All-cellulose composites from unbleached hardwood kraft pulp reinforced with nanofibrillated cellulose

In the present work, nanofibrillated cellulose (NFC) from bleached eucalyptus pulp was prepared, characterized and used as reinforcement in an unbleached eucalyptus fiber matrix. First, the NFC was fabricated through TEMPO-mediated oxidation and characterized for the degree of polymerization, water retention value, cationic demand and carboxyl content. Intrinsic mechanical properties were also calculated by applying the rule of mixtures, which determines the coupling (f _c) and efficiency factor (η _e) of cellulose nanofibrils within the matrix. The results showed that the average intrinsic tensile strength and Young’s modulus of NFC are estimated to be 6,919 MPa and 161 GPa, respectively. After characterization, the NFC was used as reinforcement in the preparation of biocomposites in the form of paper handsheets, which were physically and mechanically analyzed. The presence of NFC induced an increase in the density of biocomposites and significant enhancement of the mechanical properties as well as an important reduction in porosity. Finally, f _c and η _e were determined from the mean intrinsic properties.     

Mechanical fabrication of high-strength and redispersible wood nanofibers from unbleached groundwood pulp

In the past, the direct production of lignin-containing nanofibers from wood materials has been very limited, and nanoscale fibers (nanocelluloses) have been mainly isolated from chemically delignified, bleached cellulose pulp. In this study, we have introduced a newly adapted, heat-intensified disc nanogrinding process for the enhanced nanofibrillation of wood nanofibers (WNF) with a high lignin content (27.4 wt%). The WNF produced this way have many unique and intriguing properties in their naturally occurring form, for example, being able to be dispersed in ethanol and having ethanol solution viscosities higher than water solution viscosities. When WNF nanopapers were formed with ethanol, the properties of the nanofibers were recoverable without a notable decrease in the viscosity or mechanical strength after redispersing them in water. The preservation of lignin in the WNF was noticed as an increase in the water contact angles (89°), the rapid removal of water in the fabrication of the nanopapers, and the enhanced strength of the nanopapers when subjected to high pressure and heat. The nanopapers fabricated from the WNF were mechanically stable, having an elastic modulus of 6.2 GPa, a maximum stress of 103.4 MPa, and a maximum strain of 3.5%. Throughout the study, characteristics of the WNF were compared to those of the delignified and bleached reference cellulose nanofibers. We envision that the exciting characteristics of the WNF and their lower cost of production compared to that of bleached cellulose nanofibers may offer new opportunities for nanocellulose and biocomposite research.     

Rheological peculiarities of concentrated suspensions

The rheological properties of concentrated suspensions of metal oxides dispersed in transformer oil, which are used as electrorheological fluids, are systematically studied. Colloidal particles have intermediate sizes between nano- and microsized scales. Low-amplitude dynamic measurements show that the storage moduli of the examined suspensions are independent of frequency and these materials should be considered as solidlike elastic media. The storage modulus is proportional to the five-powdered particle volume concentration. At the same time, a transition through an apparent yield stress with a reduction in the viscosity by approximately six orders of magnitude is distinctly seen upon shear deformation. The character of the rheological behavior depends on the regime of suspension deformation. At very low shear rates, a steady flow is possible; however, upon an increase in the rate, an unsteady regime is realized with development of self-oscillations. When constant shear stresses are preset, in some range of stresses, thickening of the medium takes place, which can also be accompanied by self-oscillations. In order to gain insight into the nature of this effect, measurements are performed for samples with different volume/surface ratios, which show that, in some deformation regimes, suspension is separated into layers and slipping occurs along a low-viscosity layer with a thickness of several dozen microns. Direct observations show a distinct structural inhomogeneity of the flow. The separation and motion of layers with different compositions explain the transition to the flow with the lowest apparent Newtonian viscosity. Thus, the deformation of concentrated suspensions is associated with self-oscillations of stresses and slipping along a low-viscosity interlayer.     

Surface characterization of unbleached kraft pulps by means of ESCA

The effect of digestion conditions (amount of effective alkali, digestion time) on the surface compositions of unbleached softwood (Pinus sylvestris) kraft pulp has been investigated by electron spectroscopy for chemical analysis (ESCA). The quantities monitored were the angular dependence of the total O/C ratio, the relative amounts of carbons in different states of oxidation and the adsorption of Al and Ca ions to the carboxyl groups in the surface. Examination of the angular dependence of ESCA intensities shows that the concentration of alkyl carbon is high in a very thin surface layer and that it decreases linearly with decreasing kappa number. The concentration of alkyl carbon is decreased by extraction of the fibres with dichloromethane, but the amount remaining in the surface after extraction still decreases linearly with decreasing kappa number (i.e. it decreases with increasing digestion time). It is suggested that the observed enrichment of alkyl carbon in the outermost surface layers most probably is due to reprecipitation of lignin. In pulp that has not been extracted, there is also strong enrichment of extractives in the surface. This amount increases with increasing effective alkali but is relatively independent of digestion time. ESCA analysis of the Al and Ca bound to the carboxyl groups shows that the amount depends on digestion time; the results are consistent with the notion that the reprecipitated lignin contains carboxyl groups.     

