Phase transformations in microcrystalline cellulose due to partial dissolution

All-cellulose composites were prepared by partly dissolving microcrystalline cellulose (MCC) in an 8.0 wt% LiCl/DMAc solution, then regenerating the dissolved portion. Wide-angle X-ray scattering (WAXS) and solid-state ¹³C NMR spectra were used to characterize molecular packing. The MCC was transformed to relatively slender crystallites of cellulose I in a matrix of paracrystalline and amorphous cellulose. Paracrystalline cellulose was distinguished from amorphous cellulose by a displaced and relatively narrow WAXS peak, by a 4 ppm displacement of the C-4 ¹³C NMR peak, and by values of T₂(H) closer to those for crystalline cellulose than disordered polysaccharides. Cellulose II was not formed in any of the composites studied. The ratio of cellulose to solvent was varied, with greatest consequent transformation observed for c < 15%, where c is the weight of cellulose expressed as % of the total weight of cellulose, LiCl and DMAc. The dissolution time was varied between 1 h and 48 h, with only small additional changes achieved by extension beyond 4 h.     

钾元素对生物质及其三组分热解的影响

采用机械混合法将KCl加入到纤维素、半纤维素、木质素以及稻壳和稻壳模拟物等生物质中,得到了一系列不同K含量的生物质样品,通过热重(TG)实验考察了K元素对生物质热解特性的影响.结果表明,K元素对生物质三组分热解特性的影响比较复杂,纤维素的最大热解失重速率随着KCl添加量的增加而降低,但KCl对半纤维素和木质素热解特性的影响不显著.无论是否添加KCl,模拟生物质的热解特性均可以认为是三组分热解的简单叠加.但酸预处理稻壳三组分间的稳定结构,导致其DTG曲线在300 ℃左右的热解峰由稻壳模拟物的尖峰变为肩峰,其热解焦炭收率也比稻壳模拟物的略低.此外,实验还采用浸渍法向酸预处理稻壳中添加了KCl.TG实验结果表明,K元素的存在对生物质热解具有一定的催化作用,但KCl的添加方式不同,生物质的热解特性有明显差别,生物质样品经机械混合添加KCl后,其热解焦炭收率呈下降趋势(纤维素除外),浸渍法添加的KCl导致酸预处理稻壳的最大热解失重速率和焦炭收率升高.     

Efficient hydrolyzation of cellulose in ionic liquid by novel sulfonated biomass-based catalysts

A green and effective approach for comprehensive hydrolyzation of cellulose has been described. Several carbon-based solid acids were successfully prepared using various biomass (glucose, microcrystalline cellulose, bamboo, and rice husk) and used to catalyze cellulose hydrolysis. The acid groups (–SO₃H and –COOH) were successfully introduced onto the surface of the carbon-based solid acid catalysts as evidenced by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The structure of the prepared catalysts was characterized by scanning electron microscope and X-ray diffraction. The catalysts showed excellent catalytic performance for hydrolysis of cellulose. To improve the reaction efficiency, ball-milling and solubilization in ionic liquids of cellulose were adopted. A maximum total reducing sugar yield of 81.8 % was obtained in ionic liquid 1-butyl-3-methyl imidazolium chloride at 125 °C for 90 min when the water addition was 10 % of ionic liquid. This study provided a promising strategy to synthesize solid acids from lignocelluloses, which were further used to convert biomass into biofuels and platform chemicals.     

Novel Foaming-Agent Free Insulating Geopolymer Based on Industrial Fly Ash and Rice Husk

This study highlights the synthesis of a new thermal insulating geopolymer based on the alkaline activation of fly ashes. A porous geopolymer material can be prepared without the addition of a foaming agent, using high ratio solution/ashes (activating solutions used are water, sodium or potassium hydroxide). In order to increase the porosity of the material and to make it more ecological, rice husks are incorporated into the formulation. The geopolymer materials were prepared at room temperature and dried at moderate temperature (105 °C) by a simple procedure. The microstructural characteristics of these new porous geopolymers were assessed by optical microscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA) and X-ray fluorescence (XRF). Infrared spectroscopy (FTIR) was used to confirm the geopolymerisation. The effect of the ratio solution/ashes and the percentage of the rice husk addition on thermal and mechanical analysis was evaluated. An insulating material for a solution/ashes ratio of 0.9 and a rice husk content of 15% having a λ value of 0.087 W/(m·K), a porosity of 61.4% and an Rc value of 0.1 MPa was successfully prepared.     

