Role of mercerization of the bamboo strips on the impact properties and morphology of unidirectional bamboo strips–novolac composites

Bamboo strips were mercerized with varying concentrations of NaOH (10, 15, 20, and 25%). Impact test was made on composites made from the untreated as well as from the mercerized strips. Works of fracture for all the composites were evaluated and it was observed that the fracture energy undergoes an increase from composites made of untreated bamboo strips to those made from mercerized bamboo strips. Mercerization removed alkali sensitive material from the bamboo matrix and it leads to more cellulose fibril pull‐out from the lignocellulosic composites, which plays a great role in improving the work of fracture value. POLYM. COMPOS., 28:57–60, 2007. © 2007 Society of Plastics Engineers     

Thermogravimetric and weathering study of novolac resin composites reinforced with mercerized bamboo fiber

The effect of alkali treatment of bamboo strips on the thermal and weathering properties of unidirectional bamboo strips‐novolac resin composites were investigated in this work. Both alkali treated and untreated bamboo fiber‐reinforced composites were fabricated. All types of composite specimens were subjected to accelerated weathering and the % water absorption and dimensional changes were recorded after 120 h immersion in water at room temperature and atmospheric pressure and further characterized by flexural property measurements. The composites were also subjected to exposure at 100% humidity and UV exposure (sun light) for 75 h. The results showed that the composites with treated bamboo strips showed a better weathering characteristics compared with the untreated ones. Thermogravimatric analysis of all the samples indicated better thermal properties of alkali treated samples. These findings confirmed the improved interfacial interactions arising from covalent bonds between the alkali treated bamboo fibers and novolac resin. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Influence of alkali fiber treatment and fiber processing on the mechanical properties of hemp/epoxy composites

Industrial hemp fibers were treated with a 5 wt % NaOH, 2 wt % Na₂SO₃ solution at 120°C for 60 min to remove noncellulosic fiber components. Analysis of fibers by lignin analysis, scanning electron microscopy (SEM), zeta potential, Fourier transform infrared (FTIR) spectroscopy, wide angle X‐ray diffraction (WAXRD) and differential thermal/thermogravimetric analysis (DTA/TGA), supported that alkali treatment had (i) removed lignin, (ii) separated fibers from their fiber bundles, (iii) exposed cellulose hydroxyl groups, (iv) made the fiber surface cleaner, and (v) enhanced thermal stability of the fibers by increasing cellulose crystallinity through better packing of cellulose chains. Untreated and alkali treated short (random and aligned) and long (aligned) hemp fiber/epoxy composites were produced with fiber contents between 40 and 65 wt %. Although alkali treatment generally improved composite strength, better strength at high fiber contents for long fiber composites was achieved with untreated fiber, which appeared to be due to less fiber/fiber contact between alkali treated fibers. Composites with 65 wt % untreated, long aligned fiber were the strongest with a tensile strength (TS) of 165 MPa, Young's modulus (YM) of 17 GPa, flexural strength of 180 MPa, flexural modulus of 9 GPa, impact energy (IE) of 14.5 kJ/m², and fracture toughness (K_Ic) of 5 MPa m^1/2. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Tensile and lignocellulosic properties of Prosopis chilensis natural fabric

The uniaxial natural fabric Prosopis chilensis was treated with NaOH (alkali), poly (vinyl alcohol) (PVA), and polycarbonate (PC) solutions. The Prosopis chilensis fabric belongs to Leguminosae family. The properties of ligno‐cellulosic fabric and the effect of sodium hydroxide (NaOH) treatment were evaluated using thermal analysis by means of thermogravimetric and differential scanning calorimetry analysis, Autonated total reflection‐fourier transform infrared spectroscopy, X‐ray diffraction (XRD), and field emission scanning electron microscopy. Tensile properties of the untreated and fabric treated with NaOH, PVA, and PC were also studied to assess their performance. The fabric has good thermal resistance on alkali treatment. The FTIR method indicates lowering the hemi cellulose and lignin content by alkali treatment. Further, the XRD studies reveal that crystallinity of the fabric increases on alkali treatment. Tensile properties of the fabric were enhanced on treatments with NaOH, PVA, and PC treatments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Evaluation of improvement of physical and mechanical properties of bamboo fibers due to alkali treatment

