, my wife Susan, and to Amy. Their support and encouragement over the years have helped me during my time at MSU more than they will ever know. ACKNOWLEDGMENTS I would like to thank Dr. Jay Siegel, my professor and advisor at Michigan State University for his assistance and guidance through the Forensic Science Master's program. I would also like to thank Mindy Ferguson for her invaluable assistance and hard work on this project. TABLE OF CONTENTS LIST OF TABLES ....................................................................... vii LIST OF FIGURES .................................................................... viii LIST OF ABBREVIATIONS ......................................................... ix INTRODUCTION .......................................................................... 1 REVIEW OF LITERATURE .......................................................... 9 MATERIALS AND METHODS .................................................... 11 RESULTS AND DISCUSSION ................................................... 15 CONCLUSION ............................................................................ 19 APPENDICES ............................................................................. 22 Appendix A ....................................................................... 23 Cyanoacrylate Glue FTIR Spectra Included in the Library Appendix B ....................................................................... 34 Match "Hits" of Ten Test Samples LIST OF REFERENCES ............................................................. 46 vi LIST OF TABLES Table 1 - Commercial Adhesives ................................................................. 8 Table 2 - Library Test Results .................................... 18 vii LIST OF FIGURES Figure A - Chemical Structures of Cyanoacrylate and Hydroxyl Ions ........ 5 Figure B - Chemical Polymerization of Ethyl-2-Cyanoacrylate .................. 6 viii LIST OF ABBREVIATIONS AES - Auger Electron Spectroscopy ATR - Attenuated Total Reflection FTIR - Fourier Transform Infrared FTMS - Fourier Transform Mass Spectroscopy IR - Infrared KBr - potassium bromide PGC - Pyrolysis-Gas chromatography XPS - Photo-electron Spectroscopy INTRODUCTION Spectral libraries serve as an important part in forensic science today. There are numerous libraries in existence, butnone have exclusively dealt with adhesive compounds. In order to accomplish this, fifty cyanoacrylate FTIR spectra were collected and put into a spectral library. These spectra would act as a starting point for the addition of other adhesive types in the hopes that a comprehensive, searchable adhesive database might be created to better aid the forensic community. Forensic science laboratories handle a myriad of cases everyday, ranging from product tampering to complex homicide cases. In each instance, the evidence submitted for analysis is often as unique as the case itself, and each piece of evidence must be looked at individually in order to try to create a “whole picture” of what might have transpired. In order to do this, today’s forensic scientist must call upon a wide array of resources and techniques to provide as much information as possible. Forensic scientists often rely on instrumental analysis to provide a better understanding of the evidence in question. One of the most powerful instruments used in the analysis of chemical compounds is a Fourier transform infrared spectrophotometer. This instrument makes use of an analytical technique know as Fourier transform infrared (FTIR) spectrophotometry. The FTIR spectrophotometer works in conjunction with a computer and specially designed software. An infrared source in the instrument is used to give off an infrared beam of light, which passes through a given sample. The sample will absorb certain portions of the light depending on its chemical nature. The light transmitted by the sample is then detected by the instrument. This is repeated over a set number of scans, and the information is fed into the attached computer. The software then displays the spectrum of the sample being analyzed. The spectrum serves a very useful function in the, analysis of chemical compounds. Depending on the chemical composition of the evidence in question, the FTIR spectrum can give a