Evaluation of the phytomass source for composite preparation

The properties of lignocellulose materials from the trunk and bark of trees, and from agricultural sources were investigated by thermogravimetry (TG) and pyrolysis–gas chromatography/mass spectrometry (Py‐GC/MS). The goal was to learn which of the phytomass sources is the most accessible to dehydration and aldol reactions, and in this way could be considered suitable for composite preparation by the thermal pressing treatment. The bagasse second differential thermal analysis peak in air is at the highest temperature acceptable for intermolecular dehydration/crosslinking, and therefore we consider bagasse to be the most suitable candidate for composite preparation. From the TG results in air at 250°C, it follows that willow wood and bagasse are the most thermally resistant sources. The data obtained by Py‐GC/MS analysis showed glycolaldehyde and acetic acid as dominant markers related to adhesion properties via aldol condensation. The detected sum amount of glyceraldehyde and acetic acid decreases in the order: beech wood > bagasse > acacia wood > sugar beet pulp, whereas the remaining species produced much less of it. By comparing results run at above conditions with composite preparation using the pressing thermal treatment at a temperature of 150°C and pressures up to 800 kPa, the suggested evaluation was examined for application on sugar beet residue. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microwave‐assisted hydrothermal liquefaction of lignin for the preparation of phenolic formaldehyde adhesive

This study aimed to produce phenolic formaldehyde (PF) adhesives using the liquefaction product of bagasse lignin (LPBL) as a partial substitute for petroleum‐based phenol. Lignin was extracted from bagasse using 93% acetic acid solution and was rapidly degraded in hot‐compressed water by microwave heating using oxalic acid as catalyst. The liquefaction yield reached 78.69% under the optimal reaction condition. Gas chromatography–mass spectrometry (GC/MS) analysis showed that the main chemical compounds of the liquefaction product included mono‐substituted and bis‐substituted phenols, such as 2,6‐dimethoxyphenol, 4‐hydroxybenzaldehyde, and so on. The LPBL was employed to replace a portion of phenol at varying ratios from 0 to 20 wt % in the preparation of PF adhesives. The molecular weight, viscosity, and adhesive strength of LPBL‐PF adhesives were found to be lower than those of pure PF adhesives. With the phenol replaced by LPBL up to 20%, the viscosity and adhesive strength of the resin were 4.046 Pa s and 1.017 MPa, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44510.     

甘蔗渣的蒸爆及水解技术的研究

以甘蔗渣为原料,对蒸爆预处理进行了研究,考察了蒸爆压力和时间对甘蔗渣水解的影响。并研究了稀酸蒸焊对还原糖得率的影响。     

Preparation and characterization of Maillard reacted chitosan films with hemicellulose model compounds

The Maillard reaction between chitosan and hemicellulose model compounds such as mannose, xylose, and glucuronic acid was investigated. Chitosan and the compounds were dissolved in 1% acetic acid and were dried at 50°C. In an analysis of the film obtained, weight increase, color difference, FTIR, relative amount of free amino groups, insolubility to dilute acetic acid, and tensile properties were measured. The film weight increased gradually as the compounds were added, and the color difference changed significantly. In addition, the relative amount of free amino groups decreased rapidly, and the insoluble matter increased markedly. In particular, xylose brought about drastic changes in a small amount addition. According to the results of FTIR spectra, the cleavage of sugar unit of chitosan and the formation of heterocyclic compounds were observed in all compounds. The formation of carbonyl and carboxyl groups was observed with the addition of a large amount of the compounds. The tensile strength was improved in 10–20 wt % additions of the compounds. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Interfacial properties of chitosan and nonylphenol polyoxyethylene ether

