Detection of High Explosives Using Reflection Absorption Infrared Spectroscopy with Fiber Coupled Grazing Angle Probe/FTIR

Fiber Optic Coupled Reflection/Absorption Infrared Spectroscopy (RAIRS) has been investigated as a potential technique for developing methodologies of detection and quantification of explosive residues on metallic surfaces. TNT, DNT, HMX, PETN, and Tetryl were detected at loading concentrations less than 400 ng/cm². Data were analyzed using Chemometrics statistical analysis routines. In particular, partial least squares multivariate analysis (PLS) was used for quantification studies. Peak areas were also used for data analysis to compare with linear multivariate analysis. The measurements resulted in intense absorption bands in the fingerprint region of the infrared spectrum that were used to quantify the target threat chemicals and to calculate the limit of detection for each compound. Micro-RAIRS vibrational imaging was also used for characterization of the distribution and form of layers of explosives deposited on stainless steel sheets. The degree of homogeneity depended strongly on the method of deposition. The images were generated by calculating the area under vibrational signals of 15 μm × 15 μm grids with a separation of 15 μm. Histograms of the maps were generated and the homogeneity was evaluated by using standard deviations, mean kurtosis, skewness, and moments of distributions obtained. Methanol solutions of High Explosives (HE) resulted in the optimum distributions on the stainless steel surfaces tested and therefore, Methanol selected as the preferred solvent for the Fiber Optics Coupled-RAIRS experiments.     

EVALUATION OF SELF-ATTENUATION COEFFICIENTS OF OIL-PRODUCED SCALES FOR GAMMA-RAY SPECTROSCOPIC ANALYSIS

This study focuses on the evaluation of self-attenuation correction factors (C_f) and linear?attenuation coefficients (μ) of scale samples, produced from the oil fields. This was performed using ¹⁵²Eu point source at the optimal geometry found (i.e., 3 mm). The scale samples were of apparent density ranging 1.04 ? 3.08 g cm^?3. The results illustrated that self-attenuation correction values were as high as 5.08 for the most dense samples at γ-energy line of 45.5 keV. High correlation was observed by Pearson matrix between self-attenuation correction factor and sample density (correlation coefficient of 0.967 at γ-energy of 45.5 keV). A simplified model of the relationship between these variables was proposed. The remarkable finding was that when scale sample density increased self-absorption extended to occur to a higher energy line. Hence, self-attenuation correction was negligible at γ-energies of 122, 222, and 344 keV for samples with density ranging 1.04–1.41, 1.45–2.04, and 2.12–3.08 g cm^?3, respectively. Since linear attenuation coefficient is material sensitive, it was calculated for each sample. Analysis of variance (ANOVA) reflected the linear relationship between linear-attenuation coefficient and sample density up to 344 keV which disappeared thereafter. The data obtained allowed an accurate determination of the concentrations of γ-emitters in scale samples within the energy range of 45.5–1408 keV.     

Proposal of an FTIR Methodology to Monitor Oxidation Level in Used Engine Oils: Effects of Thermal Degradation and Fuel Dilution

This article describes a procedure, based on ASTM standards D7214 and E2412, that has been defined to improve quantification of oil oxidation in used engine oils. Taking into account typical problems that can be found in this type of sample, including thermal oxidation and fuel dilution, Fourier transform infrared (FTIR) spectra were analyzed also considering the effect of the oil formulation. Two zones were considered inside the typical wavenumber range for quantification of oxidation, where those problems can be detected and assessed more easily: zone A between 1725 and 1650 cm^?1, where the main oxidation products, such as aldehydes, carboxylic acids, and ketones, occur due to thermal degradation of the oil; and zone B between 1770 and 1725 cm^?1, where esters due to potential biodiesel dilution problems are detected.     