Bamboo strips treated with caustic solutions of different concentrations, e.g., 5%, 10%, 15%, 20%, 25%, and 50%, were subjected to mechanical testing giving stresses on tensile strength, percent elongation at break, flexural strength, flexural modulus, and toughness. The change in average density was ?15%, and the weight loss value shows a maximum of 21.94% at 50% alkali treatment. The mechanical properties of bamboo strips increase steadily with increasing concentration of caustic soda, showing a comparable increased value at 15 and 20%, and then exhibiting a gradual fall. The percent elongation at break corroborates these observations showing a continuous decreasing trend. The properties under investigation exhibit a clear transition in between 15 and 20% alkali concentration. The morphology of strips was studied by scanning electron microscope and polarizing light microscope. The crystal structure of both untreated and treated strips was compared by XRD analysis. In both cases, the breakdown of the crystal structures of the cellulose fibers and the recrystallization or reorientation of the degraded chains that are devoid of hemicellulose are quite apparent. However, at a very high concentration (to the extent of 25%) the breakdown of structure predominates much more over the reorientation or recrystallization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The effect of alkalization and fiber loading on the mechanical properties of bamboo fiber composites,Part 1: — Polyester resin matrix

Bamboo strips [10 cm × 1.5 cm × (1?1.5) mm] were treated with caustic solutions for 1 h at different concentrations e.g., 0, 10, 15, 20, and 25%. Bamboo strips reinforced polyester resin composites were fabricated by hand‐lay‐up technique using both alkali‐treated and untreated bamboo strips, using a room temperature curing system for the polyester resin. This study aims at the evaluation of the influence of caustic concentration on the mechanical properties of bamboo strips reinforced polyester resin composites at a constant 50% loading of reinforcement. Maximum improvement in property was achieved possibly with 20% of caustic treated strip reinforcements. Beyond 20%, there was degradation in all the strength properties because of failure in mechanical properties of the reinforcements itself. The effect of fiber loading variation upon mechanical properties was also studied. It was observed that superior mechanical properties were obtained with 60% filler loading. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of ramie yarn treated with sodium hydroxide and crosslinked by 1,2,3,4‐butanetetracarboxylic acid

Ramie yarns were treated with various concentrations of NaOH at room temperature and subsequently crosslinked with 1,2,3,4‐butanetetracarboxylic acid (BTCA). The microstructure and tensile properties of the treated yarns were characterized. X‐ray diffraction (XRD) and FTIR were used to study the crystalline structure of the resultant ramie yarns. The results showed that the maximum change in the structure of the alkali‐modified ramie took place at 16% NaOH, which would completely transform cellulose I to cellulose II. At the same time, the crystallinity index and fiber orientation decreased to the minimum value while the absorption properties were enhanced. The average degree of polymerization (DP ) of the treated ramie yarns slightly decreased after NaOH treatment. Tensile properties including tenacity, breaking elongation, and modulus of the treated yarns were also investigated. Scanning electron microscopy (SEM) was used to investigate the breakage of the treated yarns. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1857–1864, 2004     

Rheological behavior of pH‐responsive associating ionic polymers of diallyammonium salts and sulfur dioxide

In this study, the viscoelastic behavior of hydrophobically modified polyelectrolytes obtained from the hydrolysis of cationic acid salts (CAS's) as a function of their zwitterion fraction (x) and anion fraction (z) was studied. The dynamic viscosity (η′) dependence on frequency of polymer solutions of polybetaine/anionic polyelectrolyte (APE) with various compositions of x and z in 0.1N NaCl showed typical shear thinning behavior. η′ of a solution of CAS 4 (M₂‐4 (4 mol % hydrophobe)) attained a maximum value in the presence of 1.67 equiv of NaOH (corresponding to an x : z ratio of 33 : 67) and decreased with any further addition of NaOH. We suggest this maximum to be a result of a combined effect of coil expansion and hydrophobic association. The influence of the temperature and concentration on η′ of CAS 4 (M₂‐4) treated with 1.67 equiv of NaOH was also investigated. The rheology of CAS 4 (M₂‐4) samples treated with 1.67, 1.81, and 2.0 equiv of NaOH suggested a reversible network. However, for APE 7 (M₂‐5 (5 mol % hydrophobe)), elastic behavior was dominant, and the formation of highly interconnected three‐dimensional networks was suggested. At lower x : z ratios, the effect of coil expansion due to a higher APE fraction was more than counterbalanced by the lower degree of intermolecular hydrophobic associations, whereas at higher x : z ratios, coil contraction became the predominant effect. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhancement of thermal stability associated with the chemical treatment of bacterial (Gluconacetobacter xylinus) cellulose