Microfibril diameter in celery collenchyma cellulose: X-ray scattering and NMR evidence

Cellulose isolated from celery collenchyma is typical of the low-crystallinity celluloses that can be isolated from primary cell-walls of higher plants, except that it is oriented with high uniformity. The diameter of the microfibrils of celery collenchyma cellulose was estimated by three separate approaches: ¹³C NMR measurement of the ratio of surface to interior chains; estimation of the dimensions of the crystalline lattice from wide angle X-ray scattering (WAXS) measurements using the Scherrer equation; and the observation that microfibrils of this form of cellulose have the unusual property of packing into an irregular array from which small angle X-ray scattering (SAXS) shows features of both form and interference functions. The interference function contributing to the SAXS pattern implied a mean microfibril centre-to-centre distance of 3.6 nm, providing an upper limit for the diameter. However modelling of the scattering pattern from an irregular array of microfibrils showed that the observed scattering curve could be matched at a range of diameters down to 2.4 nm, with the intervening space more or less sparsely occupied by hemicellulose chains. The lateral extent of the crystalline lattice normal to the 200 plane was estimated as a minimum of 2.4 nm by WAXS through the Scherrer equation, and a diameter of 2.6 nm was implied by the surface: volume ratio determined by ¹³C NMR. The WAXS and NMR measurements both depended on the assumption that the surface chains were positioned within an extension of the crystalline lattice. The reliability of this assumption is uncertain. If the surface chains deviated from the lattice, both the WAXS and the NMR data would imply larger microfibril diameters within the range consistent with the SAXS pattern. The evidence presented is therefore all consistent with microfibril diameters from about 2.4 to 3.6 nm, larger than has previously been suggested for primary-wall cellulose. Some degree of aggregation may have occurred during the isolation of the cellulose, but the larger microfibril diameters within the range proposed are a consequence of the novel interpretation of the experimental data from WAXS and NMR and are consistent with previously published data if these are similarly interpreted.     

Structure of cellulose and microcrystalline cellulose from various wood species, cotton and flax studied by X-ray scattering

The structure of microcrystalline cellulose (MCC) made by mild acid hydrolysis from cotton linter, flax fibres and sulphite or kraft cooked wood pulp was studied and compared with the structure of the starting materials. Crystallinities and the length and the width of the cellulose crystallites were determined by wide-angle X-ray scattering and the packing and the cross-sectional shape of the microfibrils were determined by small-angle X-ray scattering. The morphological differences were studied by scanning electron microscopy. A model for the changes in microfibrillar structure between native materials, pulp and MCC samples was proposed. The results indicated that from softwood or hardwood pulp, flax cellulose and cotton linter MCC with very similar nanostructures were obtained with small changes in reaction conditions. The crystallinity of MCC samples was 54–65%. The width and the length of the cellulose crystallites increased when MCC was made. For example, between cotton and cotton MCC the width increased from 7.1 nm to 8.8 nm and the length increased from 17.7 nm to 30.4 nm. However, the longest crystallites were found in native spruce wood (35–36 nm).     

Some aspects of lateral chain order in cellulosics from X-ray scattering

This paper gives an overview of our recent research activities on the lateral supramolecular order of a variety of native and man-made cellulosics considering respective results from the literature. Wide-angle X-ray scattering (WAXS) was the main investigation technique used. Lateral root mean squared lattice strains between 2 and 3% were determined for the materials investigated. Crystallite sizes obtained without considering lattice distortions usually do not deviate by much more than –10% from the real, i.e. fully corrected values. This means that it is sufficient to use the simple Scherrer equation for determining lateral crystallite sizes for most routine investigations of cellulosic materials. The possible superposition of WAXS peaks of the triclinic I and monoclinic I lattice types, however, has to be considered in crystallite size determinations for Valonia cellulose. It could be shown that neglecting this fact can lead to crystallite sizes being about 20% below the true ones. Lateral crystallite dimaensions for native celluloses vary between 4nm (dissolving pulps) and 10-15 nm (Valonia). Except for bacterial cellulose, the WAXS crystallite sizes are distinctly smaller than the microfibril dimensions obtained from electron microscopy. The man-made fibres investigated showed lateral crystallite dimensions between 3 and 5nm. The importance of lateral crystallite dimensions for the properties of man-made fibres and for the alkalization process of native cellulose id demonstrated.     

