Recovery of Spray Paint Traces from Clothing by Beating

Manual recovery of spray paints from textiles using a microscope, the routine method in many laboratories, is often laborious. Beating the clothing with a plastic rod, the routine method used for recovery of glass traces within the authors’ laboratory, is proposed as an alternative. The efficiency of the method was evaluated by spray tests with fluorescent paint. In these tests, paint particles in the acquired debris samples, as well as those remaining on the textiles, were investigated. The results show that beating is an efficient way to recover and concentrate paint particles. A good efficiency for jeans fabric and rough knitwear is reported. The results appeared to be less satisfactory for smooth woven fabric. Application of the method in casework was effective for graffiti paints as well as for flaked car paint.     

Color analysis of apparently achromatic automotive paints by visible microspectrophotometry

Chromatic secondary pigments are utilized in achromatic automotive paints to create unique paint systems. These pigments may not be observable in reflected light; however, utilizing visible microspectrophotometry (MSP) discriminating data may be gathered. This study analyzed 160 apparently achromatic automotive paints via this technique for spectral evidence of secondary pigmentation. These results were compared with visual observations made via polarizing light microscopy. Positive spectral results were attained in approximately 25% of the black and gray/silver topcoat sample sets, whereas the white topcoat and gray undercoat set yielded no probative spectral data. The black sample set did yield several samples that produced spectral evidence of pigmentation when no visual chromatic data was observed. The results of this study suggest that paint analysis schemes should incorporate visible MSP for apparently achromatic black and gray/silver paint samples.     

Survey of crowbar and household paints in burglary cases-population studies, transfer and interpretation

Experimental data useful for the interpretation of paint evidence recovered during burglary cases were obtained. A population study was carried out on 41 blue crowbars seized on suspects in Switzerland and 37 blue paints traces found at burglary scenes. Paint traces were also searched on the blades of 207 crowbars seized by the police in Switzerland and 24 white traces were analysed: these paints were analysed using infrared spectroscopy (FTIR) in order to estimate relative frequencies of each paint type. Simulated contacts were carried out between crowbars and painted wood in order to study the phenomenon of transfer and to evaluate the amount of paint transferred: a total of 198 simulations were carried out including individual, successive and cross transfer. The paint properties such as the chemical composition and its age influenced the amount of paint transferred. Cross transfer from the tool paint to the wood and vice versa was regularly observed. Moreover, secondary transfer of paint coming from the preceding wooden surfaces was also systematically observed: this could establish links between several burglary scenes and a suspected tool. A scenario of a burglary case involving the cross transfer between tool and household paints is proposed as a numerical example: the evaluation of such case was formalised using likelihood ratios based on the experimental data obtained.     

The Evidentiary Significance of Automotive Paint from the Northeast: A Study of Red Paint

This population study was conducted to assess the frequency of physical, microscopical, and chemical properties of automotive paint chips. Population studies of trace evidence provide valuable analytical data for criminalists to assess evidentiary significance. Two‐hundred automotive paint chips were collected from auto body shops from the Northeastern United States. All samples were analyzed using stereomicroscopy, brightfield, and polarized light microscopy. Red paints were targeted for further analysis using a sequence of modern instrumental techniques commonly used by forensic paint examiners: Fourier‐transform infrared (FT‐IR), Raman, and ultraviolet–visible (UV–Vis) microspectroscopy. The discrimination potential of each analytical method was evaluated by inter‐comparing the paint samples. Results demonstrated that macroscopic and microscopic properties were able to differentiate 99.995% of the population (one undifferentiated pair out of 19,900). When combined with either FT‐IR or UV–Vis microspectroscopy, all paints were differentiated. The results of this research lead to the conclusion that one would not expect to encounter two indistinguishable paint chips originating from different sources during the investigation of a single event.     

Direct identification of various copper phthalocyanine pigments in automotive paints and paint smears by laser desorption ionization mass spectrometry

Direct identification of copper phthalocyanine (CuPc) and chlorinated CuPcs in paints for discrimination between blue automobile paints by means of laser desorption mass spectrometry (LDMS) in the absence of a matrix is reported. The models consisted of eight commercially available CuPc pigments applied to a piece of plain white coating paper. The relationship between the peak intensity at m/z 575 of the CuPc, the number of pulsed laser shots, and laser power was compared to optimize laser abrasion. LDMS analysis of the model paints demonstrated that all characteristic components of the CuPc pigments in the paint films were in good agreement with those in the powder pigments. Further, the chlorinated CuPcs in the paint films could be distinguished. A quantity of 42 blue paint films, representing the paints used for painting Japanese domestic trucks, was examined by LDMS analysis. Results indicate that the paints can be classified into four categories based on the chlorinated CuPc components of the paints. Therefore, LDMS spectra of CuPc pigments would be useful for the identification of paints in forensic investigations. Herein, we report the successful identification of the CuPcs in a paint smear on the frame of a bicycle damaged in a hit-and-run accident, using the LDMS spectra.     

