Kinetics of swelling of cotton fibers in aqueous ethylenediamine solutions using X-ray diffraction data

Kinetics of swelling of cotton cellulose with 75% (w/w) ethylenediamine (EDA) solution has been studied using X-ray diffraction. Apparently, the swelling reaction proceeds at three different rates, all obeying the first-order kinetics. The first rate (k₁), which is the fastest one, is hypothetically attributed to the swelling action of EDA–monohydrate in the amorphous region of cellulose; the second rate (k₂), which is extremely slow, is responsible for the penetration of swelling species into the crystallites, accompanied by breakage of the hydrogen bonds in these regions; and the third rate (k₃), which is faster than k₂ but slower than k₁, has been assigned to the decrystallization of the crystalline regions. The increase in temperature of swelling (from 10°C to 55°C) brought about increase in all these three rates with shortening of their respective periods. Thus, at temperatures of 35°C and above, k₂ and k₃ merge, giving a combined rate (k₂₊₃). These results were confirmed from the data on the activation energy values. The changes in crystallinity were comparatively less, when 65% (w/w) EDA solution was used for swelling cotton fibers. The ineffectiveness of 65% (w/w) EDA solution was explained on the basis of the absence of powerful swelling species in the solution. An attempt has also been made to examine the kinetic data on the basis of the model for cotton fiber fine structure consisting of crystalline elementary fibrils and surfaces or regions of varying extents of hydrogen bonding.     

Dissolution of semicrystalline polymer fibers: Numerical modeling and parametric analysis

The solvent processing of polymers is significantly constrained by polymer chain crystallinity. A phenomenological model is developed here that captures the phenomena governing the dissolution of semicrystalline polymers, for example, solvent penetration, transformation from crystalline to amorphous domains, specimen swelling, and polymer chain untangling. The model is validated for the case of cellulose fiber swelling and dissolution in an ionic liquid. A parametric sensitivity analysis is performed to assess the impact of decrystallization rate constant, disentanglement rate, concentration dependence of solvent diffusivity, disentanglement threshold, and thickness of external boundary layer on the swelling and dissolution of semicrystalline polymer fibers. The rate of dissolution after attaining maximum swelling is found to be mainly controlled by the polymer chain disentanglement rate. The insights obtained from this study would facilitate the design of efficient solvent systems and processing conditions for the dissolution of semicrystalline polymers such as cellulose, polyglycolic acid, and polyesters. © 2017 American Institute of Chemical Engineers AIChE J, 63: 1368–1383, 2017     

Microcrystalline-cellulose hydrolysis with concentrated sulphuric acid

The effects of temperature (25–40°C), H₂SO₄ concentration (31–70% (w/v)) and the acid/substrate relationship (1–5 cm³ of H₂SO₄ per g⁻¹ of cellulose) on the solubilization rate of microcrystalline cellulose and on the glucose production rate have been analysed. The solubilization process was by determining reducing groups present in solution. For acid/substrate relationships of more than 1 cm³ g⁻¹ and H₂SO₄ concentrations of greater than 62% (w/v), the acid promoted the total solubilization of the cellulose in the form of chains with a low degree of polymerization within 4 h. The solubilization demonstrated zero-order kinetics in which the specific rate and time of total solubilization are a function of the variables in operation. Glucose was produced according to a mechanism of two consecutive first-order pseudo-homogeneous reactions. The values of the kinetic constants k₁ and k₂ have been correlated with temperature, the H₂SO₄ concentration and the acid/substrate relationship.     

