Superhydrophobic surfaces from surface-hydrophobized cellulose fibers with stearoyl groups

In this report, surface-hydrophobized cellulose fibers by stearoyl groups were used for the construction of superhydrophobic surfaces. The product after the synthesis contains two components: cellulose microfibers as the major component and nanoscaled segments in small amounts. The crystalline structure of cellulose was maintained after surface modification based on solid-state ¹³C NMR spectroscopy. Superhydrophobic surfaces showing static water contact angles of >150° were fabricated using freshly prepared products containing both components via the facile route, e.g., solvent casting. The cellulose types, microcrystalline cellulose or cotton linter cellulose fibers, did not significantly affect the chemical modification of cellulose fibers, but the superhydrophobic surfaces using surface-hydrophobized cotton linters as starting materials exhibited higher surface hydrophobicity and better impact stability in comparison to shorter microcrystalline cellulose. Due to the presence of a crystalline cellulose skeleton, the obtained superhydrophobic surfaces are stable during the heat treatment at 80 °C.     

Differential thermal analysis of polyester/cotton blends treated with Thpc—urea—poly(vinyl bromide)

Differential thermal analyses (DTA) were made on a series of polyester/cotton blend fabrics before and after treatment with Thpc—urea—poly(vinyl bromide). This flame retardant did not affect the polyester melting endotherm, which was proportional to the polyester content and appeared at approximately 250°C. In nitrogen atmosphere, DTA of the treated blends showed exothermic peaks at 285°C for the cotton decomposition. and at 415°C for the polyester decomposition. In air, DTA of the treated blends showed exothermic peaks at 333°C for cellulose decomposition, at 431°C for polyester decomposition and at 490°C for char decomposition. The Thpc-urea component of the flame retardant is effective on the cotton cellulose portion of the blend; the poly(vinyl bromide) appears to decompose and act in the vapor state on the polyester.     

Effects of temperature and molecular weight on dissolution of cellulose in NaOH/urea aqueous solution

Dissolution of cellulose having different viscosity-average molecular weight (M _η ) in 7 wt%NaOH/12 wt%urea aqueous solution at temperature from 60 to −12.6°C was investigated with optical microscope, viscosity measurements and wide X-ray diffraction (WXRD). The solubility (S_a) of cellulose in NaOH/urea aqueous solution strongly depended on the temperature, and molecular weight. Their S_a values increased with a decrease in temperature, and cellulose having M _η below 10.0 × 10⁴ could be dissolved completely in NaOH/urea aqueous solution pre-cooled to −12.6°C. The activation energy of dissolution (E_a,s) of the cellulose dissolution was a negative value, suggesting that the cellulose solution state had lower enthalpy than the solid cellulose. The cellulose concentration in this system increased with a decrease of M _η to achieve about 8 wt% for M _η of 3.1 × 10⁴. Moreover, cellulose having 12.7 × 10⁴ could be dissolved completely in the solvent pre-cooled to −12.6°C as its crystallinity (χ _c) decreased from 0.62 to 0.53. We could improve the solubility of cellulose in NaOH/urea aqueous system by changing M _η , χ _c and temperature. In addition, the zero-shear viscosity (η ₀ ) at 0°C for the 4 wt% cellulose solution increased rapidly with an increase of M _η , as a result of the enhancement of the aggregation and entanglement for the relatively long chains.     

A new methodology to recycle polyester from fabric blends with cellulose

Development of a simple process for separating cellulose and polyester from their mixed fabrics is indispensable for the recycling of waste mixed fabrics. The authors have developed an efficient two-step procedure that consists of an acid treatment and successive mechanical treatment of the mixed fabrics, or more specifically a 1-min static acid treatment of the mixed fabrics with 95 °C aqueous 10 N H₂SO₄ and successive mechanical beating in room-temperature water. The procedure was also found to be effective for the separation of regenerated cellulosic fabrics from their mixed fabrics with polyester. Cellulose was efficiently removed from polyester fabrics as a powder, with high recovery of both cellulose powder and polyester cloth.     