chemical profile of the substance based on its spectral peaks. With this in mind, a forensic scientist can use the information generated in a sample’s profile to determine the nature, and quite often, the identity of the evidence in question. One of the most powerful ways to do this is through the creation and use of a spectral library. A spectral library is a collection of spectra obtained under controlled conditions. These spectra are usually in database form and can be easily searched using FTIR software. Spectral databases are widely used in the analysis of drug, accelerant, and fiber evidence. Many of these databases can be commercially purchased for use in forensic science laboratories. The spectrum of the evidence in question can be run against a spectral library, and the computer will attempt to find the entries that appear the most similar, usually giving a “match percentage.” While a search against a spectral library may not give one hundred percent accuracy, it can be a povIrerful tool In helping to identify or exclude evidence being analyzed. In 1997, Jeffrey Kindig published a thesis based on his research in creating a spectral library of adhesives (1). Kindig used FTIR spectrophotometry to evaluate a variety of commercially available adhesive types. The term adhesive was used very broadly and defined as “any material used to fasten one thing to another.” In his work, Kindig produced spectra of various adhesive classes including cyanoacrylate glues ("super glues"), hide glues, glue sticks, cements, and silicone-type adhesives. Kindig's paper served as the basis for the research presented in this thesis. In light of results produced by Jeffrey Kindig, Michigan State University’s School of Criminal Justice decided to create a comprehensive database of adhesive spectra. To facilitate this, MSU entered into a contract with Nicolet Instrument Corporation - “Nicolet.” In the agreement, Michigan State would produce digital spectra of various classes of adhesives using FTIR spectrophotometry. Nicolet, in turn, would receive these spectra and incorporate them into a complete, searchable spectral library available to forensic and industrial laboratories. Once complete, this would be the first comprehensive database of commercial and industrial adhesives available. The availability of a searchable adhesive library has numerous applications in the area of forensic science. Evidence involving adhesives can come into question in a wide variety of cases. Evidence involving glues can be submitted in cases of postal fraud, product tampering, and product counterfeiting. Cases involving industrial-type tape adhesives can range from drug packaging evidence to duct-tapes possibly used in abduction or homicide cases. Adhesives are so prevalent in our everyday life, that evidence involving adhesive tapes or “post-it noteTM” adhesives may be vital in cases of questioned document analysis. For this research, the area of cyanoacrylate glue analysis was chosen. Cyanoacrylate glue adhesives all have ethyl-2-cyanoacrylate, or some derivative of it as their active ingredient. When exposed to hydroxyl ions found in atmospheric moisture, the double bond between the carbon atoms in the Ethyl-2- cyanoacrylate polymerizes. Because of this, the double bonds become single bonds which act to link long chains together, forming a hard, acrylic plastic (2). The chemical reactions are shown in Figures A and B. Because cyanoacrylate glues are such popular and effective adhesives, they provide a logical starting point in the creation of the adhesives database. Cyanoacrylate glues may turn up as evidence in any number of crimes. In cases of postal fraud or product tampering, these glues would seem the logical choice due to ease of drying and clear color. Because of the wide array of surfaces to which cyanoacrylate glue easily binds, the opportunities for its use in any number of crimes are limited only by the imagination. Also, cyanoacrylate is used in the application of artificial finger nails, and cyanoacrylate glue samples may come into play in crimes where fingernail evidence may be left behind, such as in certain cases of assault or homicide. The easy availability and accessibility of cyanoacrylate glues in virtually any retail store also made commercially