Swelling behavior of crosslinked hydroxypropyl cellulose films retaining cholesteric liquid crystalline order. I. Effect of temperature

Temperature dependence of the swelling behavior in both water and propanol was determined for the crosslinked hydroxypropyl cellulose (HPC) films retaining cholesteric liquid crystalline order (CLCO) and for the crosslinked amorphous HPC films. The dependence of swelling behavior in water for the films retaining CLCO was different from that of the amorphous films. With increasing temperature, the equilibrium swelling ratio (B_e) for the films retaining CLCO decreased, whereas B_e for the amorphous films increased. In propanol, both films exhibited the same temperature dependence. B_e increased with increasing temperature. The increasing rate of the swelling in transient state showed similar temperature dependence on B_e. The increasing rate for the films retaining CLCO decreased with temperature, but that for the amorphous films increased in water; in propanol, the increasing rate for two types of films increased. The difference in the swelling behavior between the two types of films may be due to the difference in the number-average molecular weight between crosslinks. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1015–1022, 1999     

Dyeing behavior of swollen cotton fibers and swelling mechanisms of intra- and intercrystalline swelling agents

Dyeability was used to study the swelling mechanisms of intra- and intermicellar swelling agents on cotton cellulose. Reactive and direct dyes were used for dyeing, and zinc chloride, ethylenediamine (EDA), and morpholine were used for swelling reactions. Changes taking place in the accessible regions as a result of swelling were determined by moisture regain, acid hydrolysis, formylation, and the lateral order distribution in the fiber structure. The results indicate that the intracrystalline swelling agents, viz., zinc chloride and EDA, induce specific changes in the accessible portions of the fiber. The accessible portion produced by the inorganic swelling agent has a more open structure than the disordered region produced by the EDA treatment. The distinctive nature of the accessible portions in swollen cotton fibers treated with the two reagents was reflected in all the properties studied. This was attributed to the different mechanisms of swelling and decrystallization of cotton fibers by zinc chloride and EDA. Morpholine was shown to bring about considerable changes in the accessible portions of the cotton fiber which were responsible for increased dyeability with reactive dyes, and was also shown to increase the amount of “truly” accessible regions by breaking the “imperfect crystals” in the disordered regions as well as on the surface of crystallites.     

Radiation-induced graft polymerization of 4-vinyl pyridine to styrene–butadiene–styrene triblock copolymer

The radiation-induced graft polymerization of 4-vinyl pyridine to styrene–butadiene–styrene triblock copolymer (SBS) was investigated. Relations between the rate of grafting and the dose rate when SBS was irradiated in 4-vinyl pyridine–methanol solution, and between the rate of grafting and 4-vinyl pyridine concentration of 4-vinyl pyridine–methanol solution have been investigated. An experiment that had been carried out on SBS immersed in various 4-vinyl pyridine concentration of 4-vinyl pyridine–methanol solutions showed that the extent of swelling of SBS by the various 4-vinyl pyridine–methanol solutions increased with increasing 4-vinyl pyridine concentration. The largest rate was found at 20 vol % 4-vinyl pyridine–methanol solution. The rate was smaller at the volume percent of 4-vinyl pyridine higher or lower than 20 vol %. On the assumption that the theory of homogeneous homopolymerization could be applied to this grafting reaction, the value of k_p²/k_t was obtained, where k_p and k_t are the propagation and termination constant, respectively. The value of k_p²/k_t greatly decreased with increasing adsorbed concentration of vinyl pyridine–methanol solution. This decrease of k_p²/k_t was explained by the fact that 4-vinyl pyridine and methanol absorbed in SBS acted as a plasticizer which increased the molecular motion of the polymer. The solvent effect on the graft polymerization was also investigated. The result was explained by solubility parameter. When the chosen solvent had better solubility with the polymer, the degree of grafting was smaller. That was connected with the extent of the polymer chain mobility.     

