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1.
Appl Spectrosc ; 77(9): 1064-1072, 2023 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-37525887

RESUMEN

A new method to determine the make and model of a vehicle from an automotive paint sample recovered at the crime scene of a vehicle-related fatality such as a hit-and-run using Raman microscopy has been developed. Raman spectra were collected from 118 automotive paint samples from six General Motors (GM) vehicle assembly plants to investigate the discrimination power of Raman spectroscopy for automotive clearcoats using a genetic algorithm for pattern recognition that incorporates model inference and sample error in the variable selection process. Each vehicle assembly plant pertained to a specific vehicle model. The spectral region between 1802 and 697 cm-1 was found to be supportive of the discrimination of these six GM assembly plants. By comparison, only one of the six automotive assembly plants could be differentiated from the other five assembly plants using Fourier transform infrared spectroscopy (FT-IR), which is the most widely used analytical method for the examination of automotive paint) and the genetic algorithm for pattern recognition. The results of this study indicate that Raman spectroscopy in combination with pattern recognition methods offers distinct advantages over FT-IR for the identification and discrimination of automotive clearcoats.

2.
Appl Spectrosc ; 77(3): 281-291, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36241610

RESUMEN

Paint smears represent a type of automotive paint sample found at a crime scene that is problematic for forensic automotive paint examiners to analyze as there are no reference materials present in automotive paint databases to generate hit-lists of potential suspect vehicles. Realistic paint smears are difficult to create in a laboratory and have also proven challenging to analyze because of the mixing of the various automotive paint layers. A procedure based on an impact tester has been developed to create smears to simulate paint transfer between vehicles during a collision. Data collected from 24 original equipment manufacturer (OEM) paints in simulated collisions using an impact tester with a steel (inert) substrate to simulate vehicle to vehicle collisions shows that attenuated total reflection infrared microscopy can isolate individual paint layers. For each OEM paint sample, the corresponding smear obtained was dependent upon the conditions used. By varying these conditions, the number of distinct layers obtained could be tuned for each of the OEM paints investigated. Furthermore, the IR spectrum of each layer extracted from the paint smear using alternating least squares was found to compare favorably to an in-house OEM paint infrared spectral library for each layer as the correct match (make and model of the vehicle from which the smear originated) was always found as a top five hit in the hit-list. The results of this study indicate that paint smears developed using an impactor can serve as the basis of realistic proficiency tests for forensic laboratories.

3.
Appl Spectrosc ; 76(1): 118-131, 2022 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-34919478

RESUMEN

Alternate least squares (ALS) reconstructions of the infrared (IR) spectra of the individual layers from original automotive paint were analyzed using machine learning methods to improve both the accuracy and speed of a forensic automotive paint examination. Twenty-six original equipment manufacturer (OEM) paints from vehicles sold in North America between 2000 and 2006 served as a test bed to validate the ALS procedure developed in a previous study for the spectral reconstruction of each layer from IR line maps of cross-sectioned OEM paint samples. An examination of the IR spectra from an in-house library (collected with a high-pressure transmission diamond cell) and the ALS reconstructed IR spectra of the same paint samples (obtained at ambient pressure using an IR transmission microscope equipped with a BaF2 cell) showed large peak shifts (approximately 10 cm-1) with some vibrational modes in many samples comprising the cohort. These peak shifts are attributed to differences in the residual polarization of the IR beam of the transmission IR microscope and the IR spectrometer used to collect the in-house IR spectral library. To solve the problem of frequency shifts encountered with some vibrational modes, IR spectra from the in-house spectral library and the IR microscope were transformed using a correction algorithm previously developed by our laboratory to simulate ATR spectra collected on an iS-50 FT-IR spectrometer. Applying this correction algorithm to both the ALS reconstructed spectra and in-house IR library spectra, the large peak shifts previously encountered with some vibrational modes were successfully mitigated. Using machine learning methods to identify the manufacturer and the assembly plant of the vehicle from which the OEM paint sample originated, each of the twenty-six cross-sectioned automotive paint samples was correctly classified as to the "make" and model of the vehicle and was also matched to the correct paint sample in the in-house IR spectral library.

4.
Talanta ; 186: 662-669, 2018 Aug 15.
Artículo en Inglés | MEDLINE | ID: mdl-29784418

RESUMEN

In the forensic examination of automotive paint, each layer of paint is analyzed individually by infrared (IR) spectroscopy. Laboratories in North America typically hand section each layer and present each separated layer to the spectrometer for analysis, which is time consuming. In addition, sampling too close to the boundary between adjacent layers can pose a problem as it produces an IR spectrum that is a mixture of the two layers. Not having a "pure" spectrum of each layer will prevent a meaningful comparison between each paint layer or in the situation of searching an automotive database will prevent the forensic paint examiner from developing an accurate hit list of potential suspects. These two problems can be addressed by collecting concatenated IR data from all paint layers in a single analysis by scanning across the cross sectioned layers of the paint sample using a FTIR imaging microscope. Decatenation of the IR data is achieved by multivariate curve resolution using a Varimax extended rotation to select the starting point (i.e., initial estimates of the reconstructed IR spectra of each layer) for the alternating least squares algorithm to obtain a pure IR spectrum of each automotive paint layer. Comparing the reconstructed IR spectrum of each layer against the IR spectral library of the PDQ database demonstrated that it is possible to identify the correct model of the vehicle from these reconstructed spectra. This imaging approach to IR analysis of automotive paint, not only saves time and eliminates the need to analyze each layer separately, but also ensures that the final spectrum of each layer is "pure" and not a mixture.