Using Paint to Investigate Fires: An ATR‐IR Study of the Degradation of Paint Samples Upon Heating

Fire investigation is a challenging area for the forensic investigator. The aim of this work was to use spectral changes to paint samples to estimate the temperatures to which a paint has been heated. Five paint samples (one clay paint, two car paints, one metallic paint, and one matt emulsion) have been fully characterized by a combination of attenuated total reflectance Fourier transform infrared (ATR‐IR), Raman, X‐ray fluorescence spectroscopy and powder X‐ray diffraction. The thermal decomposition of these paints has been investigated by means of ATR‐IR and thermal gravimetric analysis. Clear temperature markers are observed in the ATR‐IR spectra namely: loss of ν(C = O) band, >300°C; appearance of water bands on cooling, >500°C; alterations to ν(Si–O) bands due to dehydration of silicate clays, >700°C; diminution of ν(CO₃) and δ(CO₃) modes of CaCO₃, >950°C. We suggest the possible use of portable ATR‐IR for nondestructive, in situ analysis of paints.     

Discrimination of 1990s original automotive paint systems: a collaborative study of black nonmetallic base coat/clear coat finishes using infrared spectroscopy

The 1990s saw the introduction of significantly new types of paint binder chemistries into the automotive finish coat market. Considering the pronounced changes in the binders that can now be found in automotive paints and their potential use in a wide variety of finishes worldwide, the Paint Subgroup of the Scientific Working Group for Materials (SWGMAT) initiated a validation study to investigate the ability of commonly accepted methods of forensic paint examination to differentiate between these newer types of paints. Nine automotive paint systems typical of original equipment applications were acquired from General Motors Corporation in 1992. They consisted of steel panels coated with typical electrocoat primers and/or primer surfacers followed by a black nonmetallic base coat and clear coat. The primary purpose of this study was to evaluate the discrimination power of common forensic techniques when applied to the newer generation original automotive finishes. The second purpose was to evaluate interlaboratory reproducibility of automotive paint spectra collected on a variety of Fourier transform infrared (FT-IR) spectrometers and accessories normally used for forensic paint examinations. The results demonstrate that infrared spectroscopy is an effective tool for discriminating between the major automotive paint manufacturers' formulation types which are currently used in original finishes. Furthermore, and equally important, the results illustrate that the mid-infrared spectra of these finishes are generally quite reproducible even when comparing data from different laboratories, commercial FT-IR instruments, and accessories in a "real world," mostly uncontrolled, environment.     

裂解气相色谱-质谱法和红外光谱法对红色汽车油漆的比较分析

目的应用裂解气相色谱-质谱法（Py-GC/MS）和红外光谱法（IR）鉴别3种红色汽车油漆,通过二者的比较,考察Py-GC/MS法在微量物证油漆鉴定中的适用性。方法取适量固体样品直接检测。IR检测条件：红外显微镜,透射模式,光阑尺寸100μm×100μm,检测范围为4000-675cm-1。Py-GC/MS检测条件：裂解温度：550℃,裂解时间：0.20min。HP-5MS色谱柱,分流比80∶1;升温程序：起始温度为40℃,保持1 min,然后以8℃/min升至300℃,保持1 min。质谱采用EI源,扫描范围：29~350 amu。结果 3种红色汽车油漆的红外光谱、裂解图谱均能相互区分。通过裂解产物,能获得更多油漆主要成膜物质的成分信息。结论在样品量许可的条件下,应在红外光谱的检测基础上,进一步使用裂解气相色谱-质谱方法来对汽车油漆进行检测,通过互相验证,获得更准确、可靠的油漆鉴定结果。     

A market study of green spray paints by Fourier transform infrared (FTIR) and Raman spectroscopy.

A market study of 40 different green spray paints was carried out using infrared (FTIR) and Raman spectroscopy. The infrared technique distinguished between the 12 main groups based on their binder and extender composition. After visual comparison of the spectra 22 subgroups were observed. Raman spectroscopy was also carried out on the 40 reference paints in order to determine the pigment content. Analyses were undertaken using two different excitation sources: Argon ion (514.5 nm) and Helium-Neon (632.8 nm). The first generated strong fluorescence for most of the samples and created eight groups. Using the red laser, 15 classes were observed. Finally, using an analytical sequence starting with infrared spectroscopy followed by Raman Helium-Neon and then by Raman Argon laser, most of the paints were differentiated. In this study infrared and Raman spectroscopy complemented each other. FTIR supplied information about the binder and some extenders, and Raman provided information on the main organic pigments present.     

