Survey on batch-to-batch variation in spray paints: a collaborative study.

This study represents the most extensive analysis of batch-to-batch variations in spray paint samples to date. The survey was performed as a collaborative project of the ENFSI (European Network of Forensic Science Institutes) Paint and Glass Working Group (EPG) and involved 11 laboratories. Several studies have already shown that paint samples of similar color but from different manufacturers can usually be differentiated using an appropriate analytical sequence. The discrimination of paints from the same manufacturer and color (batch-to-batch variations) is of great interest and these data are seldom found in the literature. This survey concerns the analysis of batches from different color groups (white, papaya (special shade of orange), red and black) with a wide range of analytical techniques and leads to the following conclusions. Colored batch samples are more likely to be differentiated since their pigment composition is more complex (pigment mixtures, added pigments) and therefore subject to variations. These variations may occur during the paint production but may also occur when checking the paint shade in quality control processes. For these samples, techniques aimed at color/pigment(s) characterization (optical microscopy, microspectrophotometry (MSP), Raman spectroscopy) provide better discrimination than techniques aimed at the organic (binder) or inorganic composition (fourier transform infrared spectroscopy (FTIR) or elemental analysis (SEM - scanning electron microscopy and XRF - X-ray fluorescence)). White samples contain mainly titanium dioxide as a pigment and the main differentiation is based on the binder composition (CH stretches) detected either by FTIR or Raman. The inorganic composition (elemental analysis) also provides some discrimination. Black samples contain mainly carbon black as a pigment and are problematic with most of the spectroscopic techniques. In this case, pyrolysis-GC/MS represents the best technique to detect differences. Globally, Py-GC/MS may show a high potential of discrimination on all samples but the results are highly dependent on the specific instrumental conditions used. Finally, the discrimination of samples when data was interpreted visually as compared to statistically using principal component analysis (PCA) yielded very similar results. PCA increases sensitivity and could perform better on specific samples, but one first has to ensure that all non-informative variation (baseline deviation) is eliminated by applying correct pre-treatments. Statistical treatments can be used on a large data set and, when combined with an expert's opinion, will provide more objective criteria for decision making.

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.

Analysis and discrimination of electrical tapes: part II. Backings.

The backings of 90 black electrical tapes were analyzed to evaluate the chemical components of these films, the ability of individual techniques to discriminate samples, and the ability of the techniques combined to distinguish samples. The techniques utilized and their respective discrimination results were stereomicroscopy and physical measurements, to include observation of surface features of the backing, width, and thickness measurements (c. 64%); Fourier transform infrared spectroscopy (FTIR) using a microscope accessory (c. 83%); pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS; c. 81%); and scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS; c. 87%). Ninety-four percent of the backings were discriminated through this combination of analytical methods. Finally, evaluating these results in conjunction with previously published data on the analysis of the adhesives from the same set of electrical tapes provided an overall discrimination of nearly 96%.

A validation study for vinyl electrical tape end matches.

Fracture matches are considered the strongest conclusion in the forensic examination of rigid materials, such as glass, metal, and paint. However, publications that support the fracture matching of polymeric films, such as tape backings, are limited. This study was designed to determine the validity and error rate associated with conducting end-match (fracture match) examinations on vinyl electrical tape. Test designs varied the source roll of tape, test preparer, or mode of separation from the roll. Results indicated that each affected the resulting severed tape ends. The analysts examining the end matches also had an effect on the results. Eight end matches in the study were not identified by the initial analysts and were considered inconclusive. One end match was misidentified, resulting in one false positive and an error rate of 0.049%. These results support a comprehensive physical and chemical tape comparison regardless of indications of an end match.

Analysis and discrimination of architectural paint samples via a population study.

This study involved the comparative analysis and discrimination of 964 architectural paint samples collected in the United States and Canada. The samples were evaluated to determine the extent to which randomly collected architectural finishes can be discriminated following standard operating protocols for paint analysis. The study also provides a basis for assessing the significance of a result in which a pair or group are undifferentiated. The techniques utilized were stereomicroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) with both backscatter electron imaging (BSI) and energy dispersive spectroscopy (EDS), and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). To assess the layer characteristics (e.g., number, color, sequence, thickness), stereomicroscopy was used with FTIR and/or SEM as needed. The use of visual and microscopic evaluations in concert with FTIR resulted in 42 undifferentiated pairs, a discrimination of 99.99%. Adding SEM and Py-GC/MS analysis resulted in further discrimination of 31 pairs, resulting in eleven undiscriminated pairs of samples. At the conclusion of the study, samples that remained undifferentiated proved to originate from the same source. Therefore, no random pairs were indistinguishable at the conclusion of all examinations.

Analysis and discrimination of electrical tapes: Part I. Adhesives.

This study involved the comparative analysis and discrimination of 90 electrical tape adhesives. The objectives included the evaluation of the ability of individual techniques to discriminate samples and the assessment of the ability of the techniques combined to distinguish samples. The techniques utilized were stereomicroscopy, Fourier transform infrared spectroscopy (FTIR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS), and scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS). Stereomicroscopy, to assess adhesive colors of black, clear/colorless, and clear adhesives with brown tint, resulted in a discrimination of 53%. FTIR analysis yielded eight distinct groups with a discrimination of 67%. Py-GC/MS analysis resulted in 16 groups with a discrimination of 83%. These analyses confirmed and further subdivided the FTIR groups. SEM/EDS resulted in five separate groups at 17% discrimination, increasing the overall discrimination to above 85%.

A validation study for duct tape end matches.

Fracture matches are considered to be the strongest association achievable in forensic examinations of glass, metal, wood, plastic, paint, tape, and other trace evidence. Despite being fairly routine examinations, few publications exist to support their admissibility in court. This study was designed, using duct tape as the fractured medium, to determine the validity and error rate associated with conducting end match (fracture match) examinations on this material. Five test designs, which varied either the source roll of tape or manner of separation (torn or cut) from the roll, were administered to four analysts with instructions to examine the assigned test sets for end matches. If an end match was not identified by the initial analyst, the entire test set was independently evaluated by the remaining three analysts. Results indicated that while tape grade did not hinder end match identification, the manner of separation could affect results.