Showing papers on "Fourier transform infrared spectroscopy published in 2008"

Synthesis and characterization of zinc oxide nanoparticles: application to textiles as UV-absorbers

Abstract: We report the synthesis and characterization of nanosized zinc oxide particles and their application on cotton and wool fabrics for UV shielding. The nanoparticles were produced in different conditions of temperature (90 or 150 °C) and reacting medium (water or 1,2-ethanediol). A high temperature was necessary to obtain small monodispersed particles. Fourier transformed infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray powder diffractometry (XRD) were used to characterize the nanoparticles composition, their shape, size and crystallinity. The specific surface area of the dry powders was also determined. ZnO nanoparticles were then applied to cotton and wool samples to impart sunscreen activity to the treated textiles. The effectiveness of the treatment was assessed through UV–Vis spectrophotometry and the calculation of the ultraviolet protection factor (UPF). Physical tests (tensile strength and elongation) were performed on the fabrics before and after the treatment with ZnO nanoparticles.

Functionalization of Halloysite Clay Nanotubes by Grafting with γ-Aminopropyltriethoxysilane

Abstract: Surface modification of natural halloysite clay nanotubes with γ-aminopropyltriethoxysilane (APTES) was investigated. Untreated and modified samples were characterized by nitrogen adsorption, X-ray diffraction, elemental analysis, thermogravimetry, transmission electron microscopy, atomic force microscopy, MAS nuclear magnetic resonance (29Si, 13C, 29Al), and Fourier transform infrared spectroscopy. The modification mechanism was found to include not only the direct grafting of APTES onto the hydroxyl groups of the internal walls, edges and external surfaces of the nanotubes but other processes in which oligomerized APTES condensed with the directly grafted APTES to form a cross-linked structure. The thermal and evacuation pretreatment conditions were found to play an important role in controlling the extent and mechanism of the modification. The extent of modification is also strongly affected by the morphological parameters of the original clay samples. This study demonstrates that the surface chemistry...

Bionanocomposites based on poly(ε-caprolactone)-grafted cellulose nanocrystals by ring-opening polymerization

Abstract: A ‘grafting from’ approach was used to graft poly(e-caprolactone) (PCL) polymers to cellulose nanocrystals by Sn(Oct)2-catalyzed ring-opening polymerization (ROP). The grafting efficiency was evidenced by the long-term stability of suspension of PCL-grafted cellulose nanocrystals in toluene. These observations were confirmed by Fourier Transform Infrared Spectroscopy (FT-IR) and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). Extracted nanohybrids were characterized by Differential Scanning Calorimetry (DSC), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. The morphology and crystalline structure of the PCL-grafted cellulose nanocrystals was examined by transmission electron microscopy (TEM) and X-Ray diffraction, respectively. Results showed that cellulose nanocrystals kept their initial morphological integrity and their native crystallinity. Nanocomposites with high content of cellulose nanocrystals were prepared using either neat cellulose nanocrystals or PCL-grafted cellulose nanocrystals and high molecular weight PCL as matrix using a casting/evaporation technique. Thermo-mechanical properties of processed nanocomposites were studied by DSC, dynamical mechanical analyses (DMA) and tensile tests. A significant improvement in terms of Young's modulus and storage modulus was obtained.

Influence of various chemical treatments on the composition and structure of hemp fibres

Abstract: The impact of several chemical treatments, including NaOH, polyethyleneimine, ethylenediaminetetraacetic acid, Ca(OH)2 and CaCl2 onto the composition and structure of hemp fibres was evaluated using differential thermal analysis, scanning electron microscopy, X-ray diffraction and Fourier transform infrared spectroscopy. Comparison of results obtained with the last two techniques allows us to quantify the impact of the chemical treatments onto the crystallinity index.

FTIR study of the sol–gel synthesis of cementitious gels: C–S–H and N–A–S–H

Abstract: The study explored the compatibility between the main product of Portland cement hydration and the main product of the alkali activation of fly ash: C–S–H and N–A–S–H gels, respectively. Both gels were synthesized with laboratory reagents at different pH values. Blends of the two were synthesized as well, using the sol–gel procedure. All the gels were characterized with Fourier transform IR spectroscopy (FTIR). The gels synthesized with this procedure were shown to precipitate together with a silica-rich gel. In addition, the pH level was found to play a determinant role in both C–S–H and N–A–S–H gel synthesis. The C–S–H gel is the major phase formed at pH > 11 and N–A–S–H gel for pH > 12. The results relating to the joint synthesis of the two (C–S–H and N–A–S–H) gels were not conclusive. Technique used for the characterization failed to differentiate between them in the blended material.

