Diffuse reflectance spectroscopy of powders

Diffuse reflectance (DRIFT) spectra in the mid-IR region, especially of inorganic powders, often reveal inverted or derivative-like structures (“reststrahlen” bands) which make their straightforward interpretation in terms of the Kubelka-Munk theory difficult. A simulation technique based on a combination of single scattering (Mie theory) and radiative transfer (with Kubelka-Munk as a special case) is reported that allows measured DRIFT spectra to be described without use of any free “fit” parameters. The results for silica glass microspheres and silicon carbide powder show that not specular reflectance but prominent structures in the single particle scattering cross-section are responsible for the reststrahlen features which cannot be suppressed even by diluting the powder in an excess of KBr. The efficiency of a “blocker” device in DRIFTS is also discussed.     

Surface-enhanced Raman scattering from oleate-stabilized silver colloids at a liquid/liquid interface.

Oleate-stabilized silver colloids of 5-nm-diameter were adsorbed to a toluene/water interface, and surface enhanced Raman scattering (SERS) spectra from these colloids were measured under the total internal reflection (TIR) condition. From the observed spectra, we examined the states of oleate ions and toluene molecules on silver colloids at the liquid/liquid interfacial region. The TIR-SERS spectra of oleate ions showed stronger peaks of the carboxylate group and the ethylene group than those of alkyl chains. From these results, it was found that the oleate ions were adsorbed on the silver surface in two different ways at the liquid/liquid interface; the carboxylate group adsorbed in the organic phase side, while the ethylene group adsorbed in the aqueous phase side. The shifts of the toluene in the interfacial SERS spectra were identical to those of bulk toluene, though the relative intensities among the peaks were not same. This result suggested that the toluene was adsorbed with a weak interaction, but was significantly enhanced by the local electromagnetic field at the colloid surface.     

Adsorption of polyacrylic acid on aluminium oxide: DRIFT spectroscopy and ab initio calculations

Diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy was used to study the adsorption process of the water-soluble polyacrylic acid (PAA) polymer on hydrous δ-Al₂O₃. Vibrational assignment of PAA, sodium polyacrylate, (Na–PA) and the PA-oxide surface complex was achieved by comparison of observed band position and intensity in the DRIFT spectra with wavenumbers and intensities from ab initio quantum mechanical calculations. The presented data of polyacrylic acid suggest that IR data calculated ab initio on relatively short oligomers (quantum-mechanical oligomer approach) may provide valuable information regarding the interpretation of polyelectrolyte infrared spectra. Batch adsorption experiments were performed to sorb PAA onto the δ-Al₂O₃ surface. The results obtained from DRIFT studies were compared with adsorption isotherm experiments in order to relate the level of PAA coverage to the nature of the surface complex. Ab initio molecular orbital calculations on PAA/Al₂O₃ clusters were used to model possible surface complexes. Strong correlation were found between theoretical and observed DRIFT frequencies of the antisymmetric R-COO⁻ vibration. A number of possible configurations of the polyacrylic acid/aluminate surface complex were tested via ab initio calculations. These possible configurations included different di-aluminium octahedral Al³⁺ surface models. Results obtained from adsorption isotherm experiments, DRIFT spectra and ab initio calculations indicate that the carboxylate oxygens bridge an Al³⁺-octahedral dimer [Al₂(OH)₂4(H₂O)2(OH)] in a ligand-exchange inner sphere complex.     

Surface effects in fast atom bombardment mass spectrometry of ethylene glycol-glycerol mixtures

Binary mixtures of ethylene glycols HO(CH₂CH₂O)_xH (x = 3–5) with glycerol were investigated by fast atom bombardment mass Spectrometry. The relative intensities in the ethylene glycol partial mass spectra as a function of concentration exhibit a steep slope in the low concentration range. With increasing concentration the curves asymptotically approach the 100% line. This effect increases from triethylene to pentaethylene glycol. Comparison of these results with those of surface tension measurements leads to the conclusion that the high sensitivity of fast atom bombardment mass Spectrometry for ethylene glycols is caused by the surface-active properties of these compounds, which lead to an enrichment of the surface investigated with the substance molecules.     