Fabrication,Characterisation and Tribological Investigation of Artificial Skin Surface Lipid Films

This article deals with the tribology of lipid coatings that resemble those found on human skin. In order to simulate the lipidic surface chemistry of human skin, an artificial sebum formulation that closely resembles human sebum was spray-coated onto mechanical skin models in physiologically relevant concentrations (5–100 μg/cm²). Water contact angles and surface free energies (SFEs) showed that model surfaces with ≤25 μg/cm² lipids appropriately mimic the physico-chemical properties of dry, sebum-poor skin regions. In friction experiments with a steel ball, lipid-coated model surfaces demonstrated lubrication effects over a wide range of sliding velocities and normal loads. In friction measurements on model surfaces as a function of lipid-film thickness, a clear minimum in the friction coefficient (COF) was observed in the case of hydrophilic, high-SFE materials (steel, glass), with the lowest COF (≈0.5) against skin model surfaces being found at 25 μg/cm² lipids. For hydrophobic, low-SFE polymers, the COF was considerably lower (0.4 for PP, 0.16 for PTFE) and relatively independent of the lipid amount, indicating that both the mechanical and surface-chemical properties of the sliders strongly influence the friction behaviour of the skin-model surfaces. Lipid-coated skin models might be a valuable tool not only for tribologists but also for cosmetic chemists, in that they allow the objective study of friction, adhesion and wetting behaviour of liquids and emulsions on simulated skin-surface conditions.     

Dental Enamel Caries (Early) Diagnosis and Mapping by Laser Raman Spectral Imaging

Abstract

A method for estimating the extent of tooth caries and providing imaging information based on Raman Spectral Imaging is suggested. This non‐destructive optical method is able to characterize and differentiate between normal enamel tooth surface, and initial and advanced tooth caries. Images and corresponding spectra were acquired from various tooth sites, and it was demonstrated that normal, white opaque, brown discoloured, and pitted tooth surfaces all have different distinct spectral features which characterize the different degrees of dental caries. Spectral analysis allows for detection of early changes in the surfaces of carious teeth, and the associated mapping capability allows for morphological characterization. It was found that the emission at 960 cm^?1, which corresponds to PO stretching in the hydroxyapatite bond, is the most significant and can be used for diagnosis of caries. The emissions at 1070 cm^?1 and at 590 cm^?1 can also be applied, but are less accurate. The results suggest that this technique may be further developed and applied for clinical diagnosis of initial and more advanced demineralization processes of the enamel tooth surfaces.     

Effect of Graphene and Ionic Liquid Additives on the Tribological Performance of Epoxy Resin

In the present study, we have determined the effect of graphene (PG), the ionic liquid (IL) and PG modified by mechanical blend with the IL 1-octyl-3-methylimidazolium tetrafluorobotate (IL + PG) on the tribological performance of epoxy resin (ER). IL + PG stable suspensions have been added to an epoxy resin (ER) matrix to obtain the new nanocomposite (ER + IL + PG), and its tribological performance has been compared with that of neat epoxy resin and with the nanocomposites containing PG (ER + PG) or IL (ER + IL). While neat ER presents a high dynamic friction coefficient of up to 0.31 and a severe wear with a specific wear rate of 8.1 × 10^?4 mm³ N^?1m^?1, the new nanocomposites show negligible surface damage, as determined by surface roughness and profilometry. All nanocomposites show low friction coefficients and negligible wear. The maximum friction reduction, up to a 70 %, is obtained for ER + PG. Results are discussed upon the basis of TEM microscopy, SEM microscopy and EDX analysis, differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical analysis. Addition of IL or IL + PG has a plasticizing effect on ER, while addition of PG increases the thermal stability and stiffness of ER. PG shifts the storage modulus onset and in the loss modulus and tan δ maximum peaks to higher temperatures, while a shift to lower values is observed with addition of IL or IL + PG.     

