Forensic Applications of Portable X‐ray Fluorescence Spectrometer: Glass Samples

Portable X‐ray Fluorescence Spectrometer (PXRF) is a qualitative and semi‐quantitative elemental analysis method. Recently, many researches using PXRF in the elemental analysis of materials have been reported. However, PXRF has not been extensively applied in forensic science, thus this study is devoted to demonstrate the utility of this technique through a rapid elemental analysis of glass samples for preliminary glass discrimination. Major elements such as Si, O, Ca, Al, and Na, as well as traces of Sr, Rb, K, Fe and Sn, in 25 glass samples were analyzed by PXRF. The amounts of some elements, such as Fe, K, Zr, and Sr, vary in different samples, while other elements, such as Th, are consistent in most tested glass samples. The results show that we can discriminate 98.31 % of 7,500 pair‐wise comparisons created from 25 glass samples. This study establishes PXRF as a new rapid method for the preliminary elemental analysis of glass, which shows a potential to be further applied for discrimination of glass samples in forensic field.     

INAA of ancient glass beads from Sungai Mas archaeological site,Bujang Valley,Malaysia

The multi-elemental content of sixteen glass beads and eight glass samples from archeological site Sg Mas in Bujang Valley (finding from 5 th to 14 th century) were assayed by neutron activation analysis (NAA). Ten beads differed in colour and eight of them were opaque. Contents of twentyfour elements, which might be present in the samples as a flux, stabilizer, colorants or opacifier were examined. The elements Al, Br, Cl, Co, Cr, Fe, Hf, K, Mn, Na, Sc,Th, Zn and Zr were detectable in all samples. On the other hand, concentration of the elements As, Ba, Ca, Cs, Rb, Sb, Ta, Ti, U, and V were below the detection limit in some samples. The concentration of elements found are discussed in terms of color and/or opacity of the glass bead and glass samples. Although the elemental composition does not fully explain the color and opacity of the studied materials, it can still be used as fingerprint of the glass used for the bead making.     

Study of glassy microporous filters in the sodium borosilicate glasses with appropriate carriers

Summary DúThe aim of this work is to prepare a porous filter composed of two porous layers: macro-porous carrier and micro-porous sodium borosilicate (NBS) glass with TiO₂ additive (NBST glass), a Vycor-type glass. In the present work we prepared the macroporous support from the same material (NBST glass) as the upper microporous layer and then by sintering both parts to produce the required composite. This work introduces the results of experiments in the preparation of micro-porous filter on NBST glass base, laid on macro-porous carrier. After sintering of scrap NBST glass, porous samples were prepared to be used as carriers for micro-porous samples of phase-separated NBST glass. In other cases, the following carrier materials were used: a) frita SIMAX, b) Al₂O₃. The properties of the NBST glass and the changes in the glass structure with temperature were studied in order to determine the optimal sintering temperature of the prepared glasses. For the development of the sintered glasses, valuable information was obtained from heating microscopy (HM) and scanning electron microscopy (SEM) studies. The combination of the HM and SEM results with the measurements of the micro-hardness and density directed to the further study of the phase separated NBST glasses.     

Comparison between 3-point bending and torsion methods for determining the viscoelastic properties of fiber-reinforced epoxy

Dynamic mechanical analysis is a technique used to determine the viscoelastic properties of polymers and their composites. The storage modulus, loss modulus and loss factor in correlation with the glass transition temperature can be detected by several means. In this study, these properties are determined using a dynamic mechanical analyzer in 3-point bending mode, as well as a rheometer in torsion mode. The materials under consideration are a unidirectional glass fiber-reinforced epoxy, a quasi-isotropic carbon fiber-reinforced epoxy and a quasi-isotropic glass fiber-reinforced epoxy. The results of each method and material are presented and the advantages and limitations of each method are discussed. 3-point bending proved to be more suitable to detect the effect of fiber orientation for unidirectional fiber-reinforced epoxy but requires careful control of sample dimensions for accuracy. Torsion, on the other hand, gave consistent measurements for samples of varying lengths, proving to be a suitable method if materials are scarce and limited.     

Visualization of the morphology at the interphase of glass fibre reinforced epoxy-thermoplastic polymer composites

This work deals with the effect that the use of glass fibres has on the morphology developed by a thermoplastic polymer modified epoxy. In particular, three surface modifications of the glass fibres were studied: calcinations desizing, activation with hydrochloric acid and coating with 3-aminopropyltriethoxy silane. As the epoxy polymer, a model system based on the full reaction of DGEBA and 2-methyl-1,5-diaminopentane was used. As the modifiers of the epoxy thermoset, two thermoplastic polymers were used: poly(methylmethacrylate) and polystyrene. The morphologies were examined either in the polymer bulk or at the interfaces by means of scanning electron microscopy and atomic force microscopy. After a thoroughly examination of the samples it was found that the thermoplastic polymers preferentially accumulate at the interfaces of these materials when activated and silanized glass fibres are used. These results might be attributed to a gradual phase separation process due to stoichiometric gradients which, on the other hand, seems to be conditioned by the nature of glass fibres surface.     