Rheological properties of microfibrillar suspension of TEMPO-oxidized pulp

The rheology of cellulose microfibril suspensions from TEMPO-oxidized pulp was investigated. The suspension showed a pseudo-plastic and thixotropic behavior, slowly evolving with time under a given shear rate. The viscosity was proportional to the concentration up to the critical concentration of 0.23%. Above it, the viscosity followed a power law with exponents from 2 to 6 depending on the shear rate, and the system showed shear thinning behavior and behaved gel-like. Below this concentration, the system was more Newtonian. Birefringence measurement of 0.44% and 0.78% suspension showed that microfibrils alignment saturated at a small shear rate with a Herman’s orientation parameter below 0.65 probably due to the interconnection of microfibrils.     

壳聚糖浓溶液流变学性质研究-溶剂性质的依赖性

用不同pH值的HCOOH, CH~3COOH, HCl,0.1mol.dm^-3CH~3COONa+0.2mol.dm^-3CH~3COOH水溶液为溶剂, 进行了壳聚糖浓溶液的流变学性质研究。实验结果表明, 溶剂pH值相同时, 壳聚糖在各种酸中的溶解性和溶液沾度差别较大。同一种酸中, 在可溶范围内, pH值增加, 溶剂变劣, 粘度-浓度的幂律方程指数α增大。外加盐使溶剂变劣程度增加。在任何一种酸中, 浓溶液粘度都随存放时间的延长而下降, 流动指数n减小, 流动活化能基本不变。     

Rheological transition of concentrated emulsions during successive shearing cycles

Rheological investigations have identified a shear viscosity transition from shear thinning to Newtonian at low to moderate shear rates for concentrated polydimethylsiloxane emulsions during successive shearing cycles. The viscosity "flattening" behavior is dependent on the maximum shear rate applied and on droplet deformation. Atomic force microscopy measurements indicate attraction between the "repulsive" emulsion droplets under deformation. The results suggest formation of stable droplet layers due to deformation under high shear hydrodynamic compression. Based on these findings, unique methods to control the post-shear rheology of concentrated emulsions can be envisaged.     

Grinding process for the production of nanofibrillated cellulose based on unbleached and bleached bamboo organosolv pulp

Nanofibrillated cellulose (NFC) is a type of nanomaterial based on renewable resources and produced by mechanical disintegration without chemicals. NFC is a potential reinforcing material with a high surface area and high aspect ratio, both of which increase reinforcement on the nanoscale. The raw materials used were unbleached and bleached bamboo organosolv pulp. Organosolv pulping is a cleaner process than other industrial methods (i.e. Kraft process), as it uses organic solvents during cooking and provides easy solvent recovery at the end of the process. The NFC was produced by treating unbleached and bleached bamboo organosolv pulps for 5, 10, 15 and 20 nanofibrillation cycles using the grinding method. Chemical, physical and mechanical tests were performed to determine the optimal condition for nanofibrillation. The delamination of the S2 layer of the fibers during nanofibrillation contributed to the partial removal of amorphous components (mainly lignin), which have low polarity and improved the adhesion of the fibers, particularly the unbleached cellulose. The transverse modulus of elasticity of the unbleached NFC was highest after 10 nanofibrillation cycles. Further treatment cycles decreased the modulus due to the mechanical degradation of the fibers. The unbleached NFC produced by 10 cycles have a greater transverse modulus of elasticity, the crystallite size showed increase with the nanofibrillation, and after 5 nanofibrillation cycles, no differences are observed in the morphology of the fibers.     