purchased cyanoacrylate glues a good choice for analysis. Because most crimes involving adhesive-type evidence would be perpetrated by individuals without access to industrial adhesives, most FIGURE A N H H OCI H H—C—(JS—O-Cg—O: ' .1 I. I. Ethyl-2-Cyanoacrylate O “‘H Hydroxyl Ion FIGURE B V 0 II H——c——— c—o—c—c—c — o—‘H H I I H N I I c I H I I H H I | H Polymer Chain of the samples analyzed in this research were purchased from various stores in the local area. Several different types of cyanoacrylate glues were examined, including cyanoacrylate glue liquids, cyanoacrylate “gels,” finger nail glues, and specialized cyanoacrylate glues for wood. A complete listing of the glues analyzed in this thesis is seen in Table 1. Table 1 U6 - U6 U6 er uper ue er ue ue U9 U6 mers uper U9 mers US ormance REVIEW OF LITERATURE Several articles have dealt with the analysis of adhesives through a variety of methods. Pyrolysis-gas chromatography (PGC) has been one such method used in the past to analyze adhesive-class evidence (3,4). One other method mentioned in a paper was the use of “size exclusion chromatography" to detect traces of nitrocellulose (5). This may sometimes be found in trace amounts among some adhesives. Electrically conductive adhesives have also been analyzed utilizing methods of Fourier transform mass spectroscopy pyrolysis (FTMS), Auger electron spectroscopy (AES), and photo-electron spectroscopy (XPS) (6). Many papers have mentioned FTIR spectrophotometry, or some derivation of it, in the analysis of adhesives as well. FTIR has been used to analyze adhesives found on the backs of stamps (7, 8), anaerobic sealants and adhesives (9), toners and adhesives (10), and adhesives found in packaging materials (11, 12). Attenuated total reflection Fourier transform infrared spectrophotometry (ATR FTIR) has been utilized in the analysis of water-based adhesives (13) and surface regions of various adhesives, sealants, and coatings (14). Adhesives have also been analyzed through a method using FTIR-Raman spectroscopy (15). Two articles have specifically dealt with the topics of IR and adhesive analysis. The first of these appeared in 1966 and utilized a variety of analytical methods, including spot tests, chromatography, PGC, along with IR to examine, and successfully distinguish adhesive classes (16). In 1974, a paper was published that analyzed 179 commercial adhesives using both IR and PGC in an attempt to differentiate them from one another (17). In both of these studies, the adhesives examined were distinguishable, but were not subject to Fourier transform or computer library searching. This lead the way to Jeffery Kindig's thesis, which, as mentioned before, served as the basis for this thesis. 10 MATERIALS AND METHODS Fifty commercial cyanoacrylate glues were purchased for this research. All samples were obtained from local drug stores, hardware stores, or department stores. Most of the samples purchased were name brand samples and should be easily obtainable throughout the United States. As previously mentioned, samples ranged from general-purpose cyanoacrylate glues and gels to salon quality professional nail glues. In this paper, all samples will be referred to as “cyanoacrylate glues.” A list of the glues and their drying dates is given in Table 1. Individual samples were prepared by spreading the cyanoacrylate glue onto a clean, glass slide using a wooden applicator stick. The samples were air dried as thin as possible on the slide, both for ease of analysis and to simulate actual usage of the glue. Dried samples were used because, more often than not, cyanoacrylate glue evidence would appear in a lab in a dried form, and because a dry sample was much more practical to work with than a “wet” sample. All slides were labeled with an alphabetic “sample letter” (A through XX) for identification. The samples were allowed to dry for at least two days, although it was determined that all samples were ready for analysis in less than 24 hours after they were prepared. As mentioned before, when Jeffery Kindig produced his thesis results, he used a diamond anvil cell in conjunction with an infrared microscope. For this research, it was the original intention to use a diamond cell as well, especially 11 given its effectiveness in analyzing