Bacterial cellulose produced by Gluconacetobacter xylinus was treated with sodium carbonate (Na₂CO₃) and sodium hydroxide (NaOH) to remove entrapped noncellulosic materials. Fourier transform infrared (FTIR) spectroscopy has been used to investigate the effect of alkali on the chemical structure of bacterial cellulose. The changes in the crystalline nature of these membranes were analyzed using X‐ray diffraction (XRD) technique. The morphology and the removal of noncellulosic impurities followed by alkali treatment were studied using scanning electron microscopy (SEM) and energy dispersive X‐ray spectrometry (EDS). The enhanced thermal stability of bacterial cellulose was evident from thermogravimetric analysis (TGA). Further, the alkali treatments resulted in relatively pure form of cellulose, which finds application in various spheres. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

吐温-80及碱预处理对饲用稻草木质素含量和纤维素酶解产糖的影响

探讨了添加1‰吐温-80非离子表面活性剂和不同浓度碱预处理对稻草秸秆木质素及纤维素的影响,并对预处理前后的稻草进行了X射线衍射光谱(XRD)分析,从结晶度的变化综合分析了预处理对纤维素酶解的影响。实验结果表明:在30℃下添加1‰吐温-80非离子表面活性剂时,用4%NaOH预处理稻草秸秆,木质素含量降至6.5%(较未处理稻草下降了41.9%),灰分值仅占6.9%,具有较好的粗饲料价值;在121℃(0.1 MPa)下添加1‰吐温-80非离子表面活性剂时,用4%NaOH预处理稻草秸秆,木质素含量降至2.8%(较未处理稻草下降了74.5%),酶解还原糖达到393.9 mg/g,纤维素糖化率为59.3%(较未处理稻草提高了2.4倍)。XRD分析显示,在较温和的条件下,低浓度碱预处理稻草秸秆,对纤维素结晶区带来的影响相对于无定形区弱,不足以引起纤维素结晶度的降低。     

Effects of alkalization and fiber loading on the mechanical properties and morphology of bamboo fiber composites. II. Resol matrix

Resol resin composites reinforced with alkali‐treated bamboo strips were fabricated with a hand‐lay‐up technique. This study was aimed at the evaluation of the influence of the caustic concentration on the mechanical properties of bamboo‐strip‐reinforced resol composites with a constant 50% loading of the reinforcement. The treatment of bamboo fiber in a solution of sodium hydroxide with increasing concentration percentages resulted in more and more rigid composites; as a result, the strength and modulus values exhibited improvements. The maximum improvement in the properties was possibly achieved with 20% caustic treated reinforcements. An infrared study indicated the formation of aryl alkyl ether with ? OH groups of cellulose and methylol groups of resol. Beyond 20%, there was degradation in all the strength properties due to the failure of the mechanical properties of the reinforcement itself. A correlation was found to exist between the mechanical properties and the morphology that developed. Another set of composites with variable loadings of 20% alkali treated fiber (40, 50, and 60%) was fabricated, and a 60% fiber loading showed the best mechanical properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A study on ligno‐cellulosic fabric Hardwikia binata

