Smart and Covalently Cross-Linked: Hybrid Shape Memory Materials Reinforced through Covalent Bonds by Zirconium Oxoclusters.

The first examples of organic-inorganic hybrid materials reinforced by transition-metal oxoclusters that exhibit shape memory properties, based on the covalent incorporation of zirconium-based inorganic building blocks, are reported. Methacrylate-functionalized zirconium oxoclusters Zr4 O2 (OMc)12 and [Zr6 O4 (OH)4 (OOCCH2 CH3 )3 {OOCC(CH3 )=CH2 }9 ]2 , with the covalent incorporation in a butyl acrylate (BA)/polycaprolactone dimethacrylate (PCLDMA) copolymer and the noncovalent incorporation of [Zr6 O4 (OH)4 (OOCCH2 CH3 )12 ]2 are focused upon herein. Shape recovery and fixity rates are studied to observe if the shape memory properties are preserved upon going from a simple copolymer to noncovalent or covalent-based hybrids. These rates display values higher than 90 %, which provides evidence that the oxocluster does not hinder the shape memory properties in the hybrid materials. The introduction of an inorganic phase and the progressively more stable interactions between organic and inorganic parts lead to an enhancement of the thermomechanical properties. The materials are characterized through FTIR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and swelling tests. Dynamic-mechanical analyses are used to investigate whether the hybrid materials display thermally activated shape memory properties. The stability of the hybrid materials are evaluated by a combined spectroscopic approach based on FTIR, solid-state NMR, and X-ray absorption spectroscopy.

Polyvinyl alcohol electrospun nanofibers containing Ag nanoparticles used as sensors for the detection of biogenic amines.

Polyvinyl alcohol (PVA) electrospun nanofibers containing Ag nanoparticles (NPs) have been deposited on glass substrates. The aim of the work was to test the feasibility of this approach for the detection of biogenic amines by using either the Ag localized surface plasmon resonance quenching caused by the adsorption of amines on Ag NPs or by detecting the amines by surface enhanced Raman spectroscopy (SERS) after adsorption, from the gas phase, on the metal NPs. Two different approaches have been adopted. In the first one an ethanol/water solution containing AgNO3 was used directly in the electrospinning apparatus. In this way, a simple heat treatment of the nanofibers mat was sufficient to obtain the formation of Ag NPs inside the nanofibers and a partial cross-link of PVA. In the second procedure, the Ag NPs were deposited on PVA nanofibers by using the supersonic cluster beam deposition method, so that a beam of pure Ag NPs of controlled size was obtained. Exposure of the PVA mat to the beam produced a uniform distribution of the NPs on the nanofibers surface. Ethylendiamine vapors and volatile amines released from fresh shrimp meat were chemisorbed on the nanofibers mats. A SERS spectrum characterized by a diagnostic Ag-N stretching vibration at 230 cm(-1) was obtained. The results allow to compare the two different approaches in the detection of ammines.

Structure-property relationships in heterophasic thermoplastic elastomers filled with montmorillonite.

Polypropylene (PP)/ethylene-propylene rubber (EPR)/Montmorillonite ternary nanocomposites with a phase separated morphology were studied in this work. Wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), atomic force microscopy (AFM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the samples. One of the aim of this work was to separate the effects of rubber and clay content on the structure, morphology and mechanical properties of the samples. The presence of clay favored the formation of gamma phase and disrupted the lamellar framework. Clay had moreover a major role in shaping the phase separated morphology of the samples. Atomic Force Microscopy showed that the shear exerted by the clay layers was key for inducing a shish kebab morphology in the polymer matrix. Rubber content decreased the degree of crystallinity at a crystalline cell level and induced the formation of a double population of lamellar stacks. The mechanical properties of the samples primarily depended on rubber content, and they were secondarily tuned by the effect of clay. This synergistic effect allowed to obtain composites with increased stiffness, ductility and toughness, oppositely to what is frequently found.

A direct SAXS approach for the determination of specific surface area of clay in polymer-layered silicate nanocomposites.