NMR studies of polymer solutions. II. Polyethylene

The intramolecular structure of polyethylene in solution was studied by a high-resolution nuclear magnetic resonance technique. Highly purified n-alkanes (99.5%) from C₅H₁₂ to C₃₆H₇₄ were used as its oligomers. The NMR spectra of the polyethylenes (oligomers) are very sensitive to the solvents used. The internal methylene protons of all polyethylenes of various chain length resonance at an identical frequency in carbon tetrachloride. A sharp transition in the NMR spectrum of polyethylene in α-chloronaphthalene at 35°C. was observed at n-C₁₇H₃₆, above which there exist two distinguishable NMR peaks for internal methylene protons, and below which (fewer carbons) only a single peak was seen. The NMR spectra of the internal methylene protons of the polyethylenes (oligomers) taken in benzene are very similar to those taken in pyridine. They are not as easily resolved as those NMR spectra taken in α-chloronaphthalene solutions. The effect of the size of the aromatic solvent molecule on the NMR spectra of the internal methylene protons of the polyethylenes (oligomers) in solutions was demonstrated by using aromatic solvents of various sizes, such as chlorobenzene, α-chloronaphthalene, and 9-chloronathracene. The results indicate that the formation of polymeric structure of the internal methylene groups in the polyethylene chain is very sensitive to the size of the solvent used. The interaction of the solvent with the methylene groups of the polyethylenes varies as a function of chain length; it is stronger for those low member n-alkanes and decreases gradually to an asymptotic value.     

Collision energy effects in tanden mass spectrometry as revealed by a proton-bound dimer ion

Mass spectra resulting from collision-induced decomposition of the proton-bound dimer of iso-propylamine and sec-butylamine have been obtained as a function of laboratory collision energy over the range 10-6000 eV. The ratio of the two principal fragment ions from the dimer ion measured as a function of collision energy is compared with the ratio expected as a function of internal energy as calcualted based on the statistical theory of mass spectra. This comparison indicates that the average energy deposited into the dimer ion upon collision reaches a maximum at a collision energy of ～70 eV. The average internal energy of the ions at this collision energy is ～4.3 eV. Other fragment ions which arise from higher energy decompositions are also observed in the spectra at much lower intensities. The relative intensities of these fragments indicate that the probability for large energy transfers are highest at ke V collision energies. These observations are interpreted on the basis of differences in the postcollision internal energy distributions resulting from keV and eV collisions.     

Intensities of IR stretching bands as a criterion of polarization and initial chemical activation of adsorbed molecules in acid catalysis. Ethane adsorption and dehydrogenation by zinc ions in ZnZSM-5 zeolite

A DRIFT study of ethane adsorbed by zinc cations in ZnZSM-5 prepared by chemical reaction of the hydrogen form of the zeolite with zinc vapor at 770 K, or by wet ion exchange, reveals unusual spectra of adsorbed C2H6 species. In addition to the weakly perturbed narrow bands in the region of C-H stretching vibrations, these spectra exhibit a very intense broad IR band with a frequency that is more than 200 cm(-1) lower than those of the C-H stretching vibrations of gaseous or physically adsorbed ethane. The very high relative intensity of this band indicates a very strong polarizability of the corresponding vibrational mode. It is concluded that these strongly polarized vibrations are closely connected with the subsequent heterolytic dissociation of ethane at moderately elevated temperatures, resulting in the formation of acidic hydroxyl groups and zinc ethyl fragments. At higher temperatures, the zinc ethyl fragments decomposed, resulting in the formation of zinc hydrides and ethylene. The unusual DRIFT spectrum of the molecular form of ethane adsorption by zinc cations represents a first example of anisotropy of polarizability of adsorbed molecules, which may provide a new explanation for selectivity of the acid-catalyzed reactions. In this connection, it is suggested to use the relative intensities of IR bands of adsorbed molecules as a reactivity index that is directly connected with chemical activation of adsorbed molecules via their polarization by the active sites.     

