Crystallinity of cellulose,as determined by CP/MAS NMR and XRD methods

Summary The crystallinity of six cellulose samples with different origin and treatment was determined using x-ray diffraction (XDR) and nuclear magnetic resonance with cross polarization and magic angle sample spinning (CP/MAS NMR) methods. The numerical results for crystallinity obtained by using curve fitting methods in both cases correlated very well. It was concluded that the values for the crystallinity can be determined from NMR spectra when CP times not exceeding 0.5 ms are used. The range of order of the samples was further characterized calculating the radial atomic density function from the x-ray diffraction patterns and determining the greatest distances with significant deviations from the average density.On leave from Institute of Chemical Physics and Biophysics, Estonian Academy of Sciences, SU-200105 Tallinn, USSR     

Characterization of gas hydrates with PXRD, DSC, NMR, and Raman spectroscopy

Structure I (sI) and H (sH) hydrates containing methane were synthesized and characterized with PXRD, DSC, NMR, and Raman spectroscopy. Three well-known large molecule guest substances (LMGSs) were selected as sH hydrate formers: 2,2-dimetylbutane (NH), methylcyclohexane (MCH), and tert-butyl methyl ether (TBME). The solid phase analysis confirmed the presence of sH hydrate whenever a LMGS was present. The presence of a non-hydrate former (n-heptane) did not affect the methane hydrate structure or cage occupancies. Ice to hydrate conversion was limited when the LMGS amount was less than stoichiometric and synthesized at low methane pressure, but nearly complete conversion was achieved with temperature ramping and excess LMGS. The methane occupancies were found to depend on the type of LMGS and increased with pressure. The hydrate with TBME was found to have the smallest methane content followed by the hydrates with NH and MCH. Both NMR and Raman identified methane and LMGS signals from the hydrate phase, however, the cage occupancy values of sH hydrate can only be obtained from NMR spectroscopy. The hydrate structures, ice to hydrate conversion, gas content in hydrate and cage occupancy from the various measurements are consistent with each other.     

XRD, EDX and IR analysis of solid solutions between thaumasite and ettringite

Solid solutions between thaumasite and ettringite were prepared by methods analogous to those well established for the preparation of thaumasite and ettringite. The extent of immiscibility in this system is investigated by varying the Al:Si and SO₄²⁻:CO₃²⁻ ratios in reactant mixtures. The solids produced were analysed by quantitative X-ray diffraction, with Rietveld refinement also providing accurate unit cell dimensions, energy-dispersive X-ray analysis and infrared spectroscopy. The compositional and unit cell variations in the solid solution are discussed. A wide variety of solid solution compositions were produced with both the thaumasite and ettringite structures, but all preparations were considerably diluted by secondary amorphous products.     

Characterization of Acid-Neutralizing Basic Monomers in Co-Solvent Systems by NMR

Metabolic activity of the oral microbiota leads to acidification of the microenvironment and promotes demineralization of tooth structure at the margin of composite restorations. The pathogenic impact of the biofilm at the margin of the composite restoration could be reduced by engineering novel dentin adhesives that neutralize the acidic microenvironment. Integrating basic moieties into methacrylate derivatives has the potential to buffer against acid-induced degradation, and we are investigating basic monomers for this purpose. These monomers must be compatible with existing formulations, which are hydrophobic and marginally miscible with water. As such, co-solvent systems may be required to enable analysis of monomer function and chemical properties. Here the authors present an approach for examining the neutralizing capacity of basic methacrylate monomers in a water/ethanol co-solvent system using nuclear magnetic resonance (NMR) spectroscopy. NMR is an excellent tool for monitoring the impact of co-solvent effects on pKa and buffering capacity of basic monomers because chemical shift is extremely sensitive to small changes that most other methods cannot detect. Because lactic acid (LA) is produced by oral bacteria and is prevalent in this microenvironment, it was used to analyze the effectiveness of basic monomers to neutralize acid. The ¹³C chemical shift of the carbonyl in LA was monitored as a function of ethanol and monomer concentration and each was correlated with pH to determine the functional buffering range. This study shows that the buffering capacity of even very poorly water-soluble monomers can be analyzed using NMR.     