Syntheses of hydroxypropyl methylcellulose phthalate hydrogels in Na2CO3 aqueous solutions with electron‐beam irradiation

Novel cellulose ether hydrogels were prepared by the radiation‐induced crosslinking of hydroxypropyl methylcellulose phthalate (HPMCP) in a solution of Na₂CO₃. The effects of several factors, such as the HPMCP concentration, Na₂CO₃ concentration, absorbed dose, and dose rate, on the crosslinking of HPMCP were investigated in detail. An increase in the HPMCP concentration resulted in an increasing content of the gel fraction, and this meant that the crosslinking probability increased as well. Na₂CO₃ was essential for dissolving HPMCP in water, and a 4–5% Na₂CO₃ aqueous solution was optimal for the crosslinking of HPMCP. The dose rate also affected the radiation crosslinking of HPMCP; hydrogels with higher gel fractions and transparency could be formed at lower dose rates. The ratio of degradation to crosslinking of the gel was calculated according to the Charlesby–Rosiak equation, and it showed good agreement with the experimental results. Some important properties, such as the swelling kinetics, ion and ionic strength dependence, and pH dependence, of the HPMCP hydrogels were also investigated. The HPMCP hydrogels possessed excellent swelling rates and swelling ratios in some solvents, such as water and methanol, with a high hydrogen‐bonding parameter. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2123–2130, 2003     

Graft copolymerization of acrylic acid onto cellulose: Effects of pretreatments and crosslinking agent

The graft copolymerization of acrylic acid (AA) and 2‐acrylamido 2‐methylpropane sulfonic acid (AASO₃H) onto cellulose, in the presence or absence of crosslinking agent N,N′‐methylene bisacrylamide (NMBA), by using different concentrations of ceric ammonium nitrate (CAN) initiator in aqueous nitric acid solution at either 5 or 30°C was investigated. To investigate the effect of pretreatment of cellulose on the copolymerization, before some grafting reactions cellulose was pretreated with either 2 or 20 wt % NaOH solutions or heated in distilled water/aqueous nitric acid (2.5 × 10^?3 M) at 55°C. To determine how the excess of initiator affects the grafting and homopolymerization, separate reactions were carried out by removing the excess of ceric ions by filtration of the mixture of initiator solution and cellulose before the monomer addition. Extraction‐purified products were characterized by grafting percentage and equilibrium swelling capacity. Pretreatment of cellulose with NaOH solutions decreased the grafting percentage of copolymers. In the case of AA–AASO₃H mixtures, nonpretreated cellulose gave a higher grafting percentage than NaOH‐pretreated cellulose. Filtration also lowered the grafting of AA on the cellulose in the cases of pretreatment with either water or nitric acid. Copolymers with the highest grafting percentage (64.8%) and equilibrium swelling value (105 g H₂O/g copolymer) were obtained in grafting reactions carried out in the presence of NMBA at 5°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2267–2272, 2001     

Development of a superporous hydroxyethyl cellulose‐based hydrogel by anionic surfactant micelle templating with fast swelling and superabsorbent properties

The self‐assembling anionic surfactant, sodium n‐dodecyl sulfonate (SDS) micelles were used as pore‐forming templating for fabricating novel superporous hydroxyethyl cellulose‐grafting‐poly(sodium acrylate)/attapulgite (HEC‐g‐PNaA/APT) hydrogels. The network characteristics, morphologies of the hydrogels and removing of SDS micelles from the final product by washing with ethanol/water (v/v, 7 : 3) procedure were determined by Fourier transform infrared spectroscopy and scanning electron microscopy, as well as by determination of swelling ratio, swelling rate, and stimuli response to salts and pHs. The results showed that the added‐SDS concentration significantly affected the morphologies and pore structure of the hydrogel, and 2 mM SDS facilitates to form a homogeneous and well‐defined pore structure in the gel network to extremely improve the swelling ratio and swelling rate. The 2 mM SDS‐added superporous HEC‐based hydrogel not only had highest equilibrium swelling ratio (Q_eq, 1118, 102 g g^?1 in distilled water and 0.9 wt % NaCl solution), rapid swelling rate (k_is, 5.2840 g g s^?1), also showed multistimulus responses to salts and pHs, which may allow its applications in several areas such as adsorption, separation and biomedical materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42027.     