Cellulose and microcrystalline cellulose from rice straw and banana plant waste: preparation and characterization

As part of continuing efforts to prepare cellulose and microcrystalline cellulose (MCC) from renewable biomass resources, rice straw and banana plant waste were used as the available agricultural biomass wastes in Egypt. The cellulose materials were obtained in the first step from rice straw and banana plant waste after chemical treatment, mainly applying alkaline-acid or acid-alkaline pulping which was followed by hypochlorite bleaching method. The results indicate a higher α-cellulose content, 66.2 %, in case of acid-alkaline treatment for rice straw compared to 64.7 % in case of alkaline-acid treatment. A low degree of polymerization, 17, was obtained for the cellulose resulting from acid–alkaline treatment for banana plant waste indicating an oligomer and not a polymer, while it reached 178 in case of the cellulose resulting from alkaline–acid treatment for the rice straw. MCC was then obtained by enzymatic treatment of the resulting cellulose. The resulting MCC show an average diameter ranging from 7.6 to 3.6 μm compared to 25.8 μm for the Avicel PH101. On the other hand, the morphological structure was investigated by scanning electron microscopy indicating a smooth surface for the resulting cellulose, while it indicates that the length and the diameter appeared to be affected by the duration of enzyme treatment for the preparation of MCC. Moreover, the morphological shape of the enzyme treated fibers starts to be the same as the Avicel PH101 which means different shapes of MCC can be reached by the enzyme treatment. Furthermore, Fourier transform infrared spectroscopy was used to indicate characteristic absorption bands of the constituents and the crystallinity was evaluated by X-ray diffraction measurements and by iodine absorption technique. The reported crystallinity values were between 34.8 and 82.4 %, for the resulting cellulose and MCC, and the degree of crystallinity ranged between 88.8 and 96.3 % dependent on the X-ray methods and experimental iodine absorption method.     

Fabrication and stimuli response of rice husk-based microcrystalline cellulose particle suspension under electric fields

We report on the electro-responsive electrorheological (ER) properties of microcrystalline cellulose (MCC) particles. It was synthesized from raw rice husk (Downes Rice) through the 3-step preparation of alkali treatment, bleaching, and hydrolysis. The MCC particles with mean particle size about 26 μm were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analysis. The MCC particles were then dispersed in silicone oil to create an ER fluid; its dramatic electro-responsive phase changes under an applied electric field were observed by an optical microscopy. The effect of electric field strengths on ER performances of the ER fluid were determined using a rotational rheometer equipped with a high-voltage generator from the controlled shear rate mode and dynamic oscillation measurements. The fluid showed typical ER effects of Bingham fluid behavior with yield stress and viscoelastic properties under an applied electric field.     

Comparing microcrystalline with spherical nanocrystalline cellulose from waste cotton fabrics

Microcrystalline cellulose (MCC) and spherical nanocrystalline cellulose (SNCC) were successfully prepared from waste cotton fabrics through acid hydrolysis. The comparative analysis of the morphology and structure between the obtained MCC and SNCC was carried out. The SNCC suspension exhibited higher stability than the MCC suspension. Transmission electron microscopy in combination with atomic force microscopy showed that the cellulose nanospheres with average size of 35?nm were achieved, while the average particle size of MCC was 49?μm. The MCC and SNCC had similar functional groups and crystalline structure as confirmed by Fourier transform infrared spectroscopy and X-ray diffraction analysis, respectively. Viscometric average molecular weight measurement and thermo gravimetric analysis indicated that the degree of polymerization and thermal stability of SNCC was lower than that of MCC. These results should improve understanding of the characteristics of MCC and SNCC derived from waste cotton fabrics and lead to many new applications.     