Nonylphenols are water‐soluble surfactants that are used extensively in industry and are found in many consumer products. Nonylphenol polyoxyethylene ether (known commercially as TX‐100), which is one of the most popular members of this family, has a detrimental effect on the environment. Adding chitosan to a solution of TX‐100 reduces the amount of surfactant required while maintaining its surface activity. We evaluated the interfacial properties, including the surface tension, contact angle, and particle size, as well as the fluorescence and Fourier transform infrared spectra of various test solutions prepared from three stock solutions: (1) chitosan dissolved in dilute acetic acid, (2) TX‐100 dissolved in deionized water, and (3) a mixed chitosan/TX‐100 solution. Previous results revealed that low concentrations of TX‐100 are relatively harmless to the environment; in this study, we found that its surface activity at a higher concentration was equal to that of its chemical mixture with chitosan. In addition, we found that the presence of chitosan improved the stability of emulsions of TX‐100. The micellar particles were small, and the stability of the emulsion was maximized at a TX‐100 to chitosan ratio of 7 : 3. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

甘蔗渣的蒸爆及水解技术的研究

以甘蔗渣为原料,对蒸爆预处理进行了研究,考察了蒸爆压力和时间对甘蔗渣水解的影响,并研究了稀酸蒸爆对还原糖得率的影响。     

Adhesion of surface‐grafted low‐density polyethylene plates with enzymatically modified chitosan solutions

An investigation was undertaken on application of dilute chitosan solutions modified by tyrosinase‐catalyzed reaction with 3,4‐dihydroxyphenetylamine (dopamine) to adhesion of the low‐density polyethylene (LDPE) plates surface‐grafted with hydrophilic monomers. Tensile shear adhesive strength effectively increased with an increase in the grafted amount for methacrylic acid‐grafted and acrylic acid‐grafted LDPE (LDPE‐g‐PMAA and LDPE‐g‐PAA) plates. In particular, substrate breaking was observed at higher grafted amounts for LDPE‐g‐PAA plates. The increase in the amino group concentration of the chitosan solutions and molecular mass of the chitosan samples led to the increase in adhesive strength. Adhesive strength of the PE‐g‐PMAA plates prepared at lower monomer concentrations sharply increased at lower grafted amounts, which indicates that the formation of shorter grafted PMAA chains is an effective procedure to increase adhesive strength at lower grafted amounts. Infrared measurements showed that the reaction of quinone derivatives enzymatically generated from dopamine with carboxyl groups was an important factor to increase adhesive strength in addition to the formation of the grafted layers with a high water absorptivity. The above‐mentioned results suggested that enzymatically modified dilute chitosan solutions can be applied to an adhesive to bond polymer substrates. The emphasis is on the fact that water is used as a solvent for preparation of chitosan solutions and photografting without any organic solvents. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

稀硫酸预浸渍对玉米秸秆蒸汽爆破预处理的影响

为提高纤维素乙醇生产中传统蒸汽爆破预处理的效果,以稀硫酸（质量浓度0．2％）对玉米秸秆进行预浸渍,再于190～210℃对其进行汽爆预处理。结果表明：稀硫酸预浸渍有利于增强汽爆过程中半纤维素的水解程度,并能有效减少乙酸的生成;200℃预处理玉米秸秆经过96h同步糖化发酵,最终乙醇浓度为22．5g·L-1,为理论值的76％,较预浸渍前（19．0g·L-1）明显提高。稀硫酸预浸渍能够增强玉米秸秆的汽爆预处理效果。     

Influence of nanoclay and coupling agent on the physical and mechanical properties of polypropylene/bagasse nanocomposite

In this work, the effects of nanoclay (1–4 wt %) and coupling agent (2 and 4 wt %) loading on the physical and mechanical properties of nanocomposites are investigated. Composites based on polypropylene (PP), bagasse flour, and nanoclay (montmorillonite type) was made by melt compounding and then compression molding. When 1–3 wt % nanoclay was added, the tensile properties increased significantly, but then decreased slightly as the nanoclay content increased to 4%. The impact strength was 6% lower by the addition of 1 wt % nanoclay, it was decreased further when the nanoclay content increased from 1 to 4%. Finally, the water absorption of PP/bagasse composites was lowered with the increase in nanoclay content. Additionally, the coupling agent, 4 wt % MAPP, improved the mechanical and physical properties of the composites more than the 2 wt % MAPP. From these results, we can conclude that addition of nanoclay enables to achieve better physical and mechanical properties in conventional composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