Chemical surface modifications of microfibrillated cellulose

Abstract: Microfibrillated cellulose (MFC) was prepared by disintegration of bleached softwood sulphite pulp through mechanical homogenization. The surface of the MFC was modified using different chemical treatments, using reactions both in aqueous- and organic solvents. The modified MFC was characterized with fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Epoxy functionality was introduced onto the MFC surface by oxidation with cerium (IV) followed by grafting of glycidyl methacrylate. The length of the polymer chains could be varied by regulating the amount of glycidyl methacrylate added. Positive charge was introduced to the MFC surface through grafting of hexamethylene diisocyanate, followed by reaction with the amines. Succinic and maleic acid groups could be introduced directly onto the MFC surface as a monolayer by a reaction between the corresponding anhydrides and the surface hydroxyl groups of the MFC.

The identification of hydroxyl groups on ZnO nanoparticles by infrared spectroscopy

Abstract: The interaction of water with ZnO nanoparticles has been studied by means of diffuse reflectance infrared spectroscopy (DRIFTS) and ultra-high vacuum FTIR spectroscopy (UHV-FTIRS). Exposing clean ZnO powder to water at 323 K leads to both molecular and dissociative adsorption of H2O forming a number of hydroxyl species. All the OH bands are clearly identified by the adsorption of D2O showing the expected isotopic shifts. According to the vibrational and thermal stability data obtained from single crystal surfaces, the OH species observed on ZnO nanoparticles are identified as follows: (1) OH group (3620 cm−1) on the polar O–ZnO(000) surface formed via dissociation of water on oxygen vacancy sites; (2) partial dissociation of water on the mixed-terminated ZnO(100) surface yielding coexistent H2O (∼3150 and 3687 cm−1) and OH species (3672 cm−1), where the molecularly adsorbed H2O is further identified by the characteristic scissoring mode at 1617 cm−1; (3) isolated OH species (3639 and 3656 cm−1) formed on the mixed-terminated ZnO(100) surface; (4) interaction of water with defects forming hydroxyl (or O–H⋯O) species (3564 and 3448 cm−1).

Polymorphic Transition in Disordered Poly(l-lactide) Crystals Induced by Annealing at Elevated Temperatures

Abstract: Effects of annealing conditions and molecular weight (MW) on the crystalline phase transition in poly(l-lactide) (PLLA) were studied by wide-angle X-ray diffraction (WAXD), Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC) The disordered crystal (α′-form) of PLLA was found to transform into the α one during annealing process at elevated temperatures The α′-to-α transition is quite dependent on the annealing period (ta: 0−1440 min) and annealing temperature (Ta: 120−160 °C) With increasing Ta, the polymorphic transition progresses much more rapidly The α′-to-α transition is mainly involved by the slight rearrangement of the chain conformation (especially related to the side groups) and packing manner in the unit cell to the more energy-favorable state, corresponding to the reduction of unit cell dimension Besides, it was proposed that the α′-to-α transformation mainly proceeds by the direct solid−solid transition mechanism Moreover, it was found that MW affec

Al2O3 Atomic Layer Deposition with Trimethylaluminum and Ozone Studied by in Situ Transmission FTIR Spectroscopy and Quadrupole Mass Spectrometry

Abstract: The atomic layer deposition (ALD) of Al2O3 using sequential exposures of Al(CH3)3 and O3 was studied by in situ transmission Fourier transform infrared (FTIR) spectroscopy and quadrupole mass spectrometry (QMS). The FTIR spectroscopy investigations of the surface reactions occurring during Al2O3 ALD were performed on ZrO2 particles for temperatures from 363 to 650 K. The FTIR spectra after Al(CH3)3 and ozone exposures showed that the ozone exposure removes surface AlCH3* species. The AlCH3* species were converted to AlOCH3* (methoxy), Al(OCHO)* (formate), Al(OCOOH)* (carbonate), and AlOH* (hydroxyl) species. The TMA exposure then removes these species and reestablishes the AlCH3* species. Repeating the TMA and O3 exposures in a sequential reaction sequence progressively deposited the Al2O3 ALD film as monitored by the increase in absorbance for bulk Al2O3 infrared features. The identification of formate species was confirmed by separate formaldehyde adsorption experiments. The formate species were tempera...