The role of Al in C-S-H: NMR, XRD, and compositional results for precipitated samples

X-ray diffraction, compositional analysis, and ²⁹Si and ²⁷Al MAS NMR spectroscopy of Al-substituted tobermorite-type C-S-H made by precipitation from solution provide significant new insight into the structural mechanisms of Al-substitution in this important and complicated phase. Al occurs in 4-, 5-, and 6-coordination (Al[4], Al[5], and Al[6]) and plays multiple structural roles. Al[4] occurs on the bridging tetrahedra of the drierkette Al-silicate chains, and Al[5] and Al[6] occur in the interlayer and perhaps on particle surfaces. Al does not enter either the central Ca-O sheet or the pairing tetrahedra of the tobermorite-type layers. Al[4] occurs on three types of bridging sites, Q³ sites that bridge across the interlayer; Q² sites that are charge balanced by interlayer Ca⁺², Na⁺, or H⁺; and Q² sites that are most likely charge balanced by interlayer or surface Al[5] and Al[6] through Al[4]-O-Al[5,6] linkages. Although the data presented here are for relatively well-crystallized tobermorite-type C-S-H with C/S ratios ≤ 1.2, comparable spectral features for hydrated white cement pastes in previously published papers[30], [31] and [32] [M.D. Andersen, H.J. Jakobsen, J. Skibsted, Incorporation of aluminum in the calcium silicate hydrate (C-S-H) of hydrated Portland cements: a high-field ²⁷Al and ²⁹Si MAS NMR investigation Inorg. Chem. 42 (2003) 2280-2287; M.D. Andersen, H.J. Jakobsen, J. Skibsted, Characterization of white Portland cement hydration and the C-S-H structure in the presence of sodium aliminate by ²⁷Al and ²⁹Si MAS NMR spectroscopy, Cem. Concr. Res. 43 (2004) 857-868; M.D. Andersen, H. J. Jakobsen, J. Skibsted, A new aluminum-hydrate phase in hydrated Portland cements characterized by ²⁷Al and ²⁹Si MAS NMR spectroscopy, Cem. Concr. Res., submitted for publication.] indicate the presence of similar structural environments in the C-S-H of such pastes, and by implication OPC pastes.     

疏水性电荷诱导层析——原理、性能及其应用

介绍了疏水性电荷诱导层析(hydrophobic charge induction chromatography,HCIC)的原理及特点:其功能基团结合了疏水作用和静电相互作用,是一种混合型的双模式层析方法。由于HCIC在蛋白质(特别是抗体)的分离纯化中表现出操作简便、选择性较好等优点,受到了学术界和工业界的关注。对HCIC的技术原理、发展历程、层析行为以及应用现状等进行综述,以期对HCIC的深入研究和应用开发提供指导。     

EPA—E标样的UV、IR、NMR、MS分析

本文测定了EPA－E的UV、IR、NMR、MS谱,并对其谱图进行了解析,确证了EPA－E标样的化学结构。     

Characterization and free radical polymerization of liquid crystalline acrylic acid/cellulose diacetate and N-vinyl-2-pyrrolidinone/cellulose diacetate solutions

Polymerizations of liquid crystalline solutions of cellulose diacetate (CDA) in acrylic acid (AA) and N-vinyl-2-pyrrolidinone (NVP) were conducted in an attempt to prepare molecular composites (polymer blends) processing a rigid rod polymer with liquid crystalline orientation. CDA was found to form liquid crystalline solutions in both AA and NVP at concentrations avove 40 wt% CDA. Polymerization of anisotropic 50 wt% CDA-AA and CDA-NVP solutions occurred with considerable retention of the starting solution anisotropy and yielded homogeneous blends (1 T_g) when the rate of polymerization was fast relative to the phase separation of the free radically polymerizing AA or NVP with CDA. Slow polymerizations lead to phase separated blends (2 T_g).     

UV, Raman and XRD study of polymorphism of poly(methyl-n-propylsilane)

Raman, UV and XRD studies have been performed to characterize the structures of differently prepared samples of poly(methyl-n-propylsilane). The results demonstrate polymorphism of this polymer between T_c and T_g. At room temperature the polymer can exist in up to four modifications which comprise one amorphous disordered phase and three more ordered modifications, differing in the interchain organization and in the silicon backbone conformations. The latter are considered to be deviant, transoid and all-anti, respectively. The number of the modifications present and relative amount of each strongly depends on the preparation method and thermal history of the sample as well as on the molecular weight.     