small, pure samples. However, in the analysis of cyanoacrylate glues, it was intended to use the diamond cell as a stand alone accessory. The instrument used for analysis of the cyanoacrylate glues was a Nicolet Model 460 "Protege." OMNIC 5.1 software was used for data collection, spectral analysis, and library creation. For all samples, the parameters were set to 300 scans, with a resolution of 2. The final format for each sample was set to absorbance, and no corrections were made to the spectra saved. The spectra had absorba‘nces ranging from .5 to 2.0. As previously mentioned, it was the, original intention of this project to use the diamond anvil cell to collect the spectra. This process produced spectra, but unfortunately did not produce the sharp peaks needed for an effective database. For some reason, peaks in the fingerprint region of the spectra appeared rounded. This was possibly due to the transparent, crystalline nature of cyanoacrylate glue, most likely allowing too much light to pass through the sample. This did not produce the quality of spectra useful for the adhesive database, and could possibly interfere with an effective spectral library search. In order to more effectively produce quality spectra, a new method of preparing the samples was utilized. The samples were still dried on individual slides and allowed to sit for at least two days. Once dry, the cyanoacrylate glue was carefully scraped off the slide with a scalpel and mixed with dry potassium bromide (KBr). This mixture was then amalgamated in a Wig-L-BugTM 12 amalgamator, and the mixed sample was pressed into a potassium bromide pellet. At the beginning of each day, an atmospheric reference spectrum was obtained in order to account for the levels of water and carbon dioxide present in the room. These reference scans consisted of 300 scans run with the bench cover open. The sample spectra were then obtained by running 300 scans of the background, which consisted ofjust the purged sample compartment. The sample KBr pellet was then placed in the compartment, where it was allowed to purge for five to ten minutes. 300 scans of the sample were then run and the background interferograms were automatically subtracted. This method produced much clearer, sharper peaks, and provided spectra of a much higher quality. In order to account for any variations in spectra due to drying time, one of the samples was run several times over a twenty-day period. No significant variation in spectral peaks was observed. Also, one dried sample was run several times to test for reproducibility. As with the drying test, no significant variations were seen in the final spectra. I To test for variation among different batches, or "lots" of the same brand of cyanoacrylate, five "lot" samples were run. These samples consisted of 'five samples of the same cyanoacrylate brand, but originating from different tubes with different "lot" numbers. It was determined that there were essentially no discernible differences between the spectra produced by these samples. 13 In addition to the collection of the fifty spectra for the Nicolet database, ten test samples were run in order to test the practicality and usefulness of an exclusive cyanoacrylate glue spectral library. These samples were randomly chosen and prepared as described above. Fifty scans of the samples and their backgrounds were run and then saved to be compared to the saved fifty sample spectra. 50 scans were chosen because peak resolution was well defined, and, considering that all library samples were run at 300 scans, 50 scans would act to test the "minimal capabilities" of the library. The results of the ten “test” samples are described in the “Results and Discussion" section of this thesis. 