The short-lived signaling state of the photoactive yellow protein photoreceptor revealed by combined structural probes

The signaling state of the photoactive yellow protein (PYP) photoreceptor is transiently developed via isomerization of its blue-light-absorbing chromophore. The associated structural rearrangements have large amplitude but, due to its transient nature and chemical exchange reactions that complicate NMR detection, its accurate three-dimensional structure in solution has been elusive. Here we report on direct structural observation of the transient signaling state by combining double electron electron resonance spectroscopy (DEER), NMR, and time-resolved pump-probe X-ray solution scattering (TR-SAXS/WAXS). Measurement of distance distributions for doubly spin-labeled photoreceptor constructs using DEER spectroscopy suggests that the signaling state is well ordered and shows that interspin-label distances change reversibly up to 19 ? upon illumination. The SAXS/WAXS difference signal for the signaling state relative to the ground state indicates the transient formation of an ordered and rearranged conformation, which has an increased radius of gyration, an increased maximum dimension, and a reduced excluded volume. Dynamical annealing calculations using the DEER derived long-range distance restraints in combination with short-range distance information from (1)H-(15)N HSQC perturbation spectroscopy give strong indication for a rearrangement that places part of the N-terminal domain in contact with the exposed chromophore binding cleft while the terminal residues extend away from the core. Time-resolved global structural information from pump-probe TR-SAXS/WAXS data supports this conformation and allows subsequent structural refinement that includes the combined energy terms from DEER, NMR, and SAXS/WAXS together. The resulting ensemble simultaneously satisfies all restraints, and the inclusion of TR-SAXS/WAXS effectively reduces the uncertainty arising from the possible spin-label orientations. The observations are essentially compatible with reduced folding of the I(2)' state (also referred to as the 'pB' state) that is widely reported, but indicates it to be relatively ordered and rearranged. Furthermore, there is direct evidence for the repositioning of the N-terminal region in the I(2)' state, which is structurally modeled by dynamical annealing and refinement calculations.     

Ionic conductivity enhancement in the solid polymer electrolyte PEO9LiTf by nanosilica filler from rice husk ash

Rice husk ash is a cheap raw material available in abundance in rice-growing countries. It contains around 85–90 % amorphous silica. Rice husk ash, when subjected to a simple chemical precipitation method, will produce nanosilica which can be used for many industrial and technological applications. In this work, we have successfully synthesized nano-sized silica from local rice husk ash and prepared the nanocomposite solid polymer electrolyte, PEO₉LiTf:SiO₂. The resulting electrolyte has been characterized by X-ray diffraction, differential scanning calorimetry, atomic force microscopy, Fourier transform infrared spectroscopy, and complex impedance spectroscopy. The electrolyte shows about a 12-fold increase in ionic conductivity at room temperature due to the silica filler. In the nanocomposite electrolyte, nanosilica particles obtained from rice husk ash behaved very similarly to the commercial grade nanosilica and had a size distribution in the 25- to 40-nm range. As already suggested by us and by others, the O^2? and OH^? surface groups in the filler surface interact with the Li⁺ ions and provide hopping sites for migrating Li⁺ ions through transient H bonding, creating additional high-conducting pathways. This would contribute to a substantial conductivity enhancement through increased ionic mobility. An additional contribution to conductivity enhancement, particularly at temperatures below 60 °C, appears to come from the increased fraction of the amorphous phase, as evidenced from the reduced crystallite melting temperature and the reduced enthalpy of melting due to the presence of the filler.     

NIR FT Raman Spectroscopy–a Rapid Analytical Tool for Detecting the Transformation of Cellulose Polymorphs

This is a report of the combined use of NIR FT Raman spectroscopy and X-ray diffraction measurements (WAXS) to investigate the polymorphic transformation of cellulose I into cellulose II. For this reason samples of cellulose I were swelled in different concentrations of NaOH and dissolved in different molten inorganic salts hydrates (LiCl·2ZnCl₂·6H₂O, LiClO₄·3H₂O, LiSCN·2,5H₂O and ZnCl₂·4H₂O). NIR FT Raman spectra of the alkali treated samples were recorded. They characterize the pure modifications cellulose I and II as well as mixtures of the two polymorphic phases. The results of the Raman measurements were confirmed by X-ray scattering. The paper demonstrates that FT Raman vibrational spectroscopy is a powerful, rapid analytical method which may be used to follow the polymorphic transformation of cellulose I into cellulose II.     