Cooling effects on a model rennet casein gel system: part I. Rheological characterization

The gelation of a model rennet casein system was studied during cooling at different rates. During cooling, casein network structure development was proposed to evolve over a few steps at different length scales: molecules, particles, flocs, or network. Rennet casein flocs are fractal in nature, and fractal dimension and floc size are two variables affecting the rheology and microstructure of a rennet casein gel. Casein structure formation during cooling from 80 to 5 degrees C at four different rates (0.5, 0.1, 0.05, and 0.025 degrees C/min) was monitored by dynamic rheological tests, and a stronger gel developed at a slower cooling rate. During different cooling schedules, similar fractal dimensions were observed due to a lack of difference in the colloidal interactions. Differences among rheological data were possibly caused by variability in floc size, as observed in the second part of this paper. A larger number of smaller-sized flocs enabled gelation at a higher temperature and created a stronger network at a slower cooling rate. Controlling cooling schemes thus provides an approach for manipulating casein gelation and the microstructure for a system of fixed chemical compositions.     

Stress-induced compaction of concentrated dispersions of gel particles

 When submitted to successive shear stress steps, the elastic shear modulus of a concentrated dispersion of soft gel particles shows an exponential increase from 50 to 110 Pa. A slow relaxation time (τ _r ≃500 s) attributed to the mobility of the gel particles within their free volume is obtained. The amplitude of the relaxation time distribution decreases with the number of shear stress sequences, indicating a progressive decrease in the free volume available per particle. The results are explained by an increase in the packing density as grains rearrange under the external constraint. A rate constant is determined from the evolution of the dispersion's elastic modulus (K≃4 × 10⁻⁴ s⁻¹). The rate of compaction shows a logarithmic decrease when the initial particle's packing fraction is increased. Received: 5 October 1999 In revised form: 21 December 1999 Accepted: 21 January 2000     

Rheological studies of diatom encapsulation in silica gel

The mutual influence of the mineral and biological components of a specific bio-hybrid system consisting of diatom cells entrapped in a silica gel was studied by rheological methods. Small amplitude shear stress oscillatory measurements indicate that the culture medium alone has a strong impact on the silica network formation and viscoelastic properties. In contrast, the presence of diatoms does not significantly perturb the sol–gel process, and leads to a moderate change in the gel elasticity. Compression tests show that a large difference exists between the mechanical properties of silica gels and diatom shells, suggesting a limited impact of the gel strength on the diatom survival rate. We also show that the biological activity of entrapped diatoms can modify the structural evolution of the silica gel. This work indicates that rheological methods may be important tools for the optimization of whole cells encapsulation procedures and further confirms that encapsulated diatoms are able to interact with the surrounding silica materials.     

Physico-chemical characterization of a cellulosic fraction from sugar beet pulp

The residue of sugar beet pulp from which pectin and alkaline soluble polysaccharides have been removed by microwave assisted extraction or conventional heat was treated with sodium monochloroacetate under alkaline pH to convert the residual cellulose present to carboxy methyl cellulose (CMC). Weight average molar masses ranged from about 96 to 220 × 10³ Daltons, weight average intrinsic viscosity from 1.9 to 4.1 dL/g and degree of substitution from 1.38 to 0.59. HPSEC with online molar mass detectors and Atomic Force Microscopy revealed that CMC was comprised of aggregated linear moieties in contact with spherical bodies. The linear portion was a mixture of rods and segmented rods. Some of the rods had long branches.     

Phosphono analogue of phosphatidylethanolamines from kenaf seeds

Institute of the Chemistry of Plant Substances, Uzbek SSR Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, Vol. 6, pp. 848–849, November–December, 1989.     

Rheological properties and microstructures of Carbopol gel network system

Carbopol gel systems have been studied using steady, oscillatory rheology, and cryoscanning electron microscopy (cryo-SEM) analysis in order to elucidate the nature of the different microstructures of the gel in relation to polymer concentration as well as triethanolamine (TEA) content. The effect of changing the concentration of Carbopol (0.1–4 wt%) for 0, 1, and 10 wt% TEA has been investigated. Cryo-SEM revealed that honeycomb structures were observed in the gel system depending on the amount of TEA and Carbopol while the irregular fibrous three dimensional gel network systems were seen at the lower level of polymer content even in the high concentration of TEA. In addition to that, as the amount of polymer was increased, strings of fibrous network became thicker and of honeycomb-like structure. Shape of storage modulus-shear stress curve in the dynamical rheometric study was significantly changed as a result of variation in the microstructures while frequency sweep curve and yield values obtained from the model fitting in the steady rheological measurements couldn't reflect the structural difference of Carbopol gels. Two distinct relaxation phenomena were appeared with increase in polymer concentration as well as TEA concentration. Temperature dependence of the stress sweep experiment was measured and shown that the effect of temperature (1–80 °C) on the shape of the curve was the similar trend with that of TEA and polymer concentrations, although the temperature dependency on the increment was much weaker than TEA concentration.     