5.
Appl Spectrosc ; 72(6): 886-895, 2018 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-29424551

RESUMEN

A previously published study featuring an attenuated total reflection (ATR) simulation algorithm that mitigated distortions in ATR spectra was further investigated to evaluate its efficacy to enhance searching of infrared (IR) transmission libraries. In the present study, search prefilters were developed from transformed ATR spectra to identify the assembly plant of a vehicle from ATR spectra of the clear coat layer. A total of 456 IR transmission spectra from the Paint Data Query (PDQ) database that spanned 22 General Motors assembly plants and served as a training set cohort were transformed into ATR spectra by the simulation algorithm. These search prefilters were formulated using the fingerprint region (1500 cm-1 to 500 cm-1). Both the transformed ATR spectra (training set) and the experimental ATR spectra (validation set) were preprocessed for pattern recognition analysis using the discrete wavelet transform, which increased the signal-to-noise of the ATR spectra by concentrating the signal in specific wavelet coefficients. Attenuated total reflection spectra of 14 clear coat samples (validation set) measured with a Nicolet iS50 Fourier transform IR spectrometer were correctly classified as to assembly plant(s) of the automotive vehicle from which the paint sample originated using search prefilters developed from 456 simulated ATR spectra. The ATR simulation (transformation) algorithm successfully facilitated spectral library matching of ATR spectra against IR transmission spectra of automotive clear coats in the PDQ database.

6.
Appl Spectrosc ; 72(3): 476-488, 2018 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-28959899

RESUMEN

Pattern recognition techniques have been applied to the infrared (IR) spectral libraries of the Paint Data Query (PDQ) database to differentiate between nonidentical but similar IR spectra of automotive paints. To tackle the problem of library searching, search prefilters were developed to identify the vehicle make from IR spectra of the clear coat, surfacer-primer, and e-coat layers. To develop these search prefilters with the appropriate degree of accuracy, IR spectra from the PDQ database were preprocessed using the discrete wavelet transform to enhance subtle but significant features in the IR spectral data. Wavelet coefficients characteristic of vehicle make were identified using a genetic algorithm for pattern recognition and feature selection. Search prefilters to identify automotive manufacturer through IR spectra obtained from a paint chip recovered at a crime scene were developed using 1596 original manufacturer's paint systems spanning six makes (General Motors, Chrysler, Ford, Honda, Nissan, and Toyota) within a limited production year range (2000-2006). Search prefilters for vehicle manufacturer that were developed as part of this study were successfully validated using IR spectra obtained directly from the PDQ database. Information obtained from these search prefilters can serve to quantify the discrimination power of original automotive paint encountered in casework and further efforts to succinctly communicate trace evidential significance to the courts.

7.
Appl Spectrosc ; 71(3): 480-495, 2017 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-27708178

RESUMEN

Multilayered automotive paint fragments, which are one of the most complex materials encountered in the forensic science laboratory, provide crucial links in criminal investigations and prosecutions. To determine the origin of these paint fragments, forensic automotive paint examiners have turned to the paint data query (PDQ) database, which allows the forensic examiner to compare the layer sequence and color, texture, and composition of the sample to paint systems of the original equipment manufacturer (OEM). However, modern automotive paints have a thin color coat and this layer on a microscopic fragment is often too thin to obtain accurate chemical and topcoat color information. A search engine has been developed for the infrared (IR) spectral libraries of the PDQ database in an effort to improve discrimination capability and permit quantification of discrimination power for OEM automotive paint comparisons. The similarity of IR spectra of the corresponding layers of various records for original finishes in the PDQ database often results in poor discrimination using commercial library search algorithms. A pattern recognition approach employing pre-filters and a cross-correlation library search algorithm that performs both a forward and backward search has been used to significantly improve the discrimination of IR spectra in the PDQ database and thus improve the accuracy of the search. This improvement permits inter-comparison of OEM automotive paint layer systems using the IR spectra alone. Such information can serve to quantify the discrimination power of the original automotive paint encountered in casework and further efforts to succinctly communicate trace evidence to the courts.

8.
Talanta ; 159: 317-329, 2016 Oct 01.
Artículo en Inglés | MEDLINE | ID: mdl-27474314

RESUMEN

A prototype library search engine has been further developed to search the infrared spectral libraries of the paint data query database to identify the line and model of a vehicle from the clear coat, surfacer-primer, and e-coat layers of an intact paint chip. For this study, search prefilters were developed from 1181 automotive paint systems spanning 3 manufacturers: General Motors, Chrysler, and Ford. The best match between each unknown and the spectra in the hit list generated by the search prefilters was identified using a cross-correlation library search algorithm that performed both a forward and backward search. In the forward search, spectra were divided into intervals and further subdivided into windows (which corresponds to the time lag for the comparison) within those intervals. The top five hits identified in each search window were compiled; a histogram was computed that summarized the frequency of occurrence for each library sample, with the IR spectra most similar to the unknown flagged. The backward search computed the frequency and occurrence of each line and model without regard to the identity of the individual spectra. Only those lines and models with a frequency of occurrence greater than or equal to 20% were included in the final hit list. If there was agreement between the forward and backward search results, the specific line and model common to both hit lists was always the correct assignment. Samples assigned to the same line and model by both searches are always well represented in the library and correlate well on an individual basis to specific library samples. For these samples, one can have confidence in the accuracy of the match. This was not the case for the results obtained using commercial library search algorithms, as the hit quality index scores for the top twenty hits were always greater than 99%.

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