The interfacial area between the matrix and the filler is a key parameter which shapes the performance of polymer-based composites and nanocomposites, even though it is difficult to quantify. A very easy SAXS method, based on the Porod equation, is proposed for measuring the specific surface area of nanofillers embedded in a polymer matrix. In order to assess its reliability, this approach was applied to natural rubber- or styrene butadiene-based samples containing different types of montmorillonite clay. A wide range of specific surfaces was detected. SAXS data were compared to complementary X-ray diffraction and TEM information, obtaining a good agreement. Interpretation of the tensile properties by theoretical models and comparison with the literature corroborated the validity of the specific surface area measurement. The possibility to quantify this feature of composites allows the rational design of such materials to be improved.

Crystallization of a (1-butene)-ethylene copolymer in phase I directly from the melt in nanocomposites with montmorillonite.

Nanocomposites based on a copolymer of 1-butene and ethylene filled with montmorillonite (Cloisite 15A) were studied, obtaining for the first time crystallization from the melt directly into phase I. The polymorphism of the polymer and the dispersion of the filler in the matrix were investigated. The effect of the compatibilizer (PB-g-MA) on these properties was also singled out. The dramatic increase in the rate of the II --> I phase transition due to montmorillonite was attributed to the alteration in the phase stability diagram of the matrix, due to the introduction of defects and to induction of local pressure on the crystalline domains.

Forensic differentiation of paper by X-ray diffraction and infrared spectroscopy.

The possibility to discriminate between sheets of paper can be of considerable importance in questioned document examinations. 19 similar types of office paper were characterized by infrared spectroscopy and X-ray diffraction to individuate the most discriminating features that could be measured by these techniques. The discriminating value associated to them was also assessed. By using a sequence of these two techniques, all the samples could be differentiated.

Perkalite as an innovative filler for isotactic polypropylene-based nanocomposites.

Perkalite, an organically modified synthetic layered double hydroxide, was used as a filler in the preparation of nanocomposites based on isotactic polypropylene. The polymorphism of the polymer matrix was investigated, finding that Perkalite favors beta phase in certain conditions and is not a nucleant for the gamma polymorph. Perkalite promoted the formation of a dual population of lamellae, as evidenced by SAXS data. The dispersion of the filler was studied by WAXD, SAXS, and TEM. Perkalite was intercalated by the polymer and formed small, rather disordered tactoids, that determined an increase in physical mechanical properties, such as modulus, impact strength, thermal stability and heat deflection temperature. The Tm(0) of the materials was calculated by the method proposed by Marand, the kinetics of crystallization was evaluated by the Avrami analysis and also the Hoffman-Lauritzen theory of crystallization regimes was applied. Perkalite was found to depress Tm(0), to greatly enhance the rate of crystallization and to ease the chain folding of macromolecules.

A method based on thermogravimetry/differential scanning calorimetry for the forensic differentiation of latex gloves.

Latex gloves are quite frequently employed by felons, when committing crimes, if they want to avoid shedding fingerprints or biological traces. Less forensic aware crime committers, though, may discard the gloves at the crime scene or nearby. If found and properly analyzed, these items may therefore provide useful information to investigators. An analytical procedure of such items is proposed, using thermogravimetry and differential scanning calorimetry. By these very straightforward and inexpensive techniques, without sample preparation, nearly all the considered samples could be discriminated. 99.5% of the possible pairs of latex gloves, indistinguishable by visual examination, were differentiated. The rather large degree of variability existing in latex gloves, even though they are mass produced, was shown, confirming that these items can be useful in comparisons between items related to the crime scene and those seized in the suspect's premises.

The discrimination potential of ultraviolet-visible spectrophotometry, thin layer chromatography, and Fourier transform infrared spectroscopy for the forensic analysis of black and blue ballpoint inks.

The knowledge of the discriminating power of analytical techniques used for the differentiation of writing inks can be useful when interpreting results. Ultraviolet-visible (UV-VIS) spectrophotometry, thin layer chromatography (TLC), and diffuse reflectance Fourier transform infrared spectroscopy (FT-IR) were used to examine a population of 21 black and 12 blue ballpoint writing inks. Based on corroborative results of these methods, the discrimination power for UV-VIS, TLC, and FT-IR was determined to be 100% and 98% for the black and blue inks, respectively. Generally, TLC and UV-VIS can be used to differentiate the colorant components (i.e., dyes and some pigments) found in inks. As FT-IR can be utilized to identify some of the noncolorant components, it was determined to be an excellent complementary technique that can be implemented into an analytical scheme for ink analysis.