XANES, Raman and XRD study of anthracene-based cokes and saccharose-based chars submitted to high-temperature pyrolysis

Graphitizing anthracene-based cokes and non-graphitizing saccharose-based chars were processed at temperatures from 450 °C to 2900 °C at ambient pressure. This offers a whole set of samples that greatly differ in structure. Here, their structural evolution was monitored by combining XRD and visible (green) Raman spectroscopy as well as, for the first time, near-infrared Raman and synchrotron-based C-XANES spectroscopies. These different techniques provide complementary information especially regarding the spatial resolution they achieved. However, despite its importance, the quantitative comparison between the structural parameters extracted from these techniques is difficult. Based on a new signal deconvolution procedure to extract quantitative structural information from C-XANES data and the achievement of a new dataset on a complete series of graphitization, the reliability and the precision of the information which can be retrieved from each technique are discussed. C-XANES spectroscopy appears to provide reliable proxies for the extent of aromatic layers of graphitic compounds and an empirical calibration is proposed.     

Nitridation of silicon powder studied by XRD, Si MAS NMR and surface analysis techniques

The nitridation of elemental silicon powder at 900–1475 °C was studied by X-ray photoelectron spectroscopy (XPS), X-ray excited Auger electron spectroscopy (XAES), XRD, thermal analysis and ²⁹Si MAS NMR. An initial mass gain of about 12% at 1250–1300 °C corresponds to the formation of a product layer about 0·2 μm thick (assuming spherical particles). XPS and XAES show that in this temperature range, the surface atomic ratio of N/Si increases and the ratio O/Si decreases as the surface layer is converted to Si₂N₂O. XRD shows that above 1300 °C the Si is rapidly converted to a mixture of - and β-Si₃N₄, the latter predominating >1400 °C. In this temperature range there are only slight changes in the composition of the surface material, which at the higher temperatures regains a small amount of an oxidised surface layer. By contrast, in the interval 1400–1475 °C, the ²⁹Si MAS NMR chemical shift of the elemental Si changes progressively from about −80 ppm to −70 ppm, in tandem with the growth of the Si₃N₄ resonance at about −48 ppm. Possible reasons for this previously unreported change in the Si chemical shift are discussed. ©     

Hydration products in sulfoaluminate cements: Evaluation of amorphous phases by XRD/solid-state NMR

The hydration of four sulfoaluminate cements have been studied: three sulfoaluminate systems, having different content of sulfate and silicate, and one blend Portland-CSA-calcium sulfate binder. Hydration was followed up to 90 days by means of a combination of X-ray diffraction and solid state MAS-NMR; Differential scanning calorimetry and Scanning electron microscopy were also performed in order to help the interpretation of experimental data. High amount of amorphous phases were found in all the four systems: in low-sulfate cements, amorphous part is mainly ascribed to monosulfate and aluminium hydroxide, while strätlingite is observed if belite is present in the cement; in the blend system, C-S-H contributes to the amorphous phase beyond monosulfate.     

Micro-Raman imaging of heterogeneous polymer systems: General applications and limitations

This article assesses the use of micro-Raman imaging with respect to polymer science. This relatively novel technique allows, at high spatial resolution, the acquisition of chemical and morphological information over an area of a sample. Using Raman imaging by confocal laser line scanning, a wide range of problems in polymer analysis has been studied to outline the capabilities and limitations of the technique. Three ternary polymer blends consisting of polypropene/polyethene/ethene-propene copolymer, polybutyleneterephthalate/polycarbonate/very low density polyethene, and styrene-co-acrylonitrile/styrene-co-maleicanhydrate/poly-2,6-dimethylphenylene oxide were studied with regard to compositional and morphological heterogeneities. In a binary polymer blend consisting of two different acrylate monomers, the refractive index profile established after artificially induced diffusion of the main components was determined from the concentration gradients. The distribution of unreacted free melamine in a cured melamine-formaldehyde resin was analyzed. Furthermore, the general structure of a composite sample consisting of polyethene fibers in an epoxide matrix was studied. Raman imaging proved suitable for the characterization of heterogeneities in composition and morphology on a size scale equal to or larger than 1 μm. In this sense, the technique helps to close the gap between infrared microscopy, with its comparatively poor spatial resolution, on the one hand, and transmission electron microscopy, with its limited chemical information, on the other hand. For heterogeneities on a submicron scale, the value of the technique is limited to the determination of average information. When combined with curve fitting, Raman imaging permitted us to determine the composition of the polypropene/polyethene/ethene-propene copolymer blend with an accuracy of 5–10%. The main limitations to micro-Raman imaging of polymer systems based on the confocal laser line scanning technique have been identified as the destruction of the samples due to insufficient heat dissipation of the high-incident laser power, interferences due to fluorescence, and the stability of the instrumentation during long collection times required for good signal-to-noise ratio spectra of weak Raman scatterers. © 1996 John Wiley & Sons, Inc.     