Radiation-induced graft copolymerization of styrene to cellulose

The radiation-induced graft copolymerization of styrene to cellulose has been studied in vacuo at 30°C and at dose rates from (0.37 to 8.73) × 10^?2 W/kg. Dioxan was used as solvent for monomer and polystyrene homopolymer, and water (2% total volume) was incorporated as swelling agent for cellulose. The concentration of styrene in the bulk medium was varied from 0.432 to 3.46 moles/l., and the rates of both grafting and homopolymerization were shown to be proportional to [monomer] · [intensity]^1/2. The value of 3.3 × 10^?4 l. mole^?1 sec^?1 derived for k_p²/k_t in homopolymerization is similar to that for normal free-radical polymerization of styrene. However, reduced termination during grafting yielded a much higher value (58 l. moles^?1 sec^?1). Degradation of cellulose in the absence of monomer was followed viscometrically, and values of 13.5 and 24.6 were derived for G (scission) in vacuo and in air, respectively.     

Effect of porosigen and hydrophobic monomer on the fast swelling–deswelling behaviors for the porous thermoreversible copolymeric hydrogels

A series of porous thermoreversible copolymeric hydrogels were prepared from N‐isopropylacrylamide (NIPAAm) and hydrophobic monomers such as 2,2,3,3,4,4,5,5‐octafluoropentyl methacrylate (OFPMA) and n‐butyl methacrylate (BMA) and CaCO₃ or poly(ethylene glycol) 8000 (PEG8000) as porosigen by emulsion polymerization. The effect of hydrophobic monomers and porosigens on the fundamental properties, such as equilibrium swelling ratio, swelling kinetics, gel strength, crosslinked densities, etc., and fast swelling–deswelling behavior for the present copolymeric hydrogels were investigated. Results showed that the deswelling rates for the gels porosigened by CaCO₃ were more rapid than those gels foamed by PEG8000. Results also showed that the swelling rates for the gel foamed by CaCO₃ were higher than those for the gel foamed by PEG8000. At the same time, results also showed that the gels with OFPMA foamed by CaCO₃ exhibit a faster swelling–deswelling behavior than those gels with BMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3152–3160, 2006     

Preparation of higher aliphatic acid esters of wood in an N2O4–DMF cellulose solvent medium

Esterification of wood meal with a series of aliphatic acid anhydrides and acid chlorides in a nonaqueous cellulose solvent, an N₂O₄–DMF solvent, has been studied. The N₂O₄–DMF–pyridine solution used as the reaction medium plays a role in destroying the molecular order of the cellulose within the wood, enabling the cellulose to be uniformly substituted by acyl groups along its chain. These uniformly distributed blocking groups result in the permanent decrystallization of the wood. The acyl blocking groups are best achieved by esterification using acid chlorides in the nonaqueous solvent. Acid chlorides, from caproyl to stearoyl chloride, were found to be much more effective as acylating agents than acid anhydrides, from propionic to caproic anhydride. Although no difference in reactivity can be recognized among the acid chlorides, the reactivity decreases with increase in the number of carbon atoms in the acyl group among the acid anhydrides.     

A kinetic model for pyrolysis of cellulose

It has been shown that the pyrolysis of cellulose at low pressure (1.5 Torr) can be described by a three reaction model. In this model, it is assumed that an “initiation reaction” leads to formation of an “active cellulose” which subsequently decomposes by two competitive first-order reactions, one yielding volatiles and the other char and a gaseous fraction. Over the temperature range of 259–341°C, the rate constants of these reactions, k_i (for cellulose → “active cellulose”), k_v (for “active cellulose” → “volatiles”), and k_c (for “active cellulose” → char + the gaseous fraction) are given by k_i = 1.7 × 10²¹e^{? (58,000/RT)} min ^?1, k_v = 1.9 × 10¹⁶e^{? (47,300/RT)} min^?1, and k_c = 7.9 × 10¹¹e^{? (36,600/RT)} min^?1, respectively.     