Cool temperature hinders flux from glucose to sucrose during cellulose synthesis in secondary wall stage cotton fibers

Current knowledge about the integration of cellulose synthesis into cellular carbon metabolism and the cool temperature sensitivity of cellulose synthesis is reviewed briefly. Roles for sucrose synthase (to channel UDP-glucose to the cellulose synthase) and sucrose phosphate synthase (to recycle the fructose released by sucrose synthase to more sucrose) in secondary wall cellulose synthesis are described. Data are presented that implicate sucrose synthesis within cotton fibers as a particularly cool temperature-sensitive step in the partitioning of carbon to cellulose. Sugar metabolism during fiber secondary wall deposition was analyzed in in vitro cultures of ovules from two cultivars of Gossypium hirsutum L. (cv. Acala SJ-1 and cv. Paymaster HS 200), which had different levels of cool temperature sensitivity. The sizes of the sucrose, glucose, and fructose pools within fibers at 4 and 7 h after a temperature shift to 15 or 34 °C did not change in either cultivar. Feeding exogenous U-¹⁴C-glucose in pulse and pulse/chase experiments showed that uptake of glucose and transport through the ovule into fibers occurred at the same rate at 34 and 15 °C. In contrast, the flux from glucose to sucrose within fibers was greatly hindered at 15 °C in both cultivars. Since sucrose is the preferred donor of UDP-Glc to the cellulose synthase during secondary wall deposition, this sensitivity in sucrose synthesis is likely to at least partially explain the cool temperature sensitivity of cotton fiber cellulose synthesis that is observed in the field.     

Asymmetrically superhydrophobic cotton fabrics fabricated by mist polymerization of lauryl methacrylate

A graft-polymerization process with atomized lauryl methacrylate as monomer is used to fabricate fluorine-less and asymmetrically superhydrophobic cotton fabrics. The polymers synthesized in the process can form nanoscale hierarchical structures on the cotton surface, and the surface morphology can be controlled by choosing a suitable solvent or by varying the feeding quantity of the monomer mist stream. After applying the surface modification to cotton fabrics, an asymmetrically superhydrophobic surface is achieved without any additional nanosized particles, and the solvent damages on the cotton fabrics are controllable at a very low level. Surface characterization reveals that the modified side of the cotton fabric has laundering-durable and mechanically stable superhydrophobicity with a water contact angle of more than 150°, whereas the opposite inherits the hydrophilic property of pristine cotton fabric. The modified cotton fabrics are found to have medium-level water-absorbing ability between pristine cotton and PET fabrics, as well as good vapor transmissibility similar to pristine cotton fabric. These properties are of great significance in textile and medical applications.     

Effect of cationization on adsorption of silver nanoparticles on cotton surfaces and its antibacterial activity

Cotton was cationized by exhaustion method using 3-chloro-2-hydroxypropyl trimethyl ammonium chloride (CHPTAC) as a cation-generating agent. Adsorption of silver nanoparticles on normal and cationized cotton was studied by exhaustion method at temperatures of 80°C and 100°C. Two exhaustion baths were used, containing nanosilver colloidal solutions stabilized by two different stabilizers and various concentrations of silver nanoparticles. Fourier-transform infrared (FT-IR) spectra of normal and cationized samples confirmed the existence of quaternary ammonium groups on cationized cellulose fibers. X-ray diffraction (XRD) patterns showed that crystallinity of the modified cellulose fibers was decreased. Scanning electron microscope (SEM) images revealed that the surface of the modified cotton was rougher than that of normal cotton. In addition, SEM images showed the presence of silver nanoparticles on the surface of treated fabric samples. The amount of silver particles adsorbed on the fabric samples was determined using inductively coupled plasma-optical emission spectrometer. Antibacterial tests were performed against Escherichia coli bacteria as an indication of antibacterial effect of samples. Cationized cotton samples adsorbed more silver nanoparticles and then had greater ability to inhibit bacteria.     

Immobilization of cellulose extracted from Robinia Pseudoacacia seed fibers onto chitosan: Chemical characterization and study of methylene blue removal

The design of economical adsorbents to remove pollutants from contaminated water is attracting more attention. In this study, cellulose was successfully extracted from Robinia Pseudoacacia seed fibers and immobilized onto chitosan beads. The prepared spherical beads were then used for the biosorption of methylene blue dye from aqueous media. Samples were investigated using several analytical methods, namely FT-IR, XRD, EDX, SEM, and TGA analyses. The adsorption experiments showed that combining cellulose with chitosan improved the removal of methylene blue. The maximum uptake amount of methylene blue using cellulose–chitosan composite beads was 55 mg/g. However, it was about 35 mg/g at 20 °C for chitosan beads. The kinetic data complied strongly with the pseudo-second order equation, suggesting that the biosorption phenomenon has predominantly a chemical nature. Overall, the current study has shown a promising technique to design new adsorbents from abundant natural polymers for eliminating cationic dyes from water.     