14 RESULTS AND DISCUSSION Once each spectrum was collected, it was assigned a file name and saved to submit to Nicolet. Information on each spectrum was then entered into a database to be sent along with the spectra. The database contained the following information: brand name of the sample, sample file name, atmospheric reference file name, date collected, manufacturer, contact information for the manufacturer, UPC code, re-order number of the glue, lot number, method of collection (which was a potassium bromide pellet in all cases), and active ingredient of the sample (some form of cyanoacrylate in all cases). All of this information allows for accurate identification of each sample, and may later prove very useful in study replication or when new cyanoacrylate glues and other adhesives are added to the database. In addition to recording the information for Nicolet, a prototype library was internally created of the fifty cyanoacrylateglue samples. This was accomplished using the library manager applications available on the OMNIC software. Each sample spectrum was put into the library after adjusting the baseline using the “automatic baseline correct” option. The library was set up at a resolution of 2, with a spectral format of “absorbance.” The wavenumber regions between 400 cm-1 and 4000 cm-1 were set as the frequency limits. All spectra can be found in APPENDIX A. This was the library used to run searches on the ten test spectra previously mentioned. 15 It should be noted that for many spectral libraries, the spectra are deresolved to a resolution of 4, 8, or sometimes 16 wavenumber resolution before being put into a database. This is often done in order to save space in the library. For this research, however, the resolution was kept at 2 due to the similar nature of the cyanoacrylate glue samples. To deresolve the samples would have made it nearly impossible to distinguish one sample from another in a library search. Upon inspection of the fifty spectra, it can be seen that, for the most part, the cyanoacrylate glue samples are very similar. All show the most prominent peak at wavenumber of around 1750. All samples also show peak patterns in the 3000 area. Peaks are also found in the spectral fingerprint region between the wavenumbers of around 1600 to 700. This is to be expected due to the fact that all samples contain cyanoacrylate. The samples analyzed in this research can essentially be divided into two categories - cyanoacrylate glues and cyanoacrylate glue gels. While all samples show similarities, the gel samples show much higher intensities in the 1400 to 1000 region. This is most likely due to additives in the product that create the more viscous properties of the gel. As seen in Appendix A, most of the gel samples exhibit very similar spectra, with only slight variations of peak intensity in the fingerprint region. The cyanoacrylate glue samples, like the gel samples, are also very similar, but showing variation in the fingerprint region as well. These variations also consist of differences in peak intensity in the region of 1600 to 700. A noted 16 exception, also seen in Kindig’s research, is Sample - A, Instant Krazy Glue - Skin Guard Formula. In this sample, there is a characteristic peak at around 3000. This is most likely attributed to the ingredients in the product which prevent bonding to skin. The ten test samples produced fairly good results considering the similar nature of the cyanoacrylate glue samples analyzed. Of the ten samples run, 3 hit as the first match in the database. Of those that did not match as number 1, many of the hits occurred within very small percentages of what the actual sample was. A complete listing of the test samples, their hit number, and their match percentages can be seen in Table 2. While this many not allow for a conclusive individualization of cyanoacrylate brands, it helps to include or exclude possible brands, and will certainly distinguish cyanoacrylate glues from another adhesive class. 17 TABLE 2 ample N umber Ide Letter Sample Name "Hit" Number Match Percentage % off from Actual Sample Average 18 6.1 87.12% 3.02% CONCLUSION The forensic science value of a comprehensive adhesives database can clearly be demonstrated by the research performed on the category of cyanoacrylate glues. The creation and use of a spectral library consisting of only one type of adhesive, in this case cyanoacrylate-based glues, shows that such a tool has practical use in the analysis of adhesive evidence. Although many of the samples show very similar spectral patterns, tests of the database clearly show that, while there may not be an exact match every time, brands can sometimes be identified. Even when a library hit is wrong, it is, in most cases within less than 3 percent of the true sample. It is possible that