蒸爆技术应用于甘蔗渣的回收利用

纤维素的晶体结构影响了纤维素分子降解,为了有效利用甘蔗渣,必须对原料进行预处理。介绍了蒸爆预处理的原理及类型,并考察了蒸爆压力和时间对甘蔗渣水解的影响。     

Bone‐like apatite‐coated chitosan scaffolds: Characterization and osteoblastic activity

In this study, porous scaffolds were prepared from chitosan (2% w/v in acetic acid and deacetylation degree: DD > 85%) by freeze‐drying method, and freshly lyophilized scaffolds were stabilized with ethanol solutions. Bone‐like apatite formation on chitosan scaffolds was achieved by immersing the scaffolds into a novel concentrated simulated body fluid (10× SBF‐like solution) for different periods, i.e., 6 and 24 h. Scanning electron microscope views showed that the 6‐h treatment in 10× SBF‐like solution led to the formation of calcium phosphate nucleation sites on chitosan scaffolds, whereas the apatite particles showed characteristic cauliflower‐like morphology at the end of 24‐h treatment. X‐ray diffraction results supported the fact that mineral phase was made of hydroxyapatite. Osteogenic activities of untreated and SBF‐treated chitosan scaffolds were examined by preosteoblastic MC3T3 cell culture studies. The mitochondrial activity test showed that apatite‐coated scaffolds stimulated cell proliferation compared with uncoated scaffolds. Alkaline phosphatase and osteocalcine levels indicated that the differentiation of the cells on all scaffolds increased significantly from 15th day of culture to the 21th day of culture, especially for the cells on 24‐h SBF‐treated scaffolds. The results of this study indicated that 10× SBF‐like solution‐treated chitosan scaffolds may be evaluated for bone tissue engineering. POLYM. COMPOS., 31:1418–1426, 2010. © 2009 Society of Plastics Engineers     

Cover: Macromol. Mater. Eng. 3/2005

Summary: A novel human hair protein hybrid fiber was developed by combining (i) the high‐efficiency extraction technique for preparing human hair proteins and (ii) the watery hybridization spinning method using gellan and chitosan. The resulting human hair protein‐gellan‐chitosan hybrid fibers are conveniently produced by simply mixing the 7–35 wt.‐% human hair protein‐1.0 wt.‐% gellan aqueous solution and the 1.0 wt.‐% chitosan‐0.15 M acetic acid solution at 50 °C, followed by pulling out to spin the human hair protein‐gellan‐chitosan ternary complex thus formed at the aqueous solution interface. By use of this simple procedure and ambient spinning condition, the human hair proteins were successfully incorporated into the fiber matrix of gellan‐chitosan, without any denaturation and degradation. The hybrid fiber can also be recognized as a new type of the regenerated human hair keratin fiber, because of its high purity and content of human hair keratin types I and II. Mechanical strength of the human hair protein‐gellan‐chitosan fiber varies from 108 to 153 MPa, depending on the contents of the human hair proteins. SEM observation revealed that the incorporated human hair proteins were found as the particles (1–10 μm) on the fiber surface. The type I and II keratins in the fiber matrices were rapidly biodegraded by chymotrypsin within 30 min, and the digested fragments slowly released from the fiber matrices. Thus, the human hair hybrid fiber is a very promising material to have a broad spectrum of applications as the engineering fibers, particularly for the medical uses, because the human hair proteins are easily available, biocompatible, and bioresorbable materials.

Gellan‐chitosan hybrid fiber (a), human hair protein‐gellan‐chitosan hybrid fiber (b).     