Identification of a Keratinase-Producing Bacterial Strain and Enzymatic Study for Its Improvement on Shrink Resistance and Tensile Strength of Wool- and Polyester-Blended Fabric

A wool-degrading bacterium was isolated from decomposition wool fabrics in China. The strain, named 3096-4, showed excellent capability of removing cuticle layer of wool fibers, as demonstrated by removing cuticle layer completely within 48 h. According to the phenotypic characteristics and 16S rRNA profile, the isolate was classified as Pseudomonas. Bacteria growth and keratinase activity of the isolate were determined during cultivation on raw wool at different temperatures, initial pH, and rotation speed using orthogonal matrix method. Maximum growth and keratinase activity of the bacterium were observed under the condition including 30 °C, initial pH 7.6, and rotational speeds 160 rpm. The keratinase-containing crude enzyme prepared from 3096-4 was evaluated in the treatment of wool fabrics. The optimal condition of our enzymatic improvement of shrink resistance was the combination of 30 °C, initial pH 7.6, and rotation speeds 160 rpm. After the optimized treatment, the wool fabrics felting shrink was 4.1% at 6 h, and textile strength was not lost.     

Fibrillation Tendency of Cellulosic Fibers. Part 1: Effects of Swelling

The fibrillation tendencies of various cellulosic fibers in aqueous solution containing alkali metal hydroxide and ethanol were evaluated with two specific parameters: the critical point of fibrillation (CPF_conc.), that is a concentration of swelling agent where the fibrillation begins, and the ratio of initial increase in fibril number to increase in concentration of swelling agent (I_i). The CPF_conc. and the I_i are defined as fibrillation stability and fibrillation sensitivity to swelling agent, respectively. Lyocell fiber (CLY1) has the smallest CPF_conc. and the largest I_i, representing the lowest fibrillation stability and the highest fibrillation sensitivity, leading to the highest fibrillation tendency in CLY1 among the fibers tested. Although crosslinking improved fibrillation stability in lyocell as compared to modal, the fibrillation stability remained higher owing to the high water capacity and the high affinity for alkali. In alkali solution at the same concentration CLY1 fibrillation increased in the order of LiOH > NaOH > KOH. However, the plot of fibril number against solvent retention value of CLY1 in different alkaline solutions gives a slope of 110 count · g/cm³ regardless of alkali type, the critical degree of swelling for CLY1 with no fibrillation was 0.62 cm³/g in alkali solutions and 0.45 cm³/g in ethanol/water mixture.     

Sorption of vapors of organic solvents with cyanoethyl hydroxyethyl cellulose

The interaction of cyanoethyl hydroxyethyl cellulose with acetone, methylene chloride, and trifluoroacetic acid in the temperature range 10–50°C was studied by the solvent vapor sorption technique. The temperature and concentration dependences of the Flory-Huggins parameter for polymer-solvent interaction Z₁ and the mechanism of the structural rearrangement in the systems were determined.     

Extraction of Co-Products from Biomass: Example of Thermal Degradation of Silymarin Compounds in Subcritical Water

In an effort to increase revenues from a given feedstock, valuable co-products could be extracted prior to biochemical or thermochemical conversion with subcritical water. Although subcritical water shows significant promise in replacing organic solvents as an extraction solvent, compound degradation has been observed at elevated extraction temperatures. First order thermal degradation kinetics from a model system, silymarin extracted from Silybum marianum, in water at pH 5.1 and 100, 120, 140, and 160 °C were investigated. Water pressure was maintained slightly above its vapor pressure. Silymarin is a mixture of taxifolin, silichristin, silidianin, silibinin, and isosilibinin. The degradation rate constants ranged from 0.0104 min⁻¹ at 100 °C for silichristin to a maximum of 0.0840 min⁻¹ at 160 °C for silybin B. Half-lives, calculated from the rate constants, ranged from a low of 6.2 min at 160 °C to a high of 58.3 min at 100 °C, both for silichristin. The respective activation energies for the compounds ranged from 37.2 kJ/gmole for silidianin to 45.2 kJ/gmole for silichristin. In extracting the silymarin with pure ethanol at 140 °C, no degradation was observed. However, when extracting with ethanol/water mixtures at and 140 °C, degradation increased exponentially as the concentration of water increased. An erratum to this article can be found at     

Novel UV-protective formulations for cotton, PET fabrics and their blend utilizing irradiation technique