Preparation of TNT,RDX and Ammonium Nitrate Standards on Gold-on-Silicon Surfaces by Thermal Inkjet Technology

This research examines the surface contamination properties, trace sample preparation methodologies, detection systems response and generation of explosive contamination standards for trace detection systems. Homogeneous and reproducible sample preparation is relevant for trace detection of chemical threats, such as warfare agents, highly energetic materials (HEM) and toxic industrial chemicals. The objective of this research was to develop a technology capable of producing samples and standards of HEM with controlled size and distribution on a substrate to generate specimens that would reproduce real contamination conditions. The research activities included (1) a study of the properties of particles generated by two deposition techniques: sample smearing deposition and inkjet deposition, on gold-coated silicon, glass and stainless steel substrates; (2) characterization of composition, distribution and adhesion characteristics of deposits; (3) evaluation of accuracy and reproducibility for depositing neat highly energetic materials such as TNT, RDX and ammonium nitrate; (4) a study of HEM-surface interactions using FTIR-RAIRS; and (5) establishment of protocols for validation of surface concentration using destructive methods such as HPLC.     

Characterization of an ultraviolet irradiation chamber to monitor molecular photodegradation by Raman spectroscopy

A homemade ultraviolet chamber is reported to induce photochemical changes with characterization by Raman spectroscopy. The equipment has compartments for ultraviolet-A (UV-A) (8 lamps of 8 W) and for UV-A + ultraviolet-B (UV-B) irradiation (4 lamps of 26 W and 1 lamp of 15 W). The irradiance was measured 3, 5, and 10 cm from the light sources. The maximum irradiance was obtained at 3 cm (UV-A: 2.66 mW/cm² and UV-A + UV-B: 4.30 mW/cm²). The chamber internal temperature was stabilized at 30°C after 1 hr of operation with an internal relative humidity of approximately 45%. 10% Collagen was irradiated with UV-A at 2.0 mW/cm² for 3 hr with changes in Raman peaks at 1253, 1271, 1453, and 1660 cm^?1 indicating changes in conformation. 5% Atenolol was irradiated with UV-A + UV-B at 4.30 mW/cm² for 8 hours with changes to Raman peaks at 822, 1186, 1206, 1248, and 1618 cm^?1. A commercial insect repellent was irradiated with UV-A + UV-B at 4.30 mW/cm² for 8 hr and decreases in Raman intensity were observed at 526, 690, 1003, and 1606 cm^?1 due to degradation of N, N-diethyl-m-toluamide. The results demonstrate proper operation of the irradiation chamber with Raman spectroscopic monitoring.     

Immersion‐Angle Dependence of the Resonant‐Frequency Shift of a Quartz Crystal Microbalance in Three Types of Newtonian Liquids

Abstract

The present work reports the new characteristics of the immersion‐angle dependence of the resonant‐frequency shift (ΔF) of the one‐face sealed quartz crystal microbalance (QCM) in three types of Newtonian liquids, i.e., sucrose, glucose, and glycerol solutions. Below some 1.80×10^?2 g cm^?2 · s^?1/2, the ΔF values are dependent on the immersion angles in all solutions. However, we have found that the transition phenomenon of ΔF occurs between 1.78×10^?2 and 4.80×10^?2 g · cm^?2 · s^?1/2 in the sucrose solution, between 1.75×10^?2 and 4.34×10^?2 g · cm^?2 · s^?1/2 in the glucose solution and between 1.83×10^?2 and 3.03×10^?2 g · cm^?2 · s^?1/2 in the glycerol solution, respectively. Moreover, above the concentrations of the end points of the transition phenomenon, the ΔF values of the sucrose solution are equal to those of 90° at all immersion angles. On the other hand, those of the glucose and the glycerol solutions are the same as those of 30°. This difference may be caused by inherent characteristics of adsorption to the surface of the QCM electrode.     

