A method based on thermogravimetry/differential scanning calorimetry for the forensic differentiation of latex gloves
Introduction
Latex gloves are commonly used by felons who wish to avoid shedding fingerprints on the crime scene. Although it is currently possible, albeit not in every case, to detect DNA traces or latent prints in the inside of the gloves, the forensic awareness of some crime committers is limited and gloves themselves can be found discarded at the crime scene or nearby. In some instances it has been proved useful to compare the gloves found at the crime scene with those seized at the suspect's premises. The literature on the forensic analysis of latex items is extremely limited. The only examples that could be found involve the examination of condoms, but they are focused mainly on the detection of lubricants and spermicides [1], [2], [3], [4].
Latex, a natural rubber, is a highly regular cis-1,4-polyisoprene produced by more than 400 different species of plants. The majority of the most common techniques for the characterization of polymers do not yield interesting information for the forensic differentiation of similar latex products. This material is amorphous, so X-ray diffraction will not be useful [5]. The analysis of the inorganic content [6], [7] could be in principle a viable technique, but it does not allow to single out the additives from the contaminants. Infrared spectroscopy is not very informative because all latex gloves yield extremely similar spectra, except in the case of chlorinated, powderless gloves that show some additional and potentially useful signals [8]. Physical and mechanical characterization cannot be applied in the majority of real cases because it requires samples of relatively large size and of standardized shape. Most of the times, there is not enough material to perform the replicate measurements necessary to obtain a reliable result.
Thermal analysis is a family of techniques that study the behavior of materials as a function of temperature. Differential scanning calorimetry (DSC) and thermogravimetry (TGA) are the most popular members of this family. DSC detects the variations in heat flow in or out of the sample when subject to a temperature program. It is the ideal technique to measure features such as the glass transition temperature or to study phase transitions like melting or crystallization [9], [10]. The glass transition temperature of natural rubber is located at extremely low temperatures, about −70 °C, and it is not easily measurable with accuracy by common equipment. The amorphous nature of latex makes otherwise featureless the DSC trace in the temperature scale investigated by normal stand alone DSC instruments (<300 °C).
TGA detects the variations in sample mass with temperature as a consequence of degradation, oxidation or other reactions. The usefulness of this technique for forensic purposes and in material analysis has already been suggested [11], [12]. Thermal degradation of polymer materials depends on their formulation and slight variations in additivation can bring about measurable changes in their behavior at high temperatures [13].
The purpose of this work is to investigate the value and reliability of a differentiation procedure of similar latex gloves by TGA. With this objective, 28 items were analyzed and the discriminative power of each characteristic feature of the thermogram was computed.
Section snippets
Samples
A total of 28 samples of latex gloves of different manufacturers were collected from different stores, either small hardware stores or large supermarkets. All the collected samples were similar and indistinguishable by visual observation.
Thermal analysis
Thermogravimetric analysis (TGA) was performed with a TA Instruments SDT 2960 simultaneous TGA/DSC system. With this system the mass loss associated to degradation mechanisms could be followed as a function of temperature, together with the heat flow. Tiny
Degradation in N2 atmosphere
Fig. 1, Fig. 2 show the thermograms of two samples analyzed in N2 atmosphere. The samples could be divided into two categories: those which degrade in a single main step occurring between 200 and 500 °C, and those which show two main steps, one between 200 and 500 °C and the other located at about 700 °C. The differential curves of Fig. 1, Fig. 2 show the derivative of the mass with respect to temperature as a function of temperature and are commonly used to represent TGA thermograms. These show
Conclusion
By thermal analysis, namely TGA and DSC, nearly all the latex gloves examined in this work could be discriminated. Care was taken to use very straightforward techniques and to avoid sample preparation, in order to meet the double aim of producing easily interpretable results without altering the items. The use of these techniques allowed to discriminate 99.5% of the possible pairs of apparently similar items. On the contrary, application of more basic procedures such as visual examination or
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