Measurement of <Emphasis Type="Italic">T</Emphasis><Subscript>g</Subscript> in lyophilized protein and protein excipient mixtures by dynamic mechanical analysis

The glass transition of lyophilized materials is normally measured by conventional or temperature modulated differential scanning calorimetry (TMDSC). However, because of the weakness of these transitions when protein concentrations are high, these techniques are often unable to detect the glass transition (T _g). High ramp rate DSC, where heating rates of 100 K per min and higher are used, has been shown to be able to detect weak transitions in a wide range of materials and has been applied to these materials in previous work. Dynamic mechanical analysis (DMA) is also known to be much more sensitive to the presence of relaxations in materials than other commonly used thermal techniques. The development of a method to handle powders in the DMA makes it now possible to apply this technique to protein and protein-excipient mixtures. HRR DSC, TMA and DMA were used to characterize the glass transition of lyophilized materials and the results correlated. DMA is shown to be a viable alternative to HRR DSC and TMA for lyophilized materials.     

Design-of-experiment optimization of exhaled breath condensate analysis using a miniature differential mobility spectrometer (DMS)

Analytical instruments that can measure small amounts of chemicals in complicated biological samples are often useful as diagnostic tools. However, it can be challenging to optimize these sensors using actual clinical samples, given the heterogeneous background and composition of the test materials. Here we use gas chromatography-differential mobility spectrometry (GC/DMS) to analyze the chemical content of human exhaled breath condensate (EBC). Ultimately, this system can be used for non-invasive disease diagnostics. Many parameters can be adjusted within this instrument system, and we implemented a factorial design-of-experiments to systematically test several combinations of parameter settings while concurrently analyzing effects and interactions.We examined four parameters that affect sensitivity and detection for our instrument, requiring a 2⁴ factorial design. We optimized sensor function using EBC samples spiked with acetone, a known clinical biomarker in breath. Two outputs were recorded for each experiment combination: number of chemicals detected, and the amplitude of acetone signal. Our goal is to find the best parameter combination that yields the highest acetone peak while also preserving the largest number of other chemical peaks in the spectra. By optimizing the system, we can conduct further clinical experiments with our sensor more efficiently and accurately.     

Fused glass sample preparation for quantitative laser-induced breakdown spectroscopy of geologic materials

Laser-induced breakdown spectroscopy is a powerful analytical method, but LIBS is subject to a matrix effect which can limit its ability to produce quantitative results in complex materials such as geologic samples. Various methods of sample preparation, calibration, and data processing have been attempted to compensate for the matrix effect and improve LIBS precision. This study focuses on sample preparation by comparing fused glass as a preparation for powdered material to the more commonly used method of pressing powder into pellets for LIBS analysis of major elements in complex geologic materials. Pelletizing powdered material is a common and convenient method for preparing samples but problems with the physical matrix brought on by inconsistencies in the homogeneity, density, and laser absorption, coupled with the chemical matrix problem lead to spectral peak responses that are not always consistent with the absolute concentration of representative elements. Twenty-two mineral and rock samples were analyzed for eight major oxide elements. Samples were prepared under both glass and pellet methods and compared for internal precision and overall accuracy. Fused glass provided a more consistent physical matrix and yielded more reliable peak responses in the LIBS analysis than did the pressed pellet preparation. Statistical comparisons demonstrated that the glass samples expressed stronger separability between different mineral species based on the eight elements than for the pressed pellets and showed better spot-to-spot repeatability. Regression models showed substantially better correlations and predictive ability among the elements for the glass preparation than did those for the pressed pellets.     

Testing new graphene oxide-coated glazing for papyrus manuscripts in museums: Part I

The display of papyrus and paper (as cellulosic materials) in the Egyptian museums is always critical due to the traditional placement of display of sensitive materials between two plates of glass, acrylic, or other types of glazing materials. The sensitivity of the glazing materials to abrasion, ultraviolet rays, dust adhesion, and high light reflectivity are considered concerning issues to conservators, curators, and visitors. In this paper, thin protective coatings of graphene oxide (GO) were synthesized by modified Hummers' method and deposited on selected museums' glazing materials (glass and acrylic) using spin coating. Multi-analytical techniques were employed to assess the applicability of GO-coated glazing including scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR), microhardness testing, NIR VIS, and UV spectrophotometer and static potential measurements. The results showed that the glass glazing hardness was increased by ~10% due to the deposition of the GO coating. Moreover, according to glazing type, the reflectance values of the GO-coated glazing samples, compared with the uncoated samples, confirmed that the thin film of GO improved the UV rays blocking. As is evident in the GO-coated glass where approximately 27% of UV rays have been blocked, likewise, 19% of UV rays were blocked in GO-coated acrylic (TRU VUE). Considering VIS and NIR reflection spectra of GO-coated plexiglass, a higher reflectance is presented by 29%. Furthermore, the static potential measurements showed an energy decline in GO-coated glazing compared with the uncoated samples.     