采用红外漫反射光谱研究纳米Si3N4的表面结构

采用付利叶红外漫反射光谱对激光法制取的具有不同化学组成的纳米Ｓｉ３Ｎ４粉（１５４－３０ｎｍ）的表面结构，室表面氧化及热稳定性进行了研究，结果表明新鲜的富氮粉体表面主要为硅胺基（Ｓｉ３－ｘＮＨｘ，ｘ＝１－３）结构，粉体暴露空气后硅胺基会与空气中的水分子反应形成硅醇基（ＳｉＯＨ）结构，具有不同组成的粉体随粉中氮含量的增大粒子表面硅胺基量也增加；富硅粉体表面硅胺基较少，其氧化主要为表面硅原子与空气中氧原     

Coupled calculations of vibrational frequencies and intensities. III. IR and Raman spectra of ethylene oxide and ethylene sulfide

The experimental IR and Raman spectra of ethylene oxide have been reinvestigated with particular attention to the intensities. The absolute IR intensities have been measured for the gaseous state. The spectra have been simulated by using a normal coordinate analysis coupled with a CNDO determination of the intensities. The intensity calculation using polarization functions appears to be more reliable than the standard version. Furthermore, the force field has been extended for ethylene sulfide.     

Regularity modes in Raman spectra of polyolefins: Part II. Polyethylene and ethylene copolymers

In this work, the thermal behavior of the regularity modes in Raman spectra of polyethylene with different densities and random ethylene/1-hexene copolymers with varying content of comonomer are studied. We demonstrate especially that the vibrational modes at 1062 and 2850 cm^↙1 are related to a critical sequence length of trans-conformers of 6⬜8 CH₂ groups, while the modes at 1130, 1170, 1295, and 2883 cm^↙1 indicate a critical sequence length of trans-conformers of 18 CH₂ groups. Upon increasing the 1-hexene content in the ethylene/1-hexene copolymers, the evolution of the intensities of the Raman modes at 1062, 1130, 1170, 1295, and 1417 cm^↙1, normalized to the intensity of the band at 2850 cm^↙1, is similar to the evolution of the intensities of the same modes in the Raman spectra of low density polyethylene at increasing temperature. This observation however contrasts with that in the Raman spectra of polyethylenes with middle and high densities. We suppose that these results can be explained by similarities in the structure of non-crystalline areas of low density polyethylene and the ethylene/1-hexene copolymers, which contain significant amounts of short sequences of trans-conformers.     

Solid-state C NMR and SAXS characterization of the amorphous phase in low-molecular weight poly(ethylene oxide)s

Low-molecular weight poly(ethylene oxide)s (PEO) with extended, once or twice folded chains (as characterized by SAXS), were investigated by solid-state ¹³C NMR spectra measured under conditions to detect only the signal of the narrow line component. The direct detection and integrated intensities of the signals from hydroxy-terminated chain-end units in these spectra confirm that the narrow line component corresponds to the noncrystalline (amorphous) phase. The NMR line of PEO carbons adjacent to the hydroxy end-groups was used as an intensity standard to obtain information on the mean number of carbons per chain contributing to the amorphous phase. Assuming that amorphous phase is formed by chain ends (cilia) and folds it follows from the spectra that the length of folds is 6-7 monomer units; cilia are 2-3 monomer units long.     

Carbon-13 nuclear magnetic resonance of ethylene–propylene copolymer and the determination of sequence distribution of monomeric units

The ¹³C-NMR spectra of ethylene–propylene copolymers and their model compounds were measured at 15.1 MHz. Assignments of the signals were carried out by using the equation of Grant and Paul and also by comparing the spectra with those of squalane, hydrogenated natural rubber, polyethylene, and atactic polypropylene. The accuracy and the precision of intensity measurements, that is, the deviation from the theoretical values and the scatter of the measurements, respectively, were checked for the spectra of squalane and hydrogenated natural rubber and were shown to be at most 12% for each of the signals. On the basis of these results the mole fractions of the four types of the dyad sequences, that is, the propylene–propylene (head-to-tail and head-to-head), the ethylene–propylene, and the ethylene–ethylene sequences, were determined together with the average sequence lengths of both monomer units.     