Synthesis, crystallization mechanism, and catalytic properties of titanium-rich TS-1 free of extraframework titanium species.

Abstract: A new route to the synthesis of TS-1 has been developed using (NH4)2CO3 as a crystallization-mediating agent. In this way, the framework Ti content can be significantly increased without forming extraframework Ti species. The prepared catalyst had a Si/Ti ratio as low as 34 in contrast to the ratio of 58 achieved with the methods A and B established by the Enichem group (Clerici, M. G.; Bellussi, G.; Romano, U. J. Catal. 1991, 129, 159) and Thangaraj and Sivasanker (Thangaraj, A.; Sivasanker, S. J. Chem. Soc., Chem. Commun. 1992, 123), respectively. The material contained less defect sites than the samples synthesized by the other two methods. As a result, it showed much higher activity for the oxidation of various organic substrates, such as linear alkanes/alkenes and alcohols, styrene, and benzene. The crystallization mechanism of TS-1 in the presence of (NH4)2CO3 was studied by following the whole crystallization process with X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), thermogravimetry/differential thermal analysis (TG/DTA), inductively coupled plasma atomic emission spectrometry (ICP), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), diffuse reflectance UV-vis spectroscopy, and (29)Si MAS (magic-angle spinning) NMR spectroscopy techniques. It was shown that the presence of (NH4)2CO3 not only drastically lowered down pH, slowing down the crystallization process and making the incorporation of Ti into the framework match well with nucleation and crystal growth, but also modified the crystallization mechanism. It seems that the solid-phase transformation mechanism predominated in the crystallization process initiated by dissociation, reorganization, and recoalescence of the solidified gel although a small amount of nongelatinated Ti shifted to the solid during the crystal growth period. In contrast, a typical homogeneous nucleation mechanism occurred in the method A system. Thus, although in the method A system most of Ti cations was inserted into the lattice after the crystallization was nearly completed, the inclusion of Ti started at the earlier nucleation period in the presence of (NH4)2CO3. This is favorable for the incorporation of Ti into the framework, resulting in a more homogeneous distribution of Ti in the framework. Oxidation of 1-hexene and 2-hexanol over the samples collected during the whole crystallization process indicated that condensation of Ti-OH and Si-OH proceeded even after the crystallization was completed. This resulted in an increase in hydrophobicity and an overall improvement in microscopic character of Ti species and consequently a great increase in the catalytic activity with further progress of crystallization.

Efficient Removal of Cr(VI) from Aqueous Solution with Fe@Fe2O3 Core−Shell Nanowires

Abstract: The batch removal of Cr(VI) from simulated wastewater with Fe@Fe2O3 core-shell nanowires (FCSNs) was investigated in this study. Itwas found that each gram of the FCSNs could remove 7.78 mg of Cr(VI) from simulated wastewater containing 8.0 mg L(-1) of Cr(VI) with an initial pH of 6.5 at room temperature. The Freundlich adsorption isotherm was applicable to describe the removal processes. Kinetics of the Cr(VI) removal was found to follow pseudo-second-order rate equation. Furthermore, the as-prepared and Cr(VI)-adsorbed FCSNs were carefully examined by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), Fourier transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopic analysis (XPS). The characterization results suggested that the adsorbed Cr(VI) was partially reduced to Cr(lll) in Cr2O3/Cr(OH)3 on the FCSNs. The possible mechanism of removal of Cr(VI) on FCSNs was proposed, which involved the dominant Cr(VI) adsorption, followed by the partial reduction of Cr(VI) to Cr(III) (chromium(III) oxyhydroides) on the surface of FCSNs. These Fe@Fe2O3 core-shell nanowires with high specific surface area and strong magnetic property are very attractive for the removal of Cr(VI) from wastewater.