显微光谱成像技术在汽车油漆截面检验中的应用

目的对汽车多层油漆的横截面进行分层和比对研究。方法运用显微光谱成像技术对收集的12个省市623个汽车漆片样本进行分层,并对截面结构相同或相似的油漆样本进行了区分。结果 623个油漆样本均可以分层,分析出漆层为两层及以上的油漆样本数占总数的87.26%;截面结构相同或相似的油漆样本能够多层同时区分。结论该方法具有科学及实用价值,检验结果可靠,可见光谱成像技术完全可运用拓展到微量物证的检验中。     

Evaluation of iodine-benzoflavone and ruthenium tetroxide spray reagents for the detection of latent fingermarks at the crime scene

The performance of two spray reagents, iodine-benzoflavone and ruthenium tetroxide (RTX), was evaluated and compared with the conventional technique currently used at the crime scene, that is, powdering. Neither the spray techniques nor powdering were shown to be suitable for all surfaces and ages of marks tested. On some surfaces such as glass and treated wood, powdering was still the superior technique, whereas the spray techniques produced better development on wallpaper, vinyl, and brick. Sequencing work showed that RTX was incompatible with powdering and cyanoacrylate (with a rhodamine 6G stain). Iodine-benzoflavone can be used successfully either before or after powdering in a sequence; however, it was incompatible with cyanoacrylate. Two non-CFC formulations of iodine-benzoflavone using HFC4310mee and HFE7100 solvents were tested and shown not to be as effective as the original Arklone (CFC-113) formulation; however, the HFC4310mee solvent is recommended as the most suitable replacement solvent. Due to the expense of the commercial RTX spray, attempts at formulating a more cost-effective version were also carried out. A formulation was developed that gave comparable development to the commercial version but at a much cheaper cost, and with a shelf life of up to two months. Recommendations are presented for which techniques are suitable for different surfaces and ages of marks. Powdering was shown to be the best technique on all ages of marks tested on treated wood, glass, and also on marks aged three days and older on paint. Iodine-benzoflavone was the best technique on wallpaper, vinyl, brick, and raw wood. RTX was the best detection technique for fresh marks and marks aged up to one day on wallpaper and paint.     

氨基树脂漆的傅立叶变换红外光谱分析

根据红外谱图的相似程度决定两种涂料是否属同一种类的涂料是最基本也是最初级的检验方法,不可避免地带有极大的盲目性,只有把握了特征峰所代表的基团的振动形式,才能准确地识谱,正确地鉴别.本文介绍了氨基树脂漆的傅立叶变换红外光谱分析及谱图解释.     

近红外显微分光光度法鉴别油漆的研究

本文借助显微分光光度计系统在近红外区域对几种“色觉”相似的油漆样品进行了光谱学分析。结果表明，近红外显微分光光度计能有效地鉴别颜色相似的油漆。该法准确、可靠，且不破坏检材．对实际检案有重要意义。     

The discrimination of small fragments of household gloss paint by microspectrophotometry

A microspectrophotometer has been used to discriminate between sets of household gloss paints of the same British Standard colours obtained from different manufacturers. Reflectance spectra were obtained, over the range 390 to 900 nm, from paint top surfaces and individual cross-sectional layers. Comparison of the reflectance spectra enabled visually similar paints to be discriminated.     

Methods for physical stabilization of ashed teeth in incinerated remains

Methods for physically stabilizing the extremely fragile ashed teeth that are often encountered in incinerated human remains were investigated. Results of a questionnaire sent to forensic anthropologists and forensic odontologists disclosed that, for these two groups, the most popular methods currently used are impregnation with a solution of polyvinyl acetate or application of cyanoacrylate cement, respectively. In addition, extracted human teeth were incinerated in the laboratory and impregnated with commercially available preparations of either cyanoacrylate cement, clear acrylic spray paint, hair spray, spray furniture varnish, clear fingernail polish, quick-setting epoxy cement, Duco household cement, polyvinyl acetate polymer in acetone, or self-curing clear dental acrylic resin. Every substance tested successfully stabilized the incinerated teeth. Clear acrylic spray paint was judged the most efficacious overall because of its ease of application, availability, inexpensiveness, and rapidity of setting.     