Quantitative small-angle light scattering studies of the melting of poly(ethylene terephthalate)

Quantitative H_v small-angle light-scattering (SALS) studies of the melting of poly(ethylene terephthalate) (PET) have been performed. The results are compared with those from differential scanning calorimetry (DSC). It is found that fully grown spherulites melt over a temperature range of about 20°C without change in spherulite size, number, or internal disorder. The decrease in H_v SALS intensity is due to a decrease in spherulitic crystallinity over the melting range. The corrected experimental intensities are lower than, but in reasonable agreement with, the theoretically predicted intensities based on the DSC results. Procedures are presented for the quantitative analysis of H_v SALS intensities from spherulitic systems, including the corrections for the experimental, external disorder, and internal disorder effects.     

Copolymerization of ethylene with cyclopentene or 2‐butene with half titanocenes‐based catalysts

Half titanocenes (CpCH₂CH₂O)TiCl₂ (1), (CpCH₂CH₂OCH₃)TiCl₃ (2), and CpTiCl₃ (3), activated by methylaluminoxane (MAO) were tested in copolymerization of ethylene with internal olefins such as cyclopentene. All the catalysts were able to give incorporation of cyclopentene in polyethylene matrix. ¹³C NMR analysis of obtained copolymers showed that the catalytic systems have low regiospecificity. In fact, in ethylene–cyclopentene copolymers, cyclic olefin inserts with both 1,2 and 1,3‐enchainment. X‐ray powder diffraction analysis of these copolymers confirmed that 1,2 inserted cyclopentene units are excluded from crystalline phase, whereas 1,3‐cyclopentene units are included, giving rise to expansion of unit cell of crystalline polyethylene. Titanium‐based catalysts were investigated also in the copolymerization of ethylene with E and Z‐2‐butene. Only complex (1) was able to give copolymers and ¹³C NMR analysis of products showed 2‐3, 1‐3, and 1‐2 insertion of 2‐butene. Differential scanning calorimetry analysis displayed that ethylene–cyclopentene, as well as ethylene‐2‐butene, copolymers are crystalline and their melting point decreases by increasing the comonomer content. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4725–4733, 2008     

Reactive compatibilization of polyolefin/PET blends by melt grafting with glycidyl methacrylate

The melt free radical grafting of glycidyl methacrylate (GMA) onto high‐density polyethylene (HDPE) was carried out in Brabender internal mixer. The GMA content of the grafted HDPE (HDPE‐g‐GMA) was determined through FTIR by means of a calibration curve. The influence of reaction procedure, radical initiator concentration and addition of a co‐monomer (styrene) on the grafting efficiency was examined. Blends of poly(ethylene terephthalate) (PET) with HDPE and HDPE‐g‐GMA (75/25 w/w) were prepared by melt mixing in internal mixer. The morphology of the blends was then analysed by SEM microscopy. PET/HDPE‐g‐GMA blends displayed improved phase dispersion and interfacial adhesion as compared to unfanctionalized PET/HDPE blend.     

Grafting of polycaprolactone onto poly(ethylene‐co‐vinyl alcohol) and application to polyethylene‐based bioerodable blends

Poly(ethylene‐co‐vinyl acetate) (EVA) powders containing 10 and 20 wt % of vinyl acetate (VAc) units was saponified in ethanol/KOH solution in a heterogeneous manner. Intermolecular interaction between vinyl alcohol(VOH) units in the produced poly(ethylene‐co‐vinyl alcohol) (EVOH) promoted the crystallization of intervening segments composed of ethylene units. Ring opening polymerization of caprolactone (CL) in the presence of EVOH gave EVOH‐g‐PCL graft copolymers with relatively short chain branches. Even though the graft copolymerization was carried out in a homogeneous solution, all the VOH units were not equally reactive for the PCL grafting. And the unreacted VOH units decreased very slowly with the graft copolymerization time. EVOH‐g‐PCL decreased the domain size of the dispersed phase in low density polyethylene (PE)/biodegradable master batch (MB) blends, and thus increased their tensile properties significantly. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2561–2569, 2002     

Variations in the chemical composition within pine (Pinus sylvestris) trunks determined by diffuse reflectance infrared spectroscopy and chemometrics

The feasibility of using DRIFT (diffuse reflectance infrared Fourier transform) spectroscopy combined with a multivariate analysis method (a PLS (projection to latent structures), regression) for predicting the distribution of the main organic constituents (cellulose, glucomannan, xylan, lignin, and extractives) within the Scots pine (Pinus sylvestris) stemwood was examined. PLS calibrations were carried out to establish a mathematical correlation between the data sets of conventional (“wet-chemistry-based”) wood analysis and the DRIFT spectra of the corresponding wood samples. Based on this approach, different surface maps on variations in the content of the main organic constituents within the stemwood matrix were shown.     