Elucidation of the interaction among cellulose,xylan, and lignin in steam gasification of woody biomass

The reaction mechanism for gas and tar evolution in the steam gasification of cellulose, lignin, xylan, and real biomass (pulverized eucalyptus) was investigated with a continuous cross‐flow moving bed type differential reactor, in which tar and gases can be fractionated according to reaction time. In the steam gasification of real biomass, the evolution rates of water‐soluble tar (derived from cellulose and hemicelluloses) and water‐insoluble tar (derived from lignin) decrease with increasing reaction time. It was found that the evolution of water‐soluble tar occurs earlier than in the gasification of pure cellulose, indicating an interaction of the three components. The predicted yield of water‐insoluble tar is substantially less than that of real biomass. This implies that the evolution of tar from the lignin component of biomass is enhanced, compared with pure lignin gasification, by other components. The gas evolution rate from real biomass is similar to that predicted by the superposition of cellulose, lignin, and xylan. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

Structure of the silver containing diamond like carbon films: Study by multiwavelength Raman spectroscopy and XRD

In the present study structure of silver containing diamond like carbon (DLC:Ag) films deposited by reactive magnetron sputtering was investigated by X-ray diffractometry (XRD) and multiwavelength Raman spectroscopy. In the case of the DLC:Ag films containing low amount of silver, crystalline silver oxide prevails over silver. While at higher Ag atomic concentrations formation of the silver crystallites of the different orientations was observed. Surface enhanced Raman scattering (SERS) effect was detected for high Ag content in the films. For UV excited Raman spectra sp³ bonded carbon related Raman scattering T peak at ~ 1060 cm^− 1 was detected only for the films with the highest amount of silver (34.3 at.%). The dependence of the Raman scattering spectra parameters such as position of the G peak, G peak full width at half maximum (FWHM(G)), D/G peak area ratio on Ag atomic concentration in DLC:Ag film as well as Raman scattering spectra excitation wavelength were studied. The dependence on Ag amount in film was more pronounced in the case of the Raman scattering spectra excited by higher wavelength laser beam, while in the case of the spectra excited by 325 nm and 442 nm laser beams only weak dependence (or no dependence) was observed. Overall tendency of the decrease of the dispersion of the G peak with the increase of Ag atomic concentration was found. Thus sp³/sp² bond ratio in DLC:Ag film decreased with the increase of Ag atomic concentration in the films.     

Preparation,IR, UV,NMR, and Mass Spectral Fragmentations of New Substituted Phenoxaphosphinic Acids

The synthesis and IR, UV, NMR; and mass spectral fragmentations of substituted phenoxaphosphinic acids I – XIV are reported. A diazo method gave I, and the Friedel-Crafts method II – XIV. Infrared assignments: POH, broad bands, 2600, 2250, and 1650; C-P, 1490 - 1440; C-O, 1280 - 1260; P=0, 1190 - 1140; and P-O, 978 - 974 cm^?1. Characteristic bands also occur at 1330 - 1320 and 1230 - 1210 cm^?1. The UV spectra possess maxima at 210 - 220 mμ (log ∈ 4.50 - 4.60), 240 - 250 (4.20 - 4.30), and 298 – 304 (3.65 – 3.75). The NMR spectra give τ 7.56 ppm for a 2-methyl substituent, 7.48 for a 4-methyl and a quartet at 7.26 and a triplet at 8.71 (J = 7.7 Hz) for a 2-ethyl. The chemical shifts were virtually unaffected by alkyl or halogen substituents on the other aromatic ring but were shifted upfield by ortho or meta methyl substituents on the same ring. Singlets at τ 7.44 and 7.60 ppm in the spectrum of VIII gave calculated base values of about 7.28 and 7.44 for a 1-methyl and 3-methyl, respectively. The mass spectra are greatly influenced by the substituents. All showed loss of PO₂H from the molecular ion or in the case of ethyl compounds after CH₃^· expulsion. CHO or CCIO was then eliminated. The molecular ions of methyl compounds eliminated H₂O.     