differences in absorbance among samples may account for some of the discrepancies in match percentage, especially considering the chemical similarities between the cyanoacrylate samples. This does not, however, negate the usefulness of the spectral library. This library can be used I effectively to draw correlations among samples, not absolute conclusions. The information complied here can still be used as a powerful tool in evaluating the nature of adhesive evidence in question. The results of this study also indicate that there is further cause to continue the creation of an adhesive database. More complex adhesives than those studied here may well prove to show much more variation among classifications. While cements and white glues may dry to the clear color of cyanoacrylate glues, their spectra are different from cyanoacrylate glues, and 19 most likely have similar variations within their own adhesive type. Further additions to the database will allow for better forensic investigation of adhesive evidence by including or excluding possible glues or other evidence found at the scene. Adhesive class could be easily be determined, and, as demonstrated in this research, possible adhesive brand individualization. The results of this cyanoacrylate glue research should prompt continued spectralcollection of other adhesive classes. As mentioned previously, there are seemingly countless categories of adhesives, and a wide variety of brands within those categories. While a comprehensive library may never truly be complete, further research and additions to an adhesives database would give forensic scientists another powerful tool in forensic casework and lend more credibility to the evidentiary value of adhesive evidence. There are also other avenues to pursue in adhesive research in general. Studies could easily be generated that deal with drying time of a variety of adhesives depending on solvent properties of the class of adhesive in question. While probably not a practical study in the arena of cyanoacrylate glues, this type of research may have some merit with glues and other adhesives that take a long time to dry. This has practical application in giving a possible time frame of when the adhesive evidence was applied. Studies could also be developed to test how contaminated samples may affect adhesive spectra. In future adhesive research, other FTIR sampling techniques could also be evaluated. While using a diamond anvil cell in this particular study proved to be ineffective, it may be very practical in the analysis of other adhesive classes. 20 Kindig showed that an infrared microscope can be very effective, but further research may indicate better methods for analyzing various categories of adhesives to obtain FTIR spectra. Attenuated total reflectance (ATR) may be very useful for certain tapes and thin adhesive films on the surface of evidence. Finally, other instrumental methods of analysis could be used to evaluate adhesive evidence. Techniques such as Pyrolysis Gas Chromatography, and even GC-MS, could give valuable information about the composition of adhesive- class evidence. This could lead the way to other adhesive libraries and add more information to the body of knowledge concerning adhesive evidence. 21 APPENDICES 22 APPENDIX A Cyanoacrylate Glue FTIR Spectra Included in the Library 23 Absorbance Absorbance Absorbance Absorbance Absorbance 1.5 1.0~ 0.5- 0.0‘ ,‘Instant Krazy Glue with Skin Guard ”,4 1.5 :fQuick Tite Super Glue Gel ”Quick Trte Super Glue *Future Glue Instant Thick Gel /.,J J *Paoer Tech. “High Performance' Future Glue 3000 2000 Wavenumbers (cm-1) PEPPF 1000 Absorbance Absorbance Absorbance Absorbance Absorbance «*Duro Quick Gel 1'0; *Loctite Brush-on Instant Wood Glue 0.6:‘Loctite Plastix - Bonding Agent :‘Permatex Super Glue 1.5 d‘lnstant Krazy Glue - All Purpose 0.5- 0.0“ 4000 3000 l 2000 Wavenumbers (cm-1) 1000 25 Absorbance Absorbance Absorbance Absorbance Absorbance 0.8 1 *Meijer Super Glue (Kwik-Fix) 0.6: 0.4-: 1 0.2- .*Duro Super Glue 0.0‘ ‘A—fixp 1.0“:‘Ross Super Glue 0.8-: 0.6-: 0.4-: 0.2-: 0.03 0.5- 0.0‘ .‘Super Glue for Leather and Wood -*Power Poxy Super Glue 0.6-: 0.4-: 0.2-: 0.03 4000 3000 , . . - . 