Rheological and Chemical Analysis of Reverse Gelation in a Covalently Cross-Linked Diels−Alder Polymer Network

Abstract: A network polymer, incorporating dynamic and reversible cross-links, was synthesized using the Diels−Alder reaction. Fourier transform infrared (FTIR) spectroscopy was used to characterize the reaction rate and thermodynamic equilibrium over a broad temperature range. Equilibrium conversion of the furan and maleimide varied from 74% at 85 °C to 24% at 155 °C, demonstrating significant depolymerization via the retro-Diels−Alder reaction. The gel point temperature, as determined by rheometry using the Winter−Chambon criterion, was 92 °C, corresponding to a gel-point conversion of 71%, consistent with the Flory−Stockmayer equation. The scaling exponents for the complex moduli, viscosity, and plateau modulus, in the vicinity of the gel-point, were determined and compared with experimental and theoretical literature values. Further, the material exhibited a low frequency relaxation owing to dynamic rearrangement of cross-links by the Diels−Alder and retro-Diels−Alder reactions.

Hydrogen-Bonded Multilayers of a Neutral Polymer and a Polyphenol

Abstract: We report on association of tannic acid (TA) with neutral or charged polymers in solution and at surfaces and contrast hydrogen-bonded and electrostatically associated polymer/TA complexes and TA/polymer layer-by-layer (LbL) films as per their stability in the pH scale. The neutral polymers used for hydrogen bonding with TA were poly(N-vinylcaprolactam) (PVCL), poly(N-vinylpyrrolidone) (PVPON), poly(ethylene oxide) (PEO), or poly(N-isopropylacrylamide) (PNIPAM), and the polymer used to explore electrostatic binding with TA was 90% quaternized poly(4-vinylpyridine) (Q90). Association of TA with polymers in solution was explored by measuring the turbidity of solutions. At surfaces, LbL film deposition and pH stability were followed by phase-modulated ellipsometry and in-situ Fourier transform infrared spectroscopy in attenuated total reflection mode (ATR-FTIR). While electrostatically stabilized films of TA with Q90 could not be deposited at low pH values (pH = 2), hydrogen-bonded films of TA with PVCL, PVP...

Dynamic Protein−Water Relationships during β-Sheet Formation

Abstract: We investigated the polymer−water interaction in a model fibrous protein. Bombyx mori silk fibroin film, a typical model of biodegradable material, was cast from aqueous solution and analyzed in this study. Differential scanning calorimetry (DSC), its temperature-modulated variant (TMDSC), and the time-resolved technique of Fourier transform infrared spectroscopy (FTIR) were used for the first time to monitor the detailed structural changes of silk fibroin during heating and during isothermal crystallization above the glass transition temperature, Tg ∼ 451 K (178 °C). Results show that intermolecular bound water molecules, acting as a plasticizer, will strongly affect the secondary structure of silk fibroin. DSC study shows that silk fibroin initially displays a water-induced glass transition around 80 °C during heating, resulting from a temporary bound water-silk structure. Quantitative thermal analysis of the heat capacity changes of this system during heating revealed that no β-sheet crystals were form...

Self-assembly and hydrogelation of an amyloid peptide fragment.

Abstract: The self-assembly of a fragment of the amyloid beta peptide that has been shown to be critical in amyloid fibrillization has been studied in aqueous solution. There are conflicting reports in the literature on the fibrillization of Abeta (16-20), i.e., KLVFF, and our results shed light on this. In dilute solution, self-assembly of NH 2-KLVFF-COOH is strongly influenced by aromatic interactions between phenylalanine units, as revealed by UV spectroscopy and circular dichroism. Fourier transform infrared (FTIR) spectroscopy reveals beta-sheet features in spectra taken for more concentrated solutions and also dried films. X-ray diffraction and cryo-transmission electron microscopy (cryo-TEM) provide further support for beta-sheet amyloid fibril formation. A comparison of cryo-TEM images with those from conventional dried and negatively stained TEM specimens highlights the pronounced effects of sample preparation on the morphology. A comparison of FTIR data for samples in solution and dried samples also highlights the strong effect of drying on the self-assembled structure. In more concentrated phosphate-buffered saline (PBS) solution, gelation of NH 2-KLVFF-COOH is observed. This is believed to be caused by screening of the electrostatic charge on the peptide, which enables beta sheets to aggregate into a fibrillar gel network. The rheology of the hydrogel is probed, and the structure is investigated by light scattering and small-angle X-ray scattering.