Structure-property relationship in polyethylene reinforced by polyethylene-grafted multi-walled carbon nanotubes.

Polyethylene-grafted multiwalled carbon nanotubes (PE-g-MWNT) were used to reinforce polyethylene (PE). The nanocomposites possessed not only improved stiffness and strength, but also increased ductility and toughness. The effects on the structure and morphology of composites due to pristine multiwalled carbon nanotubes (MWNT) and PE-g-MWNT were studied and compared using small angle X-ray scattering (SAXS), wide angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The SAXS long period, crystalline layer thickness and crystallinity of polymer lamellar stacks were found to decrease significantly in MWNT composites, while the decreases were much smaller in PE-g-MWNT composites. PE-g-MWNT allowed a more efficient and unhindered crystallization at a lamellar level, while MWNT disrupted the order of lamellar stacks, probably because of their tendency to aggregate. The SAXS crystallinity and the mechanical properties of the composites showed similar trends as a function of MWNT content. This suggested that the improvement of the interfacial strength between polymer and carbon nanotubes was a result of synergistic effects of better dispersion of the filler, better stress transfer, due to the grafting of polymer and MWNT, and the nucleation of a crystalline phase around MWNT. The latter effect was confirmed by measurements of kinetics of non-isothermal crystallization.

Structure-property relationships in isotactic poly(propylene)/ethylene propylene rubber/montmorillonite nanocomposites.

Nanocomposites based on isotactic polypropylene/ethylene propylene rubber (iPP/EPR) were prepared adding different amounts of montmorillonite and maleated polypropylene. The structure and morphology of the samples were characterized by small angle X-ray scattering, wide angle X-ray diffraction, electronic and optical microscopy and differential scanning calorimetry, iPP showed a polymorphic behavior. Clay disrupted the ordered crystallization of iPP and had a key role in shaping the distribution of iPP and EPR phases: larger filler contents brought about smaller, less coalesced and more homogeneous rubber domains. Clay distributed itself only in the continuous phase and not in the rubber domains. Tactoids persisted on the surface of the sample, while delamination proceeded to a greater degree in the bulk of the materials. Melt flow rate, impact strength, flexural and tensile properties, were also measured and a structure-property correlation was sought. Clay produced its most significant effect on physical-mechanical properties by controlling the size of rubber domains in the heterophasic matrix. This allowed to obtain nanocomposites with increased stiffness and impact strength, a remarkable achievement for polymer layered-silica nanocomposites that usually suffer the drawback of being stiffer than the unfilled matrix, but at the same time with a lower resistance to impact. A beneficial effect of clay on thermal stability was also observed.

A quantitative differentiation method for plastic bags by wide angle X-ray diffraction for tracing the source of illegal drugs.

Thirty-three shopping bags, commonly encountered in the packaging of drug doses, were characterized by wide angle X-ray diffraction (WAXD). Using this single technique, without sample preparation, nearly all the considered samples could be differentiated, achieving a discriminating power of 0.992. The rather large degree of variability existing in grocery bags, even though they are mass produced, was shown, confirming that these items can be useful in tracing the source of illicit drug doses.

A quantitative differentiation method for plastic bags by infrared spectroscopy, thickness measurement and differential scanning calorimetry for tracing the source of illegal drugs.

Fifty shopping bags, commonly encountered in the packaging of drug doses, were characterized by thickness measurements, infrared spectroscopy and differential scanning calorimetry. By these very straightforward and inexpensive techniques, without sample preparation, nearly all the considered samples could be discriminated. Ninety-seven percent of the possible pairs of white, apparently similar dull polymer films were differentiated. The rather large degree of variability existing in grocery bags, even though they are mass produced, was shown, confirming that these items can be useful in tracing the source of illicit drug doses.

The effect of exposure to the elements on the forensic characterization by infrared spectroscopy of poly(ethylene terephthalate) fibers.