2000 1000 Wavenumbers (cm~1) 26 Absorbance Absorbance Absorbance Absorbance Absorbance 0.8“. ‘Meljer Super Glue Gel 0.03 0.6-: 0.45 0.2: 0.03 0.8:‘P0wer Poxy Nail Art Brush-on Super Glue 05.: *Bondini-Z 0.4-: 0.31, 0.2: 0.1: 0.01 05.: Duro Super Glue 5 0.4-3 0.3-: 0.2% 0.1—: 0.0 :‘Super Glue 0.6-: 0.4—: 0.03 4000 '3000 2000 Wavenumbers (cm-1) 1000 27 Absorbance Absorbance Absorbance Absorbance Absorbance .1 02‘: [/NJ ' 0.03 1 5 1‘Thick Gel Super Glue 1.0- . 0.5— 0.0‘ 3*Cran High Performance Future Glue 0.6: 0.4—: 0.2-: 0.03 0.8:‘Elmers Wonder Bond Plus Super Glue 0.65 . PP? :‘Elmers Super Glue :‘Super Bonder Super Glue 0.21 0.0‘ 4000 3000 2000 Wavenumbers (cm-1) 1000 Absorbance Absorbance Absorbance Absorbance Absorbance j‘lnstant Krazy Glue Gel 0.5‘ 00‘ fJoneI Fast Setting Nall Glue L L J 0.4: n: 0.31 1 d 0.2- d d 0.1« 0.03 0.5": ”Sally Hansen Hypo-Allergenic Nail Glue I l J 0.4d 0.2- 00‘ ‘Instant Krazy Glue Advanced Formula Gel L 0.63 0.4-: 0.2: 0.03 j‘SaIly Hansen Professional Gel Glue 4000 3000 2000 1000 Wavenumbers (cm-1) Absorbance Absorbance Absorbance Absorbance Absorbance 0.8“: 0.4—: 0.2—: 003 I‘Jonel Instant Nail Glue 05 0.4: 03-3 0.25 0.11: 0.04 ‘Nail Fetish Brush-on Nall Glue Tm 0.63 .I 0.0“ «*Loctite 414 0.6-: 0.4; 0.2: 0.0: jf5 Second Nail Glue 0.2- 0.0' :‘Nallene Nail Glue (Super Glue) 4000 3000 2000 Wavenumbers (cm-1) 1000 30 Absorbance Absorbance Absorbance Absorbance Absorbance . Professional Solutions Fix-a-nall Brush-on Glue 1.5- ‘Nallene Professional Nail Glue 0.0 ‘ 0.6: *Sally Hansen Superhold Nail Glue d 0.43 .I 0.2- 0.01 ,‘Loctite 495 Instant Adhesive 1 .0— 0.5- 0.0‘ ,0 ed -*Kiss Professional Nail Glue Eggs 0.4— 0.2; 0.0‘ . . . . , ,fi 4000 3000 2000 1000 Wavenumbers (cm-1) Absorbance Absorbance Absorbance Absorbance Absorbance 0.25 ' 0.0‘ 041' 0.6: ‘Cosmar Ultra-Bond NaII Glue M 0.8-: 0.6% 04-3 0.2-3 0 03 1-0_3"Instant Krazy Glue - Wood Formula 0.5: ‘Permatex Super Glue Gel 0.4-: 0.3-: 0.2: 0.141 0.0‘ 3"‘Loctite Hard Evidence I‘Lee Instant Nail Glue FF FF 4000 3000 a fit 2000 1000 Wavenumbers (cm-1) 32 Absorbance Absorbance Absorbance Absorbance Absorbance -‘Nallene Unltra Quick Nail Glue 0.6- 0.2-: 0.0‘ 1 0:"Pro 10 Quick Tite Super Glue for Nails 0.8-; 0.6-: 0.4-: 0.23 0.0: i .‘Fing’rs Instant Nail Glue 0.4: 0.0‘ 1.0- 0.5“ 00‘ “Sally Hansen 2000 lb Professional Strength Nail Glue 0:6:*Pr0 10 Professional NaIl Glue 0.4- 0.25 0.0‘ - - - . 4000 3000 2000 1000 Wavenumbers (cm-1) 33 APPENDIX B Match "Hits" of Ten Test Samples 34 Test of Sample E - Pacer Tech. "High Performance" Future Glue Search restlts 10c ‘Test - Sample E(5) - 50 Scans ' Date: Tue Jan 11 152251 2000 Search algorithm: Correlation Regions searched: 39997040016 2 {Test - Sample E(5) - 50 Scans é : 0 A A A ' J m 0 5; Loctite 414 g ' : Match:98.58 , 0,0- M __,.. m 1‘Pr0 10 Quick Tlte Super Glue for Nails g I Match:98.54 0 ‘ A A A J m 2: Pacer Tech. ‘High Performance“ Future Glue g . Match:98.36 0‘ . A I (0 Power Poxy Nail Art Brush-0n Super Glue g 0-5‘: Match:98.32 0.0 ‘ A L,— J§uper Glue § 05? Match:97.69 0.0‘ f n n l m r ‘ 3000 2000 1000 Wavenumbers (cm-1) Search results IIst of matches Index Match Compound Name Library Name 1 15 98.58 Lootite 414 KB: 2 44 98.54 Pro 10 Quick Tite Super Glue for Nails KBr 3 40 98.36 Pacer Tech. 'I-figh Performanoe' Future Glue KBr 4 27 98.32 Power Poxy Nail Art Brush-on Smer Glue KBr 5 26 97.69 Smer Glue KBr 6 29 97.30 Duro Super Glue 5 KBr 7 24 . 97.28 Elmer's Wonder Bond Plus Super Glue KBr, a s4 ' 9724 Duro Super Glue KBr 9 6 97.19 Instant Krazy Glue - Wood Formula KBr 10 36 97.03 Loctlte Brush-on Instant Wood Glue KBr 35V Test of Sample M - Ross Super Glue Search results for. ‘Test - Sample M(13) - 50 Scans Date: Wed Jan 19 15:28:49 2000 Search algorithm: Correlation Regions searched: 39997040016 est- 0.5 Match:91.90 0.0 Match:91 .87 Match:90.78 Match:90.43 - 0 1 Match:90.41 0 Index Match Compomd Name Lbrary Name 1 17 91.90 Nail Fetish Brush-on Nail Glue KBr 2 40 91.87 Pacer Tech. ”High Pertomtance' Future Glue KBr 3 27 90.78 Power Poxy Nail Art Brush-on Super Glue KBr 4 44 90.43 Pro 10 Quick Trte Super Glue for Nails KBr 5 6 90.41 Instant Krazy Glue - Wood Formula KBr 6 15 90.34 Lodite 414 KBr 7 24 90.18 Ekners Wonder Bond Plus Super Glue KBr 8 83 89.98 Super Glue for Leather and Wood KBr 9 34 89.73 Duro Super Glue KBr 10 29 89.41 Duro Super Glue 5 KBr 11 14 89.34 Nailene Nail Glue (Super Glue) KBr 12 10 89.32 Sally Hansen Superhold Nall Glue KBr 13 35 89.1 1 Instant Krazy Glue - All Purpose KBr 14 37 89.09 Loctlte Plastix - Bonding Agent KBr 15 26 89.07 Super Glue KBr 16 28 88.99 BondinI-2 KBr 17 23 88.88 Oran High Performance Future Glue KBr 18 32 88.43 Ross Super Glue KBr 19 1 1 88.29 Loctite 495 Instant Adieslve KBr 20 45 88.08 Sally Hansen Professional Gel Glue KBr 36 Test of Sample N - Power Poxy Super Glue Search resdts for. ‘Test Sample N(14) - 50 scans Date: Fri Jan 14 15:48:47 2000 Search algorithm: Correlation Regions searched: 39997040016 Test Sample N(14) - 50 m 0.51 D u 4; . 