Friction and dry sliding wear of bismaleimide filled with carbon nanotubes

Three types of bismaleimide–carbon nanotubes (CNTs) nanocomposites were fabricated using two types of original multiwalled CNTs with different diameters and one amide functionalized CNTs. The influence of diameter, content and functionalization of CNTs on the flexural and dry sliding wear behaviour were measured with universal testing machine and pin-on-disc wear apparatus. The experimental results indicated that at 1.5 wt-%, the bismaleimide-functionalized MWCNTs exhibited highest flexural strength of 156 MPa which is increased by 164% as compared to the neat matrix, and lowest specific wear rate of 1.8 × 10^?4 mm³ N^?1 m^?1 which is decreased by 90% as compared to the neat matrix. This was attributed to the dispersion of CNTs in the matrix and the filler-matrix adhesion and internal strength of the composite.     

A Method for Determining the Ionization Spectra of Monodispersed Clusters of Noble Metals Adsorbed on the Surfaces of Ionic–Covalent Crystals

The method described is based on the vacuum deposition of separate monodispersed molecular metal ions from a mass-separated beam on the surfaces of ionic–covalent crystals and the detection of ultralow concentrations (10⁸ cm^–2) of adsorbed states using the method of photostimulated luminescence flash.     

Measuring the surface purity of substrates by the tribometry method

A tribometric device designed for rapid monitoring of the concentrations of atomic and molecular contaminants on the surfaces of semiconductor and dielectric substrates within the range of 10^?7–10^?10 g/cm² is described. The method is based on measurements of the static and sliding friction coefficients between the investigated surfaces. The arrangement of interacting substrates forming a point contact and allowing elimination of disturbances in the crystal structure in the slip region at loads in the range of 0–3.7 N and angles between the substrates of 0–15° is shown.     

Self-recovery of the transparency of a focusing lens in a laser mass spectrometer

An experience of operation of a laser mass spectrometer of multiply charged ions has shown an almost complete self-recovery of the transparency of a focusing lens (chamber window). Spectra of multiply charged ions from a W target recorded at laser-radiation-power densities on the surfaces of the lens and target of 2.5 × 10⁶–1.2 × 10⁷ and 2 × 10¹⁰–10¹² W/cm², respectively, do not change substantially even after 10⁵ laser shots thanks to the self-recovery of the lens transparency.     

Mechanical behavior and numerical analysis of corrugated wire mesh laminates

The objective is to show a possibility of corrugated wire mesh laminate (CWML) structure for bone application. CWML is a part of open-cell structures with low density and high strength built with bonded mesh layers. Specimens of CWML made of 316 stainless steel woven meshes with 0.22 mm wire diameter and 0.95 mm mesh aperture, bonded by transit liquid phase (TLP) at low temperatures, were fabricated and tested under quasi-static conditions to determine their compressive behavior with varying numbers of layers of the sample. The finite element software was used to model the CWML and studied their response to mechanical loading. Then, the numerical model was confirmed by the tested sample. Consequently, CWML specimens were reasonably matched with the human tibia bone ranged over apparent density from 0.05 to 0.08 g/cm³ in Young’s modulus and from 0.05 to 0.11 g/cm³ in compressive yield strength. The CWML model can have the potential for bone application.     

SURFACTANT MEDIATED EXTRACTION OF TRITERPENES AND THEIR DIRECT HPLC ANALYSIS FROM THE MICELLAR SYSTEM

The pentacyclic triterpenes oleanolic acid (OA) and ursolic acid (UA) in Salvia triloba are attractive ingredients for cosmetic and pharmaceutical formulations. These triterpenoids are constitution isomers and differ only in the position of one methyl group in their chemical structures. Therefore it is difficult to achieve a baseline separation by standard RP-HPLC systems. Another challenge is that the complex plant contains a large variety of similar compounds. To achieve precise results for the target molecules, these compounds should be removed prior to analysis. Due to the large application of these two triterpenes, a fast quantification method is favored. If the triterpenes are extracted with aqueous two-phase systems, the target substances are enriched in a surfactant-rich phase. For this application, it is desirable to develop a method that is capable of quantifying both triterpenes directly by RP-HPLC without additional purification steps.