Vibrational Spectra and Ion-Pair Properties of Lithium Hexafluorophosphate in Ethylene Carbonate Based Mixed-Solvent Systems for Lithium Batteries

The vibrational spectra of LiPF₆ 1M solutions formed in aprotic mixed solventsobtained by mixing ethylene carbonate with dimethyl carbonate and diethylcarbonate are discussed. The Raman and infrared spectra of lithium hexafluorophosphate(LiPF₆) and the quantum chemical computations of the vibrationalwavenumbers and intensities are reported. Due to the nature of the solutions,attenuated total internal reflectance spectroscopy was used to obtain the infraredspectra. The infrared active vibrational fundamentals of PF₆ ^– provided evidencefor the anion—solvent interaction as well as ion-pair formation. Similarly, theinfrared active modes of the solvent showed significant changes due to thecation—solvent interaction. The computations of the most energetically favorablegeometry in the formation of the Li⁺ PF₆ ion pair are also presented. Conductivitymeasurements carried out for the 1M solutions scanning a wide temperatureinterval (–30 to + 60 °C) confirm the viability of these electrolytes forpractical applications.     

Universal method for the determination of nonionic surfactant content in the presence of protein

A new analytical method has been developed for the quantitative determination of ethylene glycol‐containing nonionic surfactants, such as polyethylene glycol 8000, polysorbate 80, and Pluronic F‐68. These surfactants are commonly used in pharmaceutical protein preparations, thus, testing in the presence of protein is required. This method is based on the capillary gas chromatographic analysis of ethylene glycol diacetate formed by hydrolysis and acetylation of surfactants that contain ethylene glycol. Protein samples containing free surfactants were hydrolyzed and acetylated with acetic anhydride in the presence of p‐toluene sulfonic acid. Acetylated ethylene glycol was extracted with dichloromethane and analyzed by gas chromatography using a flame ionization detector. The amount of nonionic surfactant in the sample was determined by comparing the released ethylene glycol diacetate signal to that measured from calibration standards. The limits of quantitation of the method were 5.0 μg/mL for polyethylene glycol 8000 and Pluronic F‐68, and 50 μg/mL for polysorbate 80. This method can be applied to determine the polyethylene glycol content in PEGylated proteins or the final concentration of polysorbate 80 in a protein drug in a quality control environment.     

Etude par RMN 13C à 62,89 MHz des branchements éthyles dans les copolymères ethylène-butène et polyéthylène basse densité

Carbon 13 nuclear magnetic resonance spectra (at 62,89 MHz) were obtained for a series of branched heavy alcanes (12-ethyl tricosane, 11,20-diethyl tricontane, 11,18-diethyl octacosane, 11,17-diethyl heptacosane, 11,16-diethyl hexacosane, 9,12-diethyl heneicosane, 5,7-diethyl docosane, 6,7-diethyl docosane, 2 éthyl-hexyl-12 tricosane), which provide a model set for describing the ethyl branched sequences in ethylene butene copolymers and low-density polyethylene (LDPE). For ethylene-butene copolymers we do not detect any head-to-head polymerization of butene as reported recently (the existence of a 1,2-ethyl pair has not been confirmed by the low-field signal at 41,3 ppm), but only isolated ethyl and 1-3-diethyl branches. The three peaks observed in the methyl region (broad signal) of the spectrum are assigned to butene centered triads, as opposed to branches in positions having different tacticities as reported earlier. Carbon 13 nuclear magnetic resonance spectra of high-pressure polymerized low-density polyethylene have been measured at 62,89 MHz. On the basis of Willbourn's double back biting mechanism, two kinds of complex branches, the 1,3-ethyl pair and 2-ethyl-hexyl, have been assigned. Finally, these results suggest that the ethyl branches in low-density polyethylene are not isolated branches.