Molecular weight decrease in the early pyrolysis of crystalline and amorphous cellulose

Samples of ordinary “ash-free” cellulose papers and similar samples decrystallized by swelling in liquid ammonia were pyrolyzed in vacuo to a weight loss ranging from <0.1% to nearly 20%. The samples were then nitrated and their molecular weight distributions determined by gel permeation chromatography. When weight loss reached 1%, both the ordinary and the ammonia-swelled celluloses showed a large drop in average degree of polymerization (D.P.). However, the ordinary cellulose showed this sharp drop long before there was any measurable weight loss; the ammonia-swelled cellulose changed D.P. only gradually in the early stages. Further, x-ray diffraction measurements showed that by the time the D.P. of the ammonia-swelled cellulose had dropped appreciably, the material had developed a significant crystalline pattern. These results support the suggestion that initial rupture of the cellulose molecule occurs at strain points at the crystalline–amorphous boundaries.     

Basic trends in technology of manufacturing cellulose films and casings

Basic directions of work in the region of manufacturing cellulose films and casings have been defined:

Effect of cellulose, lignin, alkali and alkaline earth metallic species on biomass pyrolysis and gasification

Fundamental pyrolysis/gasification characteristics of natural biomass and acid-washed biomass without alkali and alkaline earth metals (AAEM) were investigated by a thermogravimetric analyzer (TGA) and a fixed-bed reactor. In these experiments, six types of biomass were used and the contents of cellulose, lignin and AAEM species in the biomass were measured. It was observed that the characteristic of biomass pyrolysis and gasification was dependent on its components and AAEM species on the basis of TGA experiments. During biomass pyrolysis, the tar and gas yields increased with the growth of cellulose content, but the char yield decreased. There were two reactions indicating two major decomposition mechanisms. The first stage of decomposition showed rapid mass decrease due to the volatilization of cellulose, while the second stage became slow attributed to the lignin decomposition. The higher the cellulose content, the faster the pyrolysis rate. In contrast, the pyrolysis rate of biomass with higher lignin content became slower. In addition, the rises of cellulose content elevated the peak temperature of gasification and prolonged the gasification time. Meanwhile, the effect of AAEM species on gasification behavior was studied by comparing unwashed and acid-washed biomass. AAEM species increased the peak gasification value, whereas decreased initial gasification temperature. It revealed that the activity of biomass gasification was attributed to the interaction between AAEM-cellulose/lignin.     

Synthesis and spectroscopic analysis of cellulose sulfates with regulable total degrees of substitution and sulfation patterns via C NMR and FT Raman spectroscopy

Synthesis and spectroscopic characterisation of cellulose sulfate (CS) were reported. Various CS exhibiting diverse degrees of sulfation (DS_S) were prepared through acetosulfation or direct sulfation of cellulose. During the acetosulfation, intermediate product - cellulose acetate sulfate (CAS) - was formed after the comparative esterification and subsequent deacetylation of CAS led to CS. The direct sulfation proceeded quasi-homogeneously and heterogeneously in N,N-dimethylformamide (DMF) or homogeneously in N,N-dimethylacetamide (DMAc)/LiCl mixture. The total DS_S between 0.21-2.59 and partial DS_S6 as well as DS_S2 of up to 1 were determined via elemental analysis and ¹³C NMR spectroscopy. Besides, solid-state CP/MAS ¹³C NMR could characterise CS regarding the sulfation. Subsequently, FT Raman investigation of obtained CS was conducted with the aim to establish analysis methods quantifying the total DS_S. The intensities of Raman bands ascribed to the vibrations of OSO and C-O-S groups were used as analysis parameters, yielding calibration curves with high correlation coefficients of more than 0.96.