Comparison of different reactive organophosphorus flame retardant agents for cotton: Part I. The bonding of the flame retardant agents to cotton

N-Methylol dimethylphosphonopropionamide (MDPA), known as “Pyrovatex CP” and “Pyrovatex CP New” commercially, has been one of the most commonly used durable flame retardant agents for cotton for many years. In our previous research, we developed a flame retardant finishing system for cotton based on a hydroxy-functional organophosphorus oligomer (HFPO) in combination with a bonding agent such as trimethylolmelamine (TMM) and dimethyloldihydroxyethyleneurea (DMDHEU). In this research, we investigated the bonding of these two flame retardant finishing agents to cotton. We found that the majority of MDPA is bound to cotton by its N-methylol group and that the use of TMM as a co-reactant modestly increases the fixation of MDPA onto cotton. For HFPO, however, the use of a bonding agent is necessary to form a covalent linkage between HFPO and cotton. Both the fixation of HFPO on cotton and its laundering durability are influenced by the effectiveness and concentration of the bonding agent. The commercial product of HFPO contains approximately 33% more phosphorus than that of MDPA and the percent fixation of HFPO on cotton is also moderately higher than that of MDPA. The bonding between MDPA and cotton is significantly more resistant to hydrolysis during multiple launderings than that between HFPO and cotton. The selection of catalyst also plays a significant role in influencing the bonding of the flame retardant agents to cotton.     

Electrospun cellulose acetate fibers: effect of solvent system on morphology and fiber diameter

This paper reports an investigation of the effects of solvent system, solution concentration, and applied electrostatic field strength (EFS) on the morphological appearance and/or size of as-spun cellulose acetate (CA) products. The single-solvent systems were acetone, chloroform, N,N -dimethylformamide (DMF), dichloromethane (DCM), methanol (MeOH), formic acid, and pyridine. The mixed-solvent systems were acetone–DMAc, chloroform–MeOH, and DCM–MeOH. Chloroform, DMF, DCM, MeOH, formic acid, and pyridine were able to dissolve CA, forming clear solutions (at 5% w/v), but electrospinning of these solutions produced mainly discrete beads. In contrast, electrospinning of the solution of CA in acetone produced short and beaded fibers. At the same solution concentration of 5% (w/v) electrospinning of the CA solutions was improved by addition of MeOH to either chloroform or DCM. For all the solvent systems investigated smooth fibers were obtained from 16% (w/v) CA solutions in 1:1, 2:1, and 3:1 (v/v) acetone–DMAc, 14–20% (w/v) CA solutions in 2:1 (v/v) acetone–DMAc, and 8–12% (w/v) CA solutions in 4:1 (v/v) DCM–MeOH. For the as-spun fibers from CA solutions in acetone–DMAc the average diameter ranged between 0.14 and 0.37 μm whereas for the fibers from solutions in DCM–MeOH it ranged between 0.48 and 1.58 μm. After submersion in distilled water for 24 h the as-spun CA fibers swelled appreciably (i.e. from 620 to 1110%) but the physical integrity of the fibrous structure remained intact.     

Selection of thermotolerant yeasts for simultaneous saccharification and fermentation (SSF) of cellulose to ethanol

A total of 27 yeast strains belonging to the groupsCandida, Saccharomyces, andKluyveromyces were screened for their ability to grow and ferment glucose at temperatures ranging 32-45°C. K. marxianus andK. fragilis were found to be the best ethanol producing organisms at the higher temperature tested and, so, were selected for subsequent simultaneous saccharification and fermentation (SSF) studies.     

Mercerization of primary wall cellulose and its implication for the conversion of cellulose I→cellulose II

The mercerization of homogenized primary wall cellulose extracted fromsugar beet pulp was investigated by transmission electron microscopy (TEM),X-ray diffraction together with ¹³C CP-MAS NMR, and FT-IR spectroscopy.For samples resulting from acid extraction, mercerization began at 9% NaOH, whereasfor samples purified by alkaline treatment, the mercerization started at 10%NaOH. The change in morphology when going from cellulose I to cellulose II wasspectacular, as all the microfibrillar cellulose morphology disappeared duringthe treatment. This change in morphology was very drastic as soon as the NaOHconcentrations were increased beyond 8 and 9% for the acid and alkalinepreparedsamples, respectively. On the other hand, the conversion was found to be moreprogressive in terms of increasing NaOH concentration when the transformationwas analyzed by X-ray diffraction or spectroscopy. Our observations of themercerization of isolated cellulose microfibrils are consistent with theconceptof cellulose microfibrils made of parallel chains in cellulose I and crystalsofcellulose II consisting of antiparallel chains.     

Characterization of the barrier properties of composites of HDPE and purified cellulose fibers

The present work presents and discusses the interrelation between composition, morphology, thermal history, mechanical and barrier properties to oxygen and limonene of composites of HDPE/MA-PE/cellulose fibers of significant interest in, among others, food packaging applications. From the overall results, it was observed that increasing the loading of purified alpha-cellulose fibers in the polyethylene matrix beyond 10 wt.% led to a decrease in the permeability coefficient of d-limonene, effect which was found to be primarily related to a decrease in the overall solubility of this strongly plasticizing aroma component. On the other hand, the oxygen permeability was found to decrease to a significant extend with increasing fiber content beyond 5 wt.%, but this effect was more strongly ascribed to a significant decrease in the diffusion coefficient. Therefore, the fibers are thought to generate a more tortuous path for the non-interacting gas molecules to travel across the composites thickness, even when tested at high relative humidity conditions. Optimum fiber loading levels in terms of overall property balance were found to be around 20 wt.%.     