Study of properties of the glass batch melting filter dust

The filter dust from the container glass production was studied by the X-Ray powder diffraction, differential thermal analysis (DTA), X-Ray fluorescent spectroscopy, and Raman spectroscopy. The analysis of the elemental composition indicated that the major portion (≈96 wt%) of filter dust is comprised of sulfates. Predominant abundance of sodium sulfate was confirmed by comparative DTA of investigated filter dust. The characteristic redox property (COD—Chemical Oxygen Demand) was determined. The raw materials used in manufacturing of container glass in Vetropack Nem?ová with 0, 25, 50, 75 or 100 wt% of filter dust as a substitution of sulfate raw material were used for the preparation of samples of glass batch. Thermal properties of prepared samples were characterized by means of DTA. The substitution of sulfate raw material by filter dust does not significantly affect the thermal properties of the examined glass batches and consequently the course of the glass melting.     

Comparison between X-ray fluorescence and inductively coupled plasma atomic emission spectrometry in the analysis of sediment samples

Two multielemental analytical techniques, X-ray fluorescence analysis (XRF) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were used for the analysis of the elemental composition of sediment samples from a marsh and standard reference materials. The sediment samples were pretreated with different methods which are widely used in practice. A comparison was made not only between the concentrations obtained by the different methods, but also between the statistical conclusions derived from the processing of the experimental results. Good agreement was found for some elements, e.g. Mn, Zn and Sr, while the concentrations and the statistical conclusions were shown to depend on the analytical method used in the case of other elements, e.g. Fe and Zr.     

Comparative characterization of oligomeric precursors intended for injectable implants

The use of injectable materials is a simple approach for drug delivery and tissue repair, in, e.g. minimally invasive surgery applications. If these materials are used past their glass transition temperature and have a low viscosity, they will be able to flow while delivered in situ. Whether these materials are to be used as low viscosity drug carriers or further crosslinked for tissue repair, there is a need for a better understanding of their handling properties. In this study, oligo(trimethylene carbonate) (oTMC) and oligo[D,L‐lactide‐co‐(ε‐caprolactone)] (oDLLA‐co‐CL) of various molecular weights within a relevant injectability range were synthesized via ring‐opening polymerization. The materials were comparatively characterized by ¹H NMR spectroscopy, differential scanning calorimetry, gel permeation chromatography, and rheological measurements. After comparing the viscosities and molecular weights of the materials, it was concluded that oDLLA‐co‐CLs were, generally, better suited as an injectable in situ crosslinking network, whereas oTMCs were found to be better candidates as injectable drug carriers. This study provides useful data and guidelines on the use of these and other similar oligomers intended for injectable implants. Copyright © 2012 John Wiley & Sons, Ltd.     

Elemental analysis of the marine sediment reference materials MESS-1 and PACS-1 by instrumental neutron activation analysis

Two fairly recent sediment reference materials (MESS-1, PACS-1) have been analyzed by INAA in order to determine the concentration of their elements and to ascertain the homogeneity of each standard. Two rock samples (USGS-GSP-1 and JG-1) were used as standards for the determination of element concentrations, for inter-calibration purposes and also to assess the precision of the technique used. Eighteen elements were determined in these sediments. Comparison of the certified values with our results, where this is possible, indicates the accuracy of the method for environmental studies. These materials were shown to be very homogeneous and hence useful as sediment standards. The data presented here extend the range of useful element concentrations in these reference materials.     

A broad-band dielectric study of poly(vinyl chloride): Effect of molar mass and processing conditions on space-charge mechanisms

The dielectric properties of poly(vinyl-chloride) (PVC) were investigated as a function of frequency and temperature. Attention was focused on the low frequency dielectric properties. Samples with different molar masses were studied. Two dipolar retardation processes were observed, one due to a local motion in the polymeric chain and the other at the glass transition. In compression-molded samples of high molar mass an additional low-frequency space-charge polarization mechanism was found at high temperatures. The effect was most pronounced at the highest molar masses. The space-charge mechanism was absent in samples of well-kneaded material. This macroscopic polarization process in compression molded samples is probably due to discontinuities in the poorly gelified material because of a residual grain particle structure. The detected effects of air inclusions in a PVC matrix can be described by the Maxwell-Wagner theory. The magnitude of the space-charge mechanism is an indication of the effectiveness of the processing method used in destroying the grain structure. © 1994 John Wiley & Sons, Inc.     