Effects of pressurized hot water extraction on the nanoscale structure of birch sawdust

Pressurized hot water extraction with a flow-through system was used to extract hemicelluloses and lignin from birch sawdust. The structure of the extraction residue was studied on various levels. Molecular mass distributions were determined with gel permeation chromatography and the crystal structure of cellulose was characterized using wide-angle X-ray scattering (WAXS). Information on the short-range order of cellulose microfibrils and on the nanoscale pore structure was obtained with small-angle X-ray scattering (SAXS), and the micrometre scale cellular morphology was imaged with X-ray microtomography. The pressurized hot water treatment was observed to increase the lateral width of cellulose crystallites, determined with WAXS, whereas a possible small decrease in the crystallinity of cellulose compared to native wood was detected. The molecular mass of cellulose remained at a relatively high level. According to the SAXS results, a tighter lateral association of cellulose microfibrils was observed in the extracted samples, which possibly led to opening of pores between bundles of microfibrils, as indicated by an increased specific surface area. A reduction in the thickness of the fibre cell walls was evidenced by X-ray microtomography.     

Watching nanoparticles form: an in situ (small-/wide-angle X-ray scattering/total scattering) study of the growth of yttria-stabilised zirconia in supercritical fluids

Understanding nanoparticle-formation reactions requires multi-technique in situ characterisation, since no single characterisation technique provides adequate information. Here, the first combined small-angle X-ray scattering (SAXS)/wide-angle X-ray scattering (WAXS)/total-scattering study of nanoparticle formation is presented. We report on the formation and growth of yttria-stabilised zirconia (YSZ) under the extreme conditions of supercritical methanol for particles with Y(2)O(3) equivalent molar fractions of 0, 4, 8, 12 and 25 %. Simultaneous in situ SAXS and WAXS reveals a quick formation (seconds) of sub-nanometre amorphous material forming larger agglomerates with subsequent slow crystallisation (minutes) into nanocrystallites. The amount of yttria dopant is shown to strongly affect the crystallite size and unit-cell dimensions. At yttria-doping levels larger than 8 %, which is known to be the stoichiometry with maximum ionic conductivity, the strain on the crystal lattice is significantly increased. Time-resolved nanoparticle size distributions are calculated based on whole-powder-pattern modelling of the WAXS data, which reveals that concurrent with increasing average particle sizes, a broadening of the particle-size distributions occur. In situ total scattering provides structural insight into the sub-nanometre amorphous phase prior to crystallite growth, and the data reveal an atomic rearrangement from six-coordinated zirconium atoms in the initial amorphous clusters to eight-coordinated zirconia atoms in stable crystallites. Representative samples prepared ex situ and investigated by transmission electron microscopy confirm a transformation from an amorphous material to crystalline nanoparticles upon increased synthesis duration.     

The swelling and dissolution of cellulose crystallites in subcritical and supercritical water

The swelling and dissolution phenomena of microcrystalline cellulose (MCC) were investigated in subcritical and supercritical water. Commercial MCC was treated in water at temperatures of 250–380 °C and a pressure of 250 bar for 0.25–0.75 s. As reaction products, undissolved but depolymerised cellulose residue, short-chain cellulose precipitate, water-soluble cello-oligosaccharides and monosaccharides, as well as their degradation products, were detected. The highest yield of the cellulose II precipitate was obtained after a reaction time of 0.25 s at 360 °C. Our hypothesis was that if the crystallites were swollen, the depolymerization pattern would be that of homogeneous reaction and the cellulose Iβ to cellulose II transformation would be observed. The changes in the structure of the undissolved cellulose residue were characterised by size exclusion chromatography, wide-angle X-ray scattering and ¹³C solid-state NMR techniques. In many cases, the cellulose residue samples contained cellulose II; however, due to experimental limitations, it remains unclear whether it was formed through the swelling of crystallites or the partial readsorption of the dissolved cellulose fraction. The molar mass distributions of untreated MCC and after low intensity treatments showed a bimodal shape. After high intensity treatments the high molar mass chains disappeared which indicated a complete swelling or dissolution of the crystallites.     