Synthesis,characterization and swelling behaviors of hydroxyethyl cellulose‐g‐poly(acrylic acid)/attapulgite superabsorbent composite

In this work, a series of novel hydroxyethyl cellulose‐ g‐poly(acrylic acid)/attapulgite (HEC‐g‐PAA/APT) superabsorbent composites were prepared through the graft polymerization of hydroxyethyl cellulose (HEC), partially neutralized acrylic acid (AA), and attapulgite (APT) in aqueous solution, and the composites were characterized by means of Fourier‐transform spectroscopy, scanning electron microscopy, and transmission electronmicroscopy. The effects of polymerization variables including concentrations of the initiator and crosslinker and APT content on water absorbency were studied, and the swelling properties in various pH solutions as well as the swelling kinetics in various saline solutions were also systematically evaluated. Results showed that the introduction of 5 wt% APT into HEC‐g‐PAA polymeric network could improve both water absorbency and water absorption rate of the superabsorbent composites. In addition, the superabsorbent composites retained high water absorbency over a wide pH range of 4–10, and the swelling kinetics of the superabsorbent composites in CaCl₂ and FeCl₃ solutions exhibited a remarkable overshooting phenomenon. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

The effect of multiple swelling treatment with ethylenediamine on cotton cellulose

Cotton cellulose was subjected to repeated swelling treatment with aqueous solutions of ethylenediamine (EDA). Although EDA is capable of effecting a lattice change from cellulose I to cellulose II during successive swelling treatments, resistance to lattice transformation is offered during the first treatment in spite of the formation of cellulose–EDA complex. This is attributed to a structural hinderance existing in the cellulose molecule itself. There is considerable improvement in the lateral order of the treated cellulose on subjecting it to repeated swelling operations with EDA.     

Lamellar morphology of poly(trimethylene terephthalate)/poly(ether imide) blends studied via small‐angle X‐ray scattering

The lamellar morphology of a melt‐miscible blend consisting of poly(trimethylene terephthalate) (PTT) and poly(ether imide) (PEI) prepared by solution precipitation has been investigated by means of optical polarized microscopy (POM) and small angle X‐ray scattering (SAXS). From the observation under POM, it was suggested that PEI was predominantly segregated into the interlamellar and/or interfibrillar regions upon PTT crystallization since the PTT spherulitic morphologies of blends were volume‐filling. From results of SAXS data analysis, a larger amorphous layer thickness was identified in the blends, showing that some PEI was incorporated inside the interlamellar regions after crystallization. Despite the swelling of the amorphous layer, the amorphous layer thickness was relatively independent of the blend composition. It was concluded that amorphous PEI was located in the interlamellar regions of PTT as the weight fraction of PEI (w_PEI) [≤] 0.1, while amorphous PEI was predominantly segregated into the interfibrillar regions of PTT as w_PEI > 0.1, and the extent of interfibrillar segregation increased with increasing w_PEI. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Measurements of Singlet Oxygen‐Quenching Activity of Vitamin E Homologs and Palm Oil and Soybean Extracts in a Micellar Solution

Recently, a new assay method that can quantify the singlet oxygen‐absorption capacity (SOAC) of antioxidants (AO) and food extracts in homogeneous organic solvents has been proposed. In the present study, second‐order rate constants (k_Q) for the reaction of singlet oxygen (¹O₂) with vitamin E homologs (α‐, β‐, γ‐, and δ‐tocopherols [Toc] and α‐, β‐, γ‐, and δ‐tocotrienols [Toc‐3]) were measured in an aqueous Triton X‐100 (5.0 wt%) micellar solution (pH 7.4). Toc‐3 showed k_Q values larger than those of Toc in a micellar solution, although Toc and Toc‐3 showed the same k_Q values in a homogeneous solution. Similar measurements were performed for 5 palm oil extracts 1–5 and one soybean extract 6, which contained different concentrations of Toc, Toc‐3, and carotenoids. It has been clarified that the ¹O₂‐quenching rates (k_Q) (that is, the relative SOAC value) obtained for extracts 3–6 may be explained as the sum of the product of the rate constant () and the concentration ([AO‐i]/100) of AO‐i contained. The UV–vis absorption spectra of Toc and Toc‐3 were measured in a micellar solution and chloroform. The results obtained demonstrated that the k_Q values of AO in homogeneous and heterogeneous solutions vary notably depending on (1) polarity (dielectric constant [ε]) of the reaction field between ¹O₂ and AO, (2) the local concentration of AO, and (3) the mobility of AO in solution. The results suggest that the SOAC method is applicable to the measurement of ¹O₂‐quenching activity of general food extracts in a heterogeneous micellar solution.     