Trace element characterization of medieval and post-medieval glass objects by means of INAA and EPMA

Instrumental neutron activation analysis (INAA) was applied to create a database for minor and trace elements in medieval and post-medieval glassware in order to establish a methodology for estimating the origin of the glass objects. First, general characterization of glass types was done on the basis of the results obtained by the use of electron probe microanalysis (EPMA). Information received by the use of INAA provided the additional valuable data reflecting to some extent the method of preparation or the differentiation of various sources of certain raw materials. Several glass samples and a set of various reference glass materials were used for our experiments.     

Enhancing the sensitivity of capillary electrophoresis using a microcolumn solid phase extraction setup

In this paper, a setup called micro‐column solid phase extraction (MicroSPE) was developed to enhance the sensitivity of capillary electrophoresis. The setup consists of a manual pump, several insulin syringes, and a Teflon extraction cartridge. The cartridge was made of 2–4 mm irregular C₁₈ solid phase materials in a Teflon tube (375 μm ID) with glass fiber frits. Two pieces of capillary tubing were connected to both the ends of the cartridge. Using sulindac‐spiked urine as the test sample, the extraction and analytical conditions were investigated in detail. When 1 μL 70/30 methanol/water was applied as the elution solvent, satisfactory results could be obtained. The internal standard method was used to quantitatively determine the compound in urine. The detection limit for sulindac was 2.9 ng/mL and the enrichment factor reaches more than 260. The result illustrates that the MicroSPE setup has a significant concentrating effect and is suitable for preconcentrating and cleaning‐up samples with complex matrices.     

不同结晶度的乙二醇及其水溶液玻璃化转变与焓松弛

为了考察晶体成分对无定形成分玻璃化转变和结构松弛行为的影响,利用差示扫描量热法(DSC),结合低温显微技术,研究了乙二醇(EG)及其50％水溶液在不同结晶度时的玻璃化转变和焓松弛行为.采用等温结晶方法控制骤冷的部分结晶玻璃体中的晶体份额.DSC结果表明,对于部分结晶的EG,只有单一的玻璃化转变过程,而对于50％EG,当结晶度不同时,不同程度地表现出两次玻璃化转变（无定形相Ⅰ和无定形相Ⅱ）.相Ⅰ的玻璃化转变温度和完全无定形态的含水EG的玻璃化转变温度相一致;相Ⅱ的玻璃化转变温度要比此温度约高6 ℃.低温显微观察结果印证了DSC实验结果.DSC等温退火的实验和KWW(Kohlrausch-Williams-Watts)衰变函数分析结果表明,EG无定形和50％EG中的两种无定形有不同的焓松弛行为.     

电弧炉燃烧-红外法测定碳量与硫量

电弧炉与红外碳、硫分析仪配套，用于测定硅铁、金属锰、矿石、铬铁、钒铁、合金钢铸铁、水泥、微晶玻璃，阳极泥等物质中碳量和硫量，结果满意。     

Spectroscopic linear dichroism FT-IR studies of synthetic spider silk

This work deals with the analysis of the orientation behavior of different segments of synthetic spider silk samples containing hard and soft segments. Two different types of spider silk were examined, one with an aliphatic hard segment (hexamethylene-diisocyanate) and an amorphous soft segment (polytetramethylene oxide) (A40) and the other with an aromatic hard segment (4,4′-methylene bisphenyl diisocyanate) and a semicrystalline soft segment (polyethylene oxide-polypropylene oxide- polyethylene oxide) (A143). In order to observe the orientation behavior of the hard and the soft segments it was necessary to define marker bands. While for both samples the chosen marker bands for the hard segments were the same, the marker bands for the soft segments were different. FT-IR spectra were recorded while strain was applied to the material at the same time. Two parameters, the dichroic ratio R and the order Parameter f were used to evaluate the behavior of these materials under conditions of strain. It was found that sample A143 broke at a strain level of 37,5 %, while sample A40 showed a high dynamic range up to a strain level of 307 %.     

Smart gel–glass based on the responsive properties of polymer gels

Polymer gels are unique smart materials in the sense that they can respond to many different stimuli. In this paper we report how poly(N‐isopropylacrylamide) (abbreviated as PNIPA) and other polymer hydrogels can be used to construct an intelligent gel‐glass which can moderate the amount of light and radiated heat. This environmental sensitive glass, which is a smart hydrogel layer placed between two glass or plastic sheets, becomes opaque when the temperature exceeds a critical value. It becomes transparent again if it is cooled down. The adaptive properties of gel‐glasses make them a promising materials to protect from strong sunlight and heat radiation. Copyright © 2001 John Wiley & Sons, Ltd.