Solvent extraction and purification of sugars from hemicellulose hydrolysates using boronic acid carriers

Research was performed to determine whether it was technically feasible to use boronic acid extractants to purify and concentrate the sugars present in hemicellulose hydrolysates. Initially, five types of boronic acids (phenylboronic acid, 3,5‐dimethylphenylboronic acid, 4‐tert‐butylphenylboronic acid, trans‐β‐styreneboronic acid or naphthalene‐2‐boronic acid) dissolved in an organic diluent (Shellsol^® 2046 or Exxal^® 10) containing the quaternary amine Aliquat^® 336 were tested for their ability to extract sugars (fructose, glucose, sucrose and xylose) from a buffered, immiscible aqueous solution. Naphthalene‐2‐boronic acid was found to give the greatest extraction of xylose regardless of which diluent was used. Trials were then conducted to extract xylose and glucose from solutions derived from the dilute acid hydrolysis of sugar cane bagasse and to then strip the loaded organic solutions using an aqueous solution containing hydrochloric acid. This produced a strip solution in which the xylose concentration had been increased over 7× that of the original hydrolysate while reducing the concentration of the undesirable acid‐soluble lignin by over 90%. Hence, this process can be exploited to produce high concentration xylose solutions suitable for direct fermentation. Copyright © 2004 Society of Chemical Industry     

Bio‐nanocomposite films based on cellulose nanocrystals filled polyvinyl alcohol/chitosan polymer blend

Bio‐nanocomposite films based on polyvinyl alcohol/chitosan (PVA/CS) polymeric blend and cellulose nanocrystals (CNC) were prepared by casting a homogenous and stable aqueous mixture of the three components. CNC used as nanoreinforcing agents were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis; then they were characterized and successfully dispersed into a PVA/CS (50/50, w/w) blend to produce PVA/CS–CNC bio‐nanocomposite films at different CNC contents (0.5, 2.5, 5 wt %). Viscosity measurement of the film‐forming solutions and structural and morphological characterizations of the solid films showed that the CNC are well dispersed into PVA/CS blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and CNC, thus improving their properties. The obtained bio‐nanocomposite films are mechanically strong and exhibit improved thermal properties. The addition of 5 wt % CNC within a PVA/CS blend increased the Young's modulus by 105%, the tensile strength by 77%, and the toughness by 68%. Herein, the utilization of Moroccan sugarcane bagasse as raw material to produce high quality CNC has been explored. Additionally, the ability of the as‐isolated CNC to reinforce polymer blends was studied, resulting in the production of the aforementioned bio‐nanocomposite films with improved properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42004.     

Chitosan from Muga silkworms (Antheraea assamensis) and its influence on thermal degradation behavior of poly(lactic acid) based biocomposite films

The research work is focused on extraction of chitin from Muga silkworms (MS) and its conversion into chitosan by chemical treatment process. The extracted amount of chitin and chitosan from MS were obtained ～8 wt % and ～7 wt %, respectively. Potentiometric titrations, conductometric titrations, elemental analysis, ¹H‐NMR and FTIR analyses were employed to calculate the degree of deacetylation of chitosan (extracted at 80 ºC after 10 h) and found as 77% ± 2, 81% ± 1.8, 82% ± 2.4, 97.77% ± 0.3, and 82% ± 1.8, respectively. The deacetylation process of chitin showed pseudo‐first order reaction kinetics and activation energy was estimated as ～15.5 kJ/mole. The extracted chitosan (at 80 ºC after 10 h) showed higher crystallinity and improved thermal stability with respect to chitosan extracted from other marine sources. Subsequently, poly(lactic acid) (PLA) and extracted chitosan dispersed biocomposite films were prepared by solution casting method. Significant dispersion of chitosan (extracted at 80 ºC after 10 h) micro‐particles were observed in biocomposite films using FESEM analysis. Due to chitosan interaction with PLA, significant reduction in thermal degradation and activation energy was observed during nonisothermal degradation scan of such films using Flynn‐Wall‐Ozawa and Kissinger‐Akahira‐Sunose models. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43710.     