A naturally occurring fabric belonging to the species Hardwikia binata was extracted from the sheath of stem, bark, and branches of the tree. The fabric specimens were treated with sodium hydroxide and poly (vinyl alcohol). The morphology of the fabric specimens before and after NaOH treatment was studied using scanning electron microscopy technique. Ligno‐cellulosic properties of fabric were analyzed by XRD, FTIR, and thermo gravimetric methods before and after NaOH treatment. Tensile strength and percentage of elongation at break of the fabric were also studied by using a universal testing machine (model AGS‐10kNG). The results showed that the poly (vinyl alcohol)‐treated fabric specimens showed higher tensile strength than sodium hydroxide‐treated fabric specimens. The Binata fabric has good thermal resistance and was also found to increase by alkali treatment. The FTIR method indicates lowering the hemi cellulose and lignin content by alkali treatment in the fabric. Further, the X‐ray diffraction studies revealed an increase in crystallinity of the fabric by alkali treatment. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydroxypropylation of cellulose isolated from bamboo (Dendrocalamus strictus) with respect to hydroxypropoxyl content and rheological behavior of the hydroxypropyl cellulose

Bamboo, a lignocellulosic material, is a renewable source of interest as feedstock for production of cellulose derivatives by chemical functionalization. Optimization of hydroxypropylation of cellulosic material (average DP 816), isolated from bamboo (Dendrocalamus strictus) was, therefore, performed with respect to maximum percent hydroxylpropoxyl (% HP) contents under varying reaction conditions and studying their effect on the % HP. The optimized reaction conditions were aqueous NaOH concentration 22%, propylene oxide concentration 17.4 mol/AGU, temperature 50°C, duration of hydroxypropylation 4 h to yield hydroxypropyl cellulose of % HP 65.89. The η_app of 1 and 2% solutions of the optimized product showed it to be non‐Newtonian pseudoplastic. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Graft polymerization of some vinyl monomers onto alkali-treated cellulose

Treatment of cellulose by different concentrations of alkali, namely, 5–30% NaOH, changed its fine structure and transferred cellulose I into cellulose II. The decreased crystallinity due to alkali treatment and the transformation of cellulose I into cellulose II lowered the reactivity of cellulose toward the grafting polymerization reactions. Compactness of the structure as a result of the treatment of cellulose with 5% sodium hydroxide concentration decreased the rate of the grafting reaction and the grafting yield. On the other hand, such treatment of cellulose with different concentrations of alkali increased the rate of ceric consumption, i.e., increased the rate of oxidation of cellulose. Thus, the termination reaction of the grafting polymerization process may occur as a result of such oxidation and because of the increase of the active sites onto cellulose, leading to a decrease of the grafting yields and rate of grafting polymerization reaction by using the free-radical grafting process. The use of the ionic-xanthate method of grafting polyvinyl- and polyallyl-on alkali-treated cellulose shows an increase of grafting efficiency and grafting yields. Maximum grafting efficiency and yields were achieved when cellulose was treated with sodium hydroxide concentration below 15%, and maximum crystallinity indices were obtained. Using 15–25% sodium hydroxide lowered the indices of crystallinity, and lower grafting yields and grafting efficiency were achieved. Thus, transformation of cellulose I into cellulose II decreased the reactivity of these treated celluloses toward graft polymerization reactions by the use of the ionic-xanthate method. In our opinion, termination reactions may also occur and affect the results.     

Further studies on the action of alkali metal hydroxides on cotton

X-Ray diagrams revealed that the conversion of the lattice structure from cellulose I to cellulose II is substantially complete in cotton treated at 0°C with LiOH, NaOH, or KOH of approximately 5N concentration. With concentrations less than 5N, there were marked differences in the ability of these reagents to cause lattice conversions in cotton. Below a minimum concentration which is dependent on both the alkali and the treatment temperature, conversion from cellulose I to cellulose II cannot take place in cotton irrespective of the swelling caused by the reagent. We suggest that extensive swelling by one of these alkalis is not sufficient by itself to cause conversion from cellulose 1 to cellulose II and that the concentration of the alkali is of prime importance. There was no direct relation between the swelling induced in cotton by treatment with LiCH, NaOH, or KOH at 0°C and the sorption ratio of the resulting product. Also, although treatment with 5N KOH caused less swelling than that obtained with either 5N NaOH or LiOH, KOH reduced the level-off degree of polymerization (LODP) of cotton most, indicating the importance of the size of alkali cation in reducing crystallite length. In additional experiments, cotton was treated at 21°C with a solution of 4.7N NaOH to which boric acid had been added. Although the swelling of the cotton was little affected, the addition of the boric acid caused the sorption ratio of the product to decrease, whereas the LODP increased. Also conversion of the lattice structure from cellulose I to cellulose II was inhibited.     