The optimal chromatographic conditions for pure substances as well as for crude surfactant-containing extracts were accomplished on a Nucleodur C18 ISIS column by isocratic elution with methanol/water/acetic acid/triethanolamine (90:10:0.04:0.02 v/v) as the mobile phase and a column temperature of 10°C. The flow rate was 0.6 mL/min, and the detection wavelength was 210 nm. With these parameters, a baseline separation was achieved and the calibration curve showed a very good linearity (R² > 0.999 for OA and UA) within the test range. The method is simple, rapid, and reliable for the quantification of crude extracts from plant material.     

Identification and quantification of β-caryophyllene in copaiba oil using Raman spectroscopy

Copaiba oleoresin presents several compounds with known biologic activity and physiologic effects, including analgesic and insecticide properties. Among them are the terpenoids (mainly diterpenes and sesquiterpenes) with β-caryophyllene, the main representative of the terpenoids and considered to be a chemical marker. This study employed Raman spectroscopy and principal component analysis (PCA) techniques to identify and quantify the β-caryophyllene marker in copaiba oil samples purchased from popular markets in Brazil. A dispersive Raman spectrometer (830?nm, 250?mW, 2?cm^?1 spectral resolution) was used. Results showed the identification of the main Raman peaks from the β-caryophyllene in copaiba oil samples (main peaks at 507, 771, 1442, 1638, and 1673?cm^?1). The loading vector 2 (PC2) extracted the spectral information from β-caryophyllene in the samples and the eigenvalue 2 (score 2) allowed the estimation of the concentration of this marker in commercial samples, with the concentrations from 15 to 34%. Raman spectroscopy combined with PCA may be considered to be a potential analytical tool for the quality control of Copaifera oil samples by quantifying β-caryophyllene using its unique spectral information.     

Estimating the surface density of fissures in clay soil from deterministic parallel sections

In much clay soil the pore space consists of 3-D networks of narrow, approximately planar fissures. The density of the interface between fissures and solid soil is important; a method for its estimation from the horizontal and vertical cuboid samples that are taken conventionally is described here. Undisturbed samples are impregnated with resin containing a fluorescent dye. Parallel plane faces are cut, and the exposed surfaces are photographed under u.v. light. Pairs of superimposed photographic negatives are projected onto a screen, and the lateral displacement of each interface from one section to the next is measured at points of intersection of the interface with linear probes through the soil. These distances are used to infer the local orientation of the interfaces, which are then used with the point counts to estimate the interface areas. The method was applied to subsoil of the Windsor series. The interface density was estimated to be 9.69cm²/cm³ from one horizontal and one vertical sample. Point-counting with isotropic uniform random linear probes applied to five randomly orientated samples from the same site gave an estimate of 8.78cm²/cm³. It seems probable that the error associated with the new method is no greater than that associated with the standard method.     

Heat transfer in injection molding for reproduction of sub-micron-sized features

Heat transfer in injection molding was quantitatively measured with micro heat-flux sensors. The 0.1–10 micron-wide micro-grooves with aspect ratios of 0.5–1.0 were etched by focus ion beam on a Ni-plated mold. During the short time just after injecting, heat-flux in the mold was maximized to 10–50 W/cm², and heat transfer coefficient between plastic and mold was 0.27 W/(cm²K) with PMMA and 0.085 W/(cm²K) with PS. The maximum mold surface temperature just after injecting should be above the glass transition temperature of plastic, then reproducing sub-micron-wide micro-ridges.     

Modes of energy loss on shearing of thin confined films

Analysis of friction versus time traces for stick-slip friction of mica surfaces across solidified films confined between them, reveals that most of the frictional dissipation occurs via viscous heating of the shear melted film during the part of the cycle where the surfaces slide past each other (slip). A much smaller part of the energy dissipation results from the loss of residual kinetic energy at the abrupt end of the slip. Contribution to special issue of Tribology Letters in memory of the late Professor David Tabor