The effect of drying method on the properties and nanoscale structure of cellulose whiskers

Cellulose whiskers were prepared from wood- and cotton-based microcrystalline cellulose and dried by two methods: freeze-drying or air-drying. The effect of drying method on the properties and structure of the whiskers were studied. Furthermore, the influence of the source of cellulose on the nanoscale structure was investigated. Drying method was observed to slightly influence the thermal stability of cellulose whiskers, whereas the char residue varied significantly depending on the drying process performed. Small- and wide-angle X-ray scattering and solid state nuclear magnetic resonance spectroscopy were used to examine the crystallinity and nanoscale structure of the dried whiskers. It was observed that the crystal structure and crystallinity of cellulose whiskers remained during all treatments, whereas their nanoscale structure was significantly influenced by drying method, neutralization, and source of cellulose. Relationships between thermal behavior and nanoscale structure were reported and discussed.     

New polyurethane foams modified with cellulose derivatives

New polyurethane foams were elaborated with different cellulose derivatives as raw material, by the one-shot process. The foams were submitted to soxhlet extraction in order to quantify the amount of cellulose derivative incorporated in the foam by chemical bonding. The foams were characterized by means of FTIR, solid state ¹³C NMR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy and dynamic mechanical analysis (DMA). The FTIR- and solid state ¹³C NMR showed characteristic peaks for cellulose derivatives and polyurethane. DMA measurements indicated that storage modulus increased with increasing content of cellulose derivatives. The highest value was obtained for foams prepared with cellulose sulphate.     

Effect of the Coating of the Polymer Blend (Polyacrylamide/PEG 6000) on the Efficiency of Rice Husk as a Pesticide Carrier

In recent years the utilization of fibers and powders derived from agricultural sources has become a subject of interest. However, they have been exploited only from an engineering point of view, and the strong ability of agricultural wastes as a carrier for agrochemical formulations has been ignored. A study has been made on the possibility of using such an agrochemical waste, namely rice husk, which is readily available and biodegradable, as a carrier for pesticide formulation. The solid formulations were prepared by adsorbing deltamethrin on the rice husk. The deltamethrin‐adsorbed rice husk is then coated with the polymer blend of Polyacrylamide and PEG 6000 in varying ratios between the deltamethrin‐adsorbed rice husk and the polymer blend. The formulations were characterized by analytical methods such as FTIR and XRD techniques. Important physical properties from the formulation standpoint, such as solubility, dispersion stability, and wettability, were studied.     

Thermo-Reversible Cellulose Micro Phase-Separation in Mixtures of Methyltributylphosphonium Acetate and γ-Valerolactone or DMSO

We have identified cellulose solvents, comprised of binary mixtures of molecular solvents and ionic liquids that rapidly dissolve cellulose to high concentration and show upper-critical solution temperature (UCST)-like thermodynamic behaviour - upon cooling and micro phase-separation to roughly spherical microparticle particle-gel mixtures. This is a result of an entropy-dominant process, controllable by changing temperature, with an overall exothermic regeneration step. However, the initial dissolution of cellulose in this system, from the majority cellulose I allomorph upon increasing temperature, is also exothermic. The mixtures essentially act as ‘thermo-switchable’ gels. Upon initial dissolution and cooling, micro-scaled spherical particles are formed, the formation onset and size of which are dependent on the presence of traces of water. Wide-angle X-ray scattering (WAXS) and ¹³C cross-polarisation magic-angle spinning (CP-MAS) NMR spectroscopy have identified that the cellulose micro phase-separates with no remaining cellulose I allomorph and eventually forms a proportion of the cellulose II allomorph after water washing and drying. The rheological properties of these solutions demonstrate the possibility of a new type of cellulose processing, whereby morphology can be influenced by changing temperature.