The application of chemometrics on Infrared and Raman spectra as a tool for the forensic analysis of paints

The aim of this work is to evaluate the capabilities and limitations of chemometric methods and other mathematical treatments applied on spectroscopic data and more specifically on paint samples. The uniqueness of the spectroscopic data comes from the fact that they are multivariate - a few thousands variables - and highly correlated. Statistical methods are used to study and discriminate samples. A collection of 34 red paint samples was measured by Infrared and Raman spectroscopy. Data pretreatment and variable selection demonstrated that the use of Standard Normal Variate (SNV), together with removal of the noisy variables by a selection of the wavelengths from 650 to 1830 cm(-1) and 2730-3600 cm(-1), provided the optimal results for infrared analysis. Principal component analysis (PCA) and hierarchical clusters analysis (HCA) were then used as exploratory techniques to provide evidence of structure in the data, cluster, or detect outliers. With the FTIR spectra, the Principal Components (PCs) correspond to binder types and the presence/absence of calcium carbonate. 83% of the total variance is explained by the four first PCs. As for the Raman spectra, we observe six different clusters corresponding to the different pigment compositions when plotting the first two PCs, which account for 37% and 20% respectively of the total variance. In conclusion, the use of chemometrics for the forensic analysis of paints provides a valuable tool for objective decision-making, a reduction of the possible classification errors, and a better efficiency, having robust results with time saving data treatments.     

Forensic applications of pyrolysis capillary gas chromatography

A simple system of pyrolysis capillary gas chromatography has been used to improve discrimination and long-term reproducibility in the analysis of polymers particularly alkyd based paints typically encountered in forensic casework. This involved the coupling of a Pye Curie-point pyrolyser to the inlet port of a capillary gas chromatograph operated in the splitless mode. Examples of pyrograms demonstrating improved differentiation of alkyd paints, and also examples of other architectural and automotive paints, automobile rubbers, adhesives, polyurethane foams and fibres are shown.     

Paint and tape: collection and storage of microtraces of paint in adhesive tape

The collection and preservation of microtrace evidence with the aid of an adhesive tape is a method of choice in forensic science. This technique is rapid and easy and allows the concentration of microtraces on a carrier, which facilitates further investigations in the laboratory. Adhesive tapes are currently used to secure microtraces of fibers and glass, but hardly for traces of automotive paint and other lacquers for fear of interference with the analysis of binders. A collection of automotive paint consisting of original and repair lacquers collected by tape has been evaluated. After various times of storage within the tape, these samples were compared with untreated references by microscope FT-IR and microspectrophotometry (MSP). Another set of paints was collected in 1984, stored within the tape until 1995, and examined the same way. About 170 layers of lacquer with various types of binder were examined. With the exception of one clear lacquer no difference between treated samples and references was detected. This small difference observed could be correlated to the exposure to xylene (extractant) and was not caused by the storage within the adhesive tape.     

A Two‐Level Model for Evidence Evaluation in the Presence of Zeros*

Abstract: Likelihood ratios (LRs) provide a natural way of computing the value of evidence under competing propositions. We propose LR models for classification and comparison that extend the ideas of Aitken, Zadora, and Lucy and Aitken and Lucy to include consideration of zeros. Instead of substituting zeros by a small value, we view the presence of zeros as informative and model it using Bernoulli distributions. The proposed models are used for evaluation of forensic glass (comparison and classification problem) and paint data (comparison problem). Two hundred and sixty‐four glass samples were analyzed by scanning electron microscopy, coupled with an energy dispersive X‐ray spectrometer method and 36 acrylic topcoat paint samples by pyrolysis gas chromatography hyphened with mass spectrometer method. The proposed LR model gave very satisfactory results for the glass comparison problem and for most of the classification tasks for glass. Results of comparison of paints were also highly satisfactory, with only 3.0% false positive answers and 2.8% false negative answers.     

Analysis and Discrimination of Single‐Layer White Architectural Paint Samples,

Comparative analyses of 50 single‐layer white architectural paints were conducted to determine the discrimination power using standard techniques and to provide a basis for assessing significance when paints with limited features are not discriminated. Utilizing Fourier transform infrared spectroscopy (FTIR), 68 undifferentiated pairs resulted, yielding a discrimination of 94.45%. Adding stereomicroscopy, scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS) and backscatter electron (BSE) imaging, and pyrolysis‐gas chromatography/mass spectrometry (Py‐GC/MS), the overall discrimination was 99.35%. The study included blind verification replicates, which resulted in the only pairs without indications of physical or chemical differences. The remaining groups of undifferentiated samples contained subtle differences by at least one technique, but were considered undifferentiated for the discrimination power evaluations. This study demonstrates a high degree of discrimination of single‐layer white architectural paints using methods of analysis often encountered in forensic science laboratories.