0.0‘ 0.5jPen'natex Super Glue Gel § . Match:86.33 0.0' A m 0 5; ailene Unltra Quick Nail e g ' : Match:84.81 0.0‘ . m jEImers Super Glue g 05: Match:70.36 ‘ m 0 5: Power Poxy Super Glue 2 ° Matchz68. 0.0‘ m ‘eijer Super Glue (Kwik—th) g 05 Match:68.18 0.0 M 7 . . . . I . . . . , . . . - , . 3000 2000 1000 _ Wavenumbers (cm-1) Search results list of matches . Index Match Compound Name Library Name 1 47 86.33 Permatex Super Glue Gel KBr 2 4 84.81 Nallene Unltta Quick Nail Glue KBr . 3 48 70.36 Einers Super Glue KBr 4 31 68.47 Power Poxy Super Glue KBr 5 50 68.18 Meljer Super Glue (lek-Fix) - KBr 6 3 64.03 Sally Hansen 2000 b Professional Strength NaKBr Glue ‘ 7 11 63.07 Lootlte 495 Instant Adtesive KBr , 8 20 62.28 Instant Krazy Glue Advanced Formula Gel KBr 9 46 61.31 Pro 10 Professional Nall Glue KBr 10 45 59.94 Sally Hansen Professional Gel Glue KBr 37 Test of Sample 0 - Meijer Super Glue (Kwik-F ix) Search results ton ‘Test - Sample 0(15) - 50 scans Date: Tue Jan 11 1524:02 2000 Search algorithm: Correlation Regions searched: 3999.70-400-16 1I‘Test - Sample 0(15) - 50 s 0: _ Meijer Super Glue (Kwik-Fix) 05: Match:55.57 0.03 0.5:Permatex Super Glue Gel I . Match:52.05 0.0' ' A 0 5; ailene Unltra Quick Nail e ' 1 Match:50.77 0.0‘ IEImers Super Glue 05-: Match:48.67 0.01 M 0.5. Pro 10 Profe ional Nail Glue ' j Match247. 0.0‘ Abs Abs Abs Abs Abs Abs *I ‘ V j I 3000 2000 1000 Wavenumbers (cm-1) Search results list of matches Index Match Con—pound Name Library Name 1 50 55.57 Meijer Super Glue (Kwik-F‘rx) . KBr 2 47 52.05 Permatex Super Glue Gel KBr 3 4 50.77 Nailene Unltra Quick Nail Glue KBr 4 48 48.67 Ekners Super Glue KBr 5 46 47.65 Pro 10 Professional Nall Glue KBr 6 . 31 47.60 Power Poxy Super Glue KBr 7 20 47.06 Instant Krazy Glue Advanced Formula Gel KBr 8 11 46.11 Loctite 495 Instant Adiesive KBr 9 30 46.04 Meijer Super Glue Gel KBr 1O 45 45.19 Sally Hansen Professional Gel Glue KBr 38 ' Test of Sample AA - Instant Krazy Glue Advanced Formula Gel Search results for. ‘Test - Sample AA(27) - 50 Scans Date: Tue Jan 11 15:31:09 2000 Search algorithm: Conelation Regions searched: 39997040016 :‘Test - Sample AA(27) - 50 Scans 8 0.5- < I 0.0‘ M w eijer Super Glue Get 43 0-5 Match:95.20 _ 0.0 M m 0.5 nstant Krazy Glue Advanced Formula Get :3 Match:94. 0.0 m 0 5:IInstant Krazy Glue Gel g ' 1 Match:94.36 0.0‘ m 05. Pro 10 Profe lonal Nail Glue g j Match:93. 0.0‘ m 0 5:Lee Instant Nail Glue g ' : Match:91.70 0.0 ‘M A . . s . 1 . . . . , . . . . 1 #4”. ' 3000 2000 1000 Wavenumbers (cmot) Search results list of matches Index Match Compound Name Lbrary Name 1 30 95.20 Meijer Super Glue Gel ' KBr 2 20 94.64 Instant Krazy Glue Advanced Formula Gel KBr 3 21 94.36 Instant Krazy Glue Gel KBr 4 46 93.55 Pro 10 Professional Nail Glue KBr 5 5 91.70 Lee Instant Nail Glue KBr 6 16 91.53 5 Second Nail Glue KBr 7 49 91.28 Cosmar Ultra-Bond Nail Glue KBr 8 10 9121 Sally Hansen Superhold Nail Glue KBr 9 45 91.07 Sally Hansen Professional Gel Glue KBr 10 24 91.05 EhiersWonderBondPIusSuperGlue KBr 39 Test of Sample ll - Jonel Instant Nail Glue Search maltsfor: ‘Test-Il -50$cans Date: Tue Jan 11 15:26:51 2000 Search algorithm: Correlation Regions searched: 399970410016 m 05: est - ll - 50 Scans .O < . 0.0 ‘ N m 0.5; Quick Trte Super Glue MAM g : Match:97.22 ' 0.0‘ A A co 0 sisuper Glue M g ' 3 Match:96.84 0.0‘ N a) 1 jLoctite Brush-0n Instant Wood Glue g . Match:96.49 0‘ A m :Jonel Instant Nail Glue g 05: Match:96.39 0.0? N m 0.5; octite 414 g i Match:96.11 0.0: M . . . . 1 . . . . , . . . . 1 3000 2000 1000 _ Wavenumbers (cm-1) Search results list of matches Index Match Conpound Name Lbrary Name 1 12 97.62 Profesional Solutions Fix-a-nail Brush-on GIud