A novel coating formulation to impart ultraviolet (UV) protection property to cotton, Polyethylene trephethalate (PET) and cotton/PET fabrics was prepared and gamma rays as an ionizing radiation was utilized for surface curing. Natural occurring aluminum potassium sulfate (Alum) was used individually and in binary coat with Zinc Oxide (ZnO), to induce the UV-blocking properties. It was found that using Alum (0.3 g/ml) caused a prompt increase in ultraviolet protection factor (UPF) over the uncoated fabrics. Moreover, the incorporated ZnO in the binary coat increased the UPF for two to threefold than the stand-alone Alum coating, specially in case of PET coated fabric. Water absorbance and moisture regain of ZnO and Alum/ZnO coated fabrics showed a decrease over the blank samples, due to the usage of oligomer/monomer combination. On contrary, Alum showed a hydrophilic effect with the increase in its content in the formulation. Surface Electron Microscope showed the homogenous coating of fibers. X-ray diffraction (XRD), energy dispersive X-ray (EDX) and water vapor permeability were also tested for coated samples.     

Interactions with water of mixed acetic-fatty cellulose esters

Cellulose powder was acylated with mixtures containing acetic, fatty and acetic-fatty anhydrides to form acetic-fatty cellulose esters. The total degree of substitution (DS) of the mixed cellulose esters (MCE) ranged from 2 × 10⁻² to 2.92. MCE were characterized by their interactions with water. Static contact angles with water were measured on a regular smooth surface. The values found were dependent on the fatty acyl content and independent of the acetyl content. In the case of acetic-oleic cellulose esters, the minimum DS of the oleoyl moiety required to obtain permanent water repellency was 3 × 10⁻⁴. The microporosity of the samples may account for this exceptional hydrophobic character. Nevertheless, water vapor adsorption measurements on powder samples revealed only a limited increase in hydrophobicity of the MCE compared to cellulose acetate with the same acetyl content. It was thus demonstrated that water repellency and vapor water adsorption are not correlated.     

Cellulose II nanoelements prepared from fully mercerized, partially mercerized and regenerated celluloses by 4-acetamido-TEMPO/NaClO/NaClO2 oxidation

A softwood bleached kraft pulp (SBKP) and cotton lint cellulose were fully or partially mercerized, and these along with celluloses and commercially available regenerated cellulose fiber and beads were oxidized by 4-acetamido-TEMPO/NaClO/NaClO₂ at 60 °C and pH 4.8. Weight recovery ratios and carboxylate contents of the oxidized celluloses were 65–80% and 1.8–2.2 mmol g⁻¹, respectively. Transparent and viscous dispersions were obtained by mechanical disintegration of the TEMPO-oxidized celluloses in water. These aqueous dispersions showed birefringence between cross-polarizers, indicating that mostly individualized cellulose nanoelements dispersed in water were obtained by these procedures. Transmission electron microscopy observation showed that the cellulose nanoelements prepared from mercerized SBKP, repeatedly mercerized SBKP, mercerized cotton lint cellulose, regenerated cellulose beads and 18% NaOH-treated SBKP, i.e. partially mercerized SBKP, had similar morphologies and sizes, 4–12 nm in width and 100–200 nm in length. The 18% NaOH-treated SBKP was converted to cellulose nanoelements consisting of both celluloses I and II.     

Synthesis and characterization of novel amino cellulose esters

The homogeneous conversion of cellulose dissolved in N-methyl-2-pyrrolidone/LiCl and 1-N-butyl-3-methylimidazolium chloride with N-methyl-2-pyrrolidone, ε-caprolactam, N-methyl-ε-caprolactam, and N-methyl-2-piperidone in the presence of p-toluenesulphonic acid chloride was studied. Depending on the reaction conditions, novel cellulose esters with degree of substitution (DS) values ranging from 0.12 to 1.17 could be prepared. The structure of the amino group containing cellulose esters was elucidated by elemental analysis, FTIR- and NMR spectroscopy. NMR spectroscopy revealed an almost complete esterification of position 6 of the anhydroglucose unit at DS of 1. The conversion can be conducted between room temperature and 40 °C, while side-reactions became predominant at 60 °C. Starting with DS of 0.24, the samples were soluble both in water and dimethyl sulphoxide. The derivatives described are capable of forming polyelectrolyte complexes. The samples were stable at room temperature in aqueous solution at pH 2 and 7. Lower viscosities were found for samples with higher DS in aqueous solution at comparable molar mass.     