纤维素基磁性聚偕胺肟树脂的研究——循环吸溴中吸附与还原能力的变化

研究了酸式纤维素基磁性聚偕胺肟树脂（ＡＭＡＯ）在循环吸溴过程中吸附容量和还原能力的变化，发现原树脂的吸溴初速和溴的还原率比再生树脂高一倍以上，但第一次和第二次再生树脂的吸附速度和还原效率几乎相同，暗示着树脂吸溴后基本结构已发生了彻底的变化．树脂在循环使用时吸溴容量变化不大而溴的还原量却显著降低，表明ＡＭＡＯ作为吸溴剂有较高的实用价值．     

Role of micro-crystalline parameters in the physical properties of cotton fibers

Karnataka state in India is very well known for its cotton cultivation and there are innumerable varieties of these cotton fibers. Although, the yield and other types of characterization have been carried out on these fibers, the structure-property relation is not well studied till today. We have examined four different raw cotton fibers using Wide Angle X-ray Scattering (WAXS) technique and also we have computed micro-crystalline parameters. This study brings out the structure-property relation in cotton fibers.     

Microporous, fast response cellulose ether hydrogel prepared by freeze-drying

A simple and effective method of preparing fast-response gels is developed. The freeze-drying and subsequent rehydration of thermosensitive gels alters the microstructural properties of the gels in a way that leads to rapid shrinking rates. Microporous hydroxypropyl cellulose (HPC) gels were created by this method to investigate the influence of the process on the swelling and shrinking kinetics of the gels in response to temperature changes. Micropores of different size ranges were produced by freezing gels with different amounts of water at −20 °C. Water content was the key factor to control the microporosity and the shrinking rates of gels. After the freezing treatment, an effective diffusion coefficient for shrinking could be determined by fitting Fick's law to the data (5.2 × 10⁻⁴ cm²/s). This was an increase of two orders of magnitude over that of the untreated, non-porous gel (6.0 × 10⁻⁶ cm²/s). The magnitude of the shrinking coefficient indicates that the shrinking rate of the microporous gel is probably limited by the convective flow, as unsteady flow through porous media follows the same differential equation as Fick's law, but with much greater transport coefficients, as observed here. Physically, the shrinking rate may be determined by the level of interconnected-cells in a microporous structure present at the beginning of shrinking process because the convection through the interconnected-cells is estimated to be much slower than the polymer network diffusion rate of the struts of micropores (0.1–3.0 μm) as well as heat transfer.     

Enhancing the enzymatic hydrolysis of cellulosic materials using simultaneous ball milling

One of the limiting factors restricting the effective and efficient bioconversion of softwood-derived lignocellulosic residues is the recalcitrance of the substrate following pretreatment. Consequently, the ensuing enzymatic process requires relatively high enzyme loadings to produce monomeric carbohydrates that are readily fermentable by ethanologenic microorganisms. In an attempt to circumvent the need for larger enzyme loadings, a simultaneous physical and enzymatic hydrolysis treatment was evaluated. A ball-mill reactor was used as the digestion vessel, and the extent and rate of hydrolysis were monitored. Concurrently, enzyme adsorption profiles and the rate of conversion during the course of hydrolysis were monitored. α-Cellulose, employed as a model substrate, and SO₂-impregnated steam-exploded Douglas-fir wood chips were assessed as the cellulosic substrates. The softwood-derived substrate was further posttreated with water and hot alkaline hydrogen peroxide to remove >90% of the original lignin. Experiments at different reaction conditions were evaluated, including substrate concentration, enzyme loading, reaction volumes, and number of ball beads employed during mechanical milling. It was apparent that the best conditions for the enzymatic hydrolysis of α-cellulose were attained using a higher number of beads, while the presence of air-liquid interface did not seem to affect the rate of saccharification. Similarly, when employing the lignocellulosic substrate, up to 100% hydrolysis could be achieved with a minimum enzyme loading (10 filter paper units/g of cellulose), at lower substrate concentrations and with a greater number of reaction beads during milling. It was apparent that the combined strategy of simultaneous ball milling and enzymatic hydrolysis could improve the rate of saccharification and/or reduce the enzyme loading required to attain total hydrolysis of the carbohydrate moieties.     

Capillary electrochromatographic separation of enantiomers under aqueous mobile phases on a covalently bonded cellulose derivative chiral stationary phase

A chemically bonded cellulose tris(3,5-dimethylphenylcarbamate) chiral stationary phase (CSP) was prepared by a radical polymerization reaction. The prepared CSP was packed into fused-silica capillaries with inner diameter of 75 microm to perform enantiomer separations in CEC. The electrochromatographic behavior of the CSP was investigated. On the prepared CSP, high EOF could be generated under acidic mobile phases, which represented an advantage for the separation of acidic enantiomers. Several neutral, acidic, and basic enantiomers were resolved on the prepared CSP under aqueous mobile phases. The column efficiencies were between 20,000 and 100,000 plates/m, which were much higher than those of HPLC. In addition, it was observed that the separation of some enantiomers benefited from the adoption of THF as mobile phase modifier.