Modification of the fine structure of cellulose by halogen and heat treatments

Treatment of various celluloses such as cotton, sulphite, and sulphate pulp with bromine water brings about profound changes in the fine structure of the fiber. Depending on the conditions of the treatment and on the nature of the cellulose, increases or decreases in the accessibility of the cellulose are observed, indicating crystallization and decrystallization processes. In the case of bleached sulphate pulp, similarly to rayon previously studied, an initial decrystallization proceeds the crystallization step. These changes were determined by the IR method, which was correlated previously to the bromine accessibility method. They are accompanied by highly significant changes in moisture absorption. The crystallization proceeds according to first-order kinetics with respect to the concentration of the less-ordered regions (LOR) of the cellulose. The rates of crystallization for the various celluloses varied in a range of 4 orders of magnitude. The activation energies of the bromide induced crystallization were found for all celluloses to be in the range of 10–15 kcal/mol, as compared to 30–40 kcal/mol obtained upon crystallizing the same celluloses by heating in the temperature range of 180–200°C. These values correspond to those of solvent and thermal crystallizations of poly(ethylene terephthalate), indicating the similarity between the crystallization mechanisms of the two polymers.     

Diffusion with simultaneous reaction of reactive dyes in cellulose. II. Effect of hydrolysis

Theoretical equations that describe the concentration profiles of immobilized and active species for reactive dyes were derived from the diffusion equation accompanied by the reaction with cellulose and water in the substrate. The diffusion coefficient D and the rate constant of the reaction with cellulose, k_cell, and that with water in cellulose, k_w, were estimated by using the theoretical equations and the cylindrical film roll method. The theory predicted that the apparent diffusion coefficients decreased with the hydrolysis of active species in cellulose. Results from diffusion experiments with C.I. Reactive Yellow 4 and Orange 1 show that the ratio P of k_w to k_cell for Orange 1 increased with increase in pH to about pH 13 and that the P for Yellow 4 was smaller than unity. Using an alternative experiment to diffusion, P of Orange 1 was measured to be 1.0–1.5, and that of Yellow 4 was smaller than unity at pH 11.6 at 30°C. It was therefore concluded that the D of active species was constant to a highly alkaline region and that the decrease in the apparent diffusion coefficient of Orange 1 was mainly due to the hydrolysis of active species in cellulose.     

溶胀剂对黏胶纤维催化脱水的影响

主要研究了不同浓度的乙二胺、尿素水溶液对黏胶纤维的溶胀作用,以及溶胀对催化剂催化效果的影响。通过保水值、吸碘值、~(13)C NMR和热失重分析等测试手段,对溶胀后的纤维性能进行了表征。结果发现:溶胀破坏了纤维内部的氢键结构,使分子链间距加大,催化剂分子更容易进入到纤维内部起到更好的催化效果。通过测定纤维的保水值和吸碘值,对比了乙二胺和尿素水溶液对黏胶纤维的溶胀效果,发现乙二胺对黏胶纤维的溶胀作用更强。~(13)C NMR结果表明,乙二胺对黏胶纤维有更大的消晶作用。热失重曲线表明:经乙二胺溶胀后的纤维的初始热失重温度进一步降低,有利于纤维在更低的温度下进行热处理,节约能耗。纤维强度测试结果表明,溶胀处理可以有效提高催化剂的催化效率。