Atmospheric control of gel-oxide transformation in sol–gel derived Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> fibers

Via sol–gel processing metal–organic fibers were produced and dried up to 140 °C. For these gel fibers the influence of a treatment in different atmospheres was investigated for the temperature range of 200–850 °C. The atmospheres were nitrogen, water vapor, evaporated nitric and hydrochloric acid and evaporated hydrogen peroxide. In the presence of moisture and especially with acidic moisture fibers were transformed almost completely to their oxide composition (82 mol% Al₂O₃·18 mol% Y₂O₃). In these inorganic amorphous structures considerable differences were observed on several structural levels. On the atomic scale, the coordination of Al ions was investigated by ²⁷Al MAS NMR and skeletal density by He-pycnometry. Porosity in the nm scale was characterized by N₂-sorption. As a macroscopic effect of different treatment atmospheres, the longitudinal shrinkage was observed. For fibers treated at 500 °C the relative shrinkage varied by 100% (comparing water vapor and nitrogen atmosphere). No simple correlation between the release of organic constituents, the formation of porosity and the shrinkage could be found. These aspects were controlled by the rigidity of the inorganic network against atomic reconstitution. The kind of atmosphere was found to be an effective parameter to control various aspects of the xerogel structure.     

Production,Partial Characterization,and Use of a Red Biochrome Produced by <Emphasis Type="Italic">Serratia sakuensis</Emphasis> subsp. nov Strain KRED for Dyeing Natural Fibers

We have described a novel red biochrome, 514 Da in size, produced by solid-state cultivation of a bacterial isolate obtained from garden soil. The growth requirements of the isolate, the chemical characteristics of the biochrome produced, and the application of the biochrome in dying of silk, wool, and cotton fabrics have been studied. The biochrome obtained after 52 h of incubation and having a λ _max of 535 nm was used for dyeing the fabrics. We found that silk, wool, and cotton fabrics dyed with this new natural red compound have high color strength values and dye uptake along with good color fastness as well as antibacterial activity.     

Cellulose fiber biodegradation in natural waters: river water,brackish water,and seawater

Cellulose, the main component of plant cell walls, is degradable in nature. However, to the best of our knowledge, this is the first report that compares the biodegradability of cellulose fibers with different structures in natural waters. River water, brackish water, and seawater were collected from the Kamo River and Osaka Bay, Japan. Biodegradation of cellulose fibers with different structures and crystallinities, ramie, mercerized ramie, and regenerated cellulose fibers in the collected natural water was investigated in the dark at 20 °C for 30 days. The primary and aerobic ultimate biodegradability were evaluated by weight loss and biochemical oxygen demand (BOD) tests, respectively. In the weight-loss test, cellulose fibers were found to be degraded by more than 50% in any natural water within 30 days. However, in the BOD test, biodegradation was diminished, with values of 40%, 20–30%, and 2–10% in river water, brackish water, and seawater, respectively. These results indicate that cellulose fibers are easily degraded into fine fragments, but it is difficult to cause their ultimate decomposition into water and carbon dioxide. Existence of such a tendency in the degree of biodegradation among the cellulose fibers remains unclear. The molecular weight of cellulose fibers in natural water was also measured during their degradation. The degradation behavior in river water and seawater was observed to be different from that in brackish water. The results thus obtained indicate that the microorganisms and enzymes that degrade cellulose fibers differ depending on the natural water, which influences the degree and mechanism of biodegradation.

     

How does the never-dried state influence the swelling and dissolution of cellulose fibres in aqueous solvent?

The swelling and dissolution capacity of dried and never-dried hardwood and softwood pulps and cotton linters was compared in two aqueous solvents, N-methylmorpholine-N-oxide (NMMO)-water at 90 °C with water contents ranging from 16 to 22% and NaOH—water at −6 °C with NaOH contents ranging from 5 to 8%. Swelling and dissolution mechanisms were observed by optical microscopy and dissolution efficiency was evaluated by recovering insoluble fractions. The results show a contrasted picture towards the effect of the never-dried state on the swelling and the dissolution capacity depending on the origin of the fibres and the type of aqueous solvent. In the case of NMMO—water, the presence of water within and around the fibre does not seem to favour dissolution initiation but after 2 h of mixing the dissolution yield appears to be similar for either dried or never-dried state. The limiting factor for dissolution in NMMO—water is not the penetration of the solvent inside the cellulose fibres, but only the local concentration of NMMO molecules around the fibre. For NaOH—water, both optical microscopy observations on individual fibres and dissolution yield measurements show that the never-dried state is more reactive for softwood pulps and cotton linters and has no significant effect on hardwood pulps. In this case, the local decrease of solvent strength is counteracted by the opening of the structure in the never-dried state which should enable the Na⁺ hydrated ions to penetrate easier.