Delignification of Bagasse with Acetic Acid and Ozone. Part 1. Acetic Acid Pulping

Two-stage delignification of sugarcane bagasse with acetic acid and ozone was investigated. The better pulp was obtained pulping bagasse in aqueous solution of acetic acid (80% volume) at 145°C during 60 min. The liquor/bagasse ratio (L/B) was 10:1 and the kappa number was 44; it fell to 10 in the ozone stage due to selectivity of acetic acid medium. Pulp reaches a brightness of almost 70% Elrepho and the strength properties are similar to those of soda pulps without refining and better than acetosolv pulps.     

间接法生产甲壳素纤维

由于天然甲壳素结晶度高,在湿法纺丝过程中溶解甲壳素时需要使用价格较高的有机溶剂。甲壳素脱乙酰基后得到的甲壳胺可以很方便地溶解在稀醋酸水溶液中,经喷丝孔挤出后用稀碱中和沉淀即可得到甲壳胺纤维。在甲壳胺纤维上加上乙酰基后可以得到再生甲壳素纤维。介绍了在用乙酸酐处理甲壳胺纤维制备再生甲壳素纤维过程中,反应时间、反应温度、乙酸酐用量对乙酰化的影响。     

Beneficiation of low grade carbonate-rich phosphate rocks using dilute acetic acid solution

The carbonate-rich phosphate rocks have no direct use and are rejected all over the world. Substantial amounts of low-grade phosphorites are found along with high grade ore in some areas of Hazara (Pakistan). In the technique described dilute acetic acid solution has been used for leaching of the carbonates contained in Hazara low-grade, carbonate-rich phosphate rocks. In this work, the effect of acetic acid concentration, reaction time and liquid/solid ratio (vol/wt. basis) have been studied. It was found that upon treatment of the ground ore with acetic acid, the tricalcium phosphate (TCP) percent can be raised by up to 23% corresponding to a reduction of up to 62% in the calcium carbonate content of the samples, depending on the conditions of the reaction as well as the nature and size of the raw phosphate particles used for analysis.     

Effects of different parameters on the characteristics of chitosan–poly(acrylic acid) nanoparticles obtained by the method of coacervation

Chitosan–poly(acrylic acid) polyelectrolyte complex nanoparticles were prepared by coacervation under mild experimental conditions without the use of any organic solvents or surfactants. The influence of some experimental parameters such as the pH of the polyelectrolyte solutions, their concentrations, and the purification procedure on the particle dimensions and their size distribution was studied in detail. The physicochemical properties of the obtained complex were characterized with Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. It was found that for solution concentrations below 0.1 wt %, it was possible to obtain suspensions of nanometer‐sized particles. Furthermore, it was established that the pH values of the reactant solutions had a great influence on both the particle size and the yield of the complex that was formed. The most convenient pH values for obtaining chitosan–poly(acrylic acid) particles with a nanometric size and optimum yield (near 90%) were found to be 4.5–5.5 for chitosan and 3.2 for poly(acrylic acid). Additionally, the effects of dialysis and ultrasonic treatment on the stability of complex suspensions, prepared under different experimental conditions, were clarified so that recommendations could be made to bring this system into practical use. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The enhanced mechanical properties of a covalently bound chitosan‐multiwalled carbon nanotube nanocomposite

In the present work, chitosan (CS)‐grafted multiwalled carbon nanotube (MWCNT) nanocomposites were prepared via covalently bonded CS onto MWCNTs that had weight fractions of MWCNTs ranging from 0.1 to 3.0 wt % by a simple method of solution casting. The structure, morphology, and mechanical properties of the films were investigated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy, optical microscopy, wide‐angle X‐ray diffraction, contact angle, and tensile testing. The results indicated that the CS chains were attached onto the MWCNTs successfully via covalent linkages. More interestingly, the MWCNTs provided a matrix that facilitated the crystallization of CS. Compared with the pure CS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 39.6 to 105.6 MPa and from 2.01 to 4.22 GPa with an increase in the MWCNT loading level from 0 to 3.0 wt %, respectively. The improvement in the tensile strength and modulus were ascribed to the uniform dispersion of MWCNTs covalently linked to the CS matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009