Validation of a recently proposed differentiation method for single poly (ethylene terephthalate) (PET) fibers, based on integration of IR absorption bands, is presented. IR microscopy in the transmission mode, differential scanning calorimetry and optical microscopy were employed. The reliability of the technique has been extended to the cases in which the fibers being compared have experienced long exposure to the elements, as may happen if these items are recovered from open-air crime scenes. The effect of immersion in water and irradiation by the sun for a three-month period have been considered. The fibers remained morphologically and structurally unaltered. The significance of comparisons between fibers kept in different environments is thus enhanced, because the detrimental effect of the elements can be ruled out. This further validation of the proposed technique contributes to render the data presented by the forensic scientist less vulnerable to context effect and bias.

A quantitative differentiation method for acrylic fibers by infrared spectroscopy.

Absorbance peak areas of nitrile (2240 cm(-1)), carbonyl (1730 cm(-1)) and CH (1370 cm(-1)) groups were obtained for 48 colorless acrylic fibers by infrared (IR) microspectroscopy. The carbonyl signal, related to the comonomers most commonly used in acrylic fibers, was ratioed against the nitrile and CH bands, pertaining to the backbone of the polymer chains. The ratios A1730/A2240 and A1730/A1370, a relative measure of the comonomer content in the fiber, were used to differentiate the samples. A decrease in the crystallinity of fibers has been noted with increasing comonomer content. Relative standard deviation (R.S.D.) of the ratios were 1 and 3% for repetitive analyses on the same location and along the length of the same single fiber, respectively. When different fibers of the same sample were examined, results were reproducible within 6%. This simple method can greatly enhance the evidential value of colorless acrylic fibers, being able to discriminate them and thus helping the Court to better assess their significance.

Employing glass refractive index measurement (GRIM) in fiber analysis: a simple method for evaluating the crystallinity of acrylics.

The refractive index (RI) of 40 colorless acrylic fiber samples was determined by the immersion oil and Mettler hot stage method, implemented in the glass refractive index measurement (GRIM) instrument by Foster and Freeman. Low standard deviations for nearly all the samples were obtained and differentiation of fibers even with the same trade name was possible just on the basis of RI. Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) were employed to establish a linear correlation between RI and the degree of crystallinity. Insights on the structural order of this group of fibers is then obtainable by a quick and easy technique, adding value to casework comparisons.

Forensic analysis of poly(ethylene terephthalate) fibers by infrared spectroscopy.

Poly(ethylene terephthalate) (PET) is one of the most commonly employed polymers in the textile industry. Its relevance as a source of evidence in the reconstruction of criminal cases is nevertheless very limited because the properties and morphologies of fibers from different producers tend to be very similar. By integrating bands, obtained on single fibers by infrared (IR) microscopy, associated with trans and gauche conformation and to the O-H end-groups of the molecules, a method is proposed that can discriminate otherwise similar PET fibers. The absorbancies at 1370 and at 846 cm(-1) relative, respectively, to the gauche and trans conformation, were measured and ratioed. The end-group content was evaluated by ratioing the absorbancies of the signals at 3440 and at 874 cm(-1). Relative standard deviation (R. S. D.) was 1% for repetitive analyses on the same location of the same single fiber. Precision was reduced if the ratios were measured along the length of a single fiber (R. S. D. = 3%) and even further when different fibers of the same sample were examined (R. S. D. varied from 2 to 10%). This simple method can greatly enhance the evidential value of PET fibers by subclassifying them, thus helping the Court to better assess their significance.

Bayesian framework for the evaluation of fiber evidence in a double murder--a case report.

Fiber evidence found on a suspect vehicle was the only useful trace to reconstruct the dynamics of the transportation of two corpses. Optical microscopy, UV-Vis microspectrophotometry and infrared analysis were employed to compare fibers recovered in the trunk of a car to those of the blankets composing the wrapping in which the victims had been hidden. A "pseudo-1:1" taping permitted to reconstruct the spatial distribution of the traces and to further strengthen the support to one of the hypotheses. The Likelihood Ratio (LR) was calculated, in order to quantify the support given by forensic evidence to the explanations proposed. A generalization of the Likelihood Ratio equation to cases analogous to this has been derived. Fibers were the only traces that helped in the corroboration of the crime scenario, being absent any DNA, fingerprints and ballistic evidence.