Production, bleaching, and characterization of pulp from Stipa tenacissima

Alfa grass pulping was successfully performed in hydro-organic acid medium under mild conditions (107°C, atmospheric pressure, cooking time: 3 h). Use of an acetic acid/formic acid/water mixture as pulping liquor was perfectly suitable for selective isolation of pulp, lignin, and hemicelluloses. The unbleached pulp obtained in good yield was first delignified by peroxyacids in organic acid medium and then bleached with hydrogen peroxide in a basic medium to give pulp offering good physico-chemical and mechanical characteristics.     

Thermal characterization of benzylcellulose derivatives prepared from bleached pinus kraft pulp

The thermal characterization (DSC and TG) of benzylcellulose derivatives prepared from the benzylation of bleached Pinus Kraft pulp is described in this paper. The objective of this study was to examine the changes in glass transition temperature (T _g) and the thermal stability of the benzylated product as a function of the benzylation extent (degree of substitution). The DSC analysis showed that the benzylcelluloses can display glass transition temperature at two different regions and that thermal stability is slightly higher than that of the parent cellulose. This revised version was published online in August 2006 with corrections to the Cover Date.     

A comparison of softwood and birch kraft pulp fibers as raw materials for production of TEMPO-oxidized pulp, MFC and superabsorbent foam

This study compares the suitability of using birch kraft pulp or softwood kraft pulp in the preparation of TEMPO-oxidized pulp, MFC and superabsorbent foam. TEMPO oxidation was performed using five different dosages of primary oxidant. The time of disintegration treatment was varied to study its influence on the properties of the produced MFCs and foams. Both the birch and the softwood pulps could be used for producing superabsorbent foams, depending on the process conditions, the absorption capacities were about the same for the two pulps and varied between 25 and 55 g saline solution/g absorbent. The foams based on birch pulp had, however, on average, 30 % higher retention capacity than the foams based on softwood pulp. The maximum retention capacity obtained was 16.6 g saline solution/g absorbent. The greater retention capacity of birch-based foams is not fully understood, but a smaller pore size may be the reason, which in turn would generate greater capillary forces. In addition to this, it was found that birch pulps, contrary to softwood pulps, had a substantial amount of fibers that were relatively unaffected by the disintegration treatment. These oxidized fibers are likely to reinforce the foam, thereby making the foam more resistant to external pressures, which is in accordance with earlier findings.     

高湿度条件下分解高浓度O3催化剂的研究

Ｏ3 (臭氧 )具有极强的氧化能力 ,因此被广泛地用于水和空气的除臭、杀菌以及染料废水的脱色、ＣＯＤ的去除及芳香族有机物的降解[1,2 ] 。但Ｏ3 是一种毒性物质 ,处理过程中剩余的Ｏ3 排放到空气中会造成环境污染。目前 ,处理含Ｏ3 尾气的方法主要有活性炭吸附法、药液吸收法、高温热解法和催化分解法[1] ,其中催化分解法不仅有高的分解率 ,而且满足长期稳定、安全、经济等要求 ,是较为理想的Ｏ3 分解方法。催化分解法使用的催化剂主要有含Ｍｎ催化剂、含Ｔｉ催化剂和过渡金属催化剂等。各种催化剂在低湿度条件下的催化性能都比较好 ,但在…     

Rheological properties of concentrated aqueous solutions of anionic and cationic polyelectrolyte mixtures

The rheological properties of aqueous solutions of poly(acrylic acid), poly(diallyldimethyldiammonium chloride), and their mixtures at 25°C have been studied. The concentrated solutions of the mixtures contain 18 wt % of both polymers taken at different ratios. The ratio of cationogenic and anionogenic groups φ varied from 0 to 0.4 is taken as a criterion for selection of mixture composition. An increase in φ, reflecting a more intense formation of polyelectrolyte complexes in solution, is accompanied by a significant rise in the low-frequency loss modulus and, especially, in the storage modulus, as well as by an increase in viscosity over the entire studied range of shear rates. This behavior may be explained by the presence of an additional spatial structure with junctions formed by interacting complementary charged groups. In the general case, the formation of poly(acrylic acid)-poly(diallyldimethyldiammonium chloride) polyelectrolyte complexes is said to take place in solution. The excess of rheological characteristics of mixture solutions over the corresponding characteristics of poly(acrylic acid) solutions is found to be the power function of parameter φ. The additional spatial network derived from polyelectrolyte complexes and occurring in solution is destroyed at lower shear stresses than is the network of intermolecular entanglements. At high shear stresses, orientational effects may cause phase separation of the systems owing to a change in the hydrophilic-hydrophobic balance between complexes of poly(acrylic acid) with poly(diallyldimethyldiammonium chloride) and water.