Composite effect of silica nanoparticle on the mechanical properties of cellulose‐based hydrogels derived from cottonseed hulls

Recently, cellulose‐based hydrogel nanocomposite materials have been attracted increasing attention owing to their potential applications in different areas including medical, electrical, optical, and magnetic fields. This is due to the fact that cellulose is one of the most abundant resources and possesses several unique properties required in medical fields, whereas silica nanoparticles (nSiO₂) play an important role in developing materials with high functionality. In this study, cottonseed hull (CSH) was used as a source of cellulose and nSiO₂ was used to prepare hydrogel nanocomposite films via phase inversion method without chemical crosslinking agent of cellulose. CSH was first pre‐treated with sodium hydroxide (NaOH) and sodium hypochlorite (NaOCl) for delignification and bleaching, respectively. The pre‐treated CSH exhibited whiter fiber and lower amount of lignin as compared with the untreated CSH. The properties of cellulose‐base hydrogel were found to be improved as a result of the addition of nSiO₂ at 2–6 wt % for tensile strength and up to 10 wt % for modulus and elastic modulus (G′). However, the elongation at break was decreased with the incorporation of nSiO₂. Moreover, the TEM images displayed the nano‐grape structure of nSiO₂ surrounded by cellulose molecules. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44557.     

Extraction and characterization of rice straw cellulose nanofibers by an optimized chemomechanical method

In this study, a chemomechanical method was performed to extract nanofibers from rice straw. This procedure included swelling, acid hydrolysis, alkali treatment, bleaching, and sonication. X‐ray diffractometer was employed to investigate the effect of acid hydrolysis conditions and other chemical treatments on the chemical structure of the extracted cellulose fibers. It was concluded that by increasing the acid concentration and hydrolysis time, the crystallinity of the extracted fibers was increased. The optimum acid hydrolysis conditions were found to be 2M and 2 h for the acid concentration and hydrolysis time, respectively. The chemical compositions of fibers including cellulose, hemicelluloses, lignin, and silica were determined by different examinations. It was noticed that almost all the silica content of fibers was solubilized in the swelling step. Moreover, the achieved results showed that the cellulose content of the alkali treated fibers was increased around 71% compared to the raw materials. ATR‐FTIR was applied out to compare the chemical structure of untreated and bleached fibers. The dimensions and morphology of the chemically and mechanically extracted nanofibers were investigated by scanning electron microscopy, field emission scanning electron microscopy, and transmission electron microscopy. The results of the image analyzer showed that almost 50% of fibers have a diameter within a range of 70–90 nm and length of several micrometers. The thermal gravimetric analyses were performed on the untreated and bleached fibers. It was demonstrated that the degradation temperature was increased around 19% for the purified fibers compared to raw materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40063.     

Office waste paper as cellulose nanocrystal source

Cellulose nanocrystals (CNC) are isolated from office waste paper using an alkali solution and a subsequent acid hydrolysis process. The Fourier transform infrared spectroscopy and X‐ray diffraction (XRD) results demonstrate that ink and fillers used in the papermaking industry are almost totally removed after alkali treatments. The XRD results show that CNCs obtained after 2 wt % NaOH solution treatment and a subsequent hydrolysis process exhibit only a cellulose I crystalline structure, and the crystallinity index value increases around 42% with respect to initial office waste paper. Nevertheless, CNCs obtained after 7.5 wt % NaOH solution treatment and a subsequent acid hydrolysis process show a mixture of cellulose I and cellulose II polymorphs. The thermal analysis shows that the CNCs obtained after 7.5 wt % NaOH solution treatment and a subsequent acid hydrolysis process are thermally less stable than other samples, suggesting that the cellulose chains could depolymerize into low molecular weight sugar compounds. Even though the atomic force microscopy images confirm the presence of CNCs, the optical images show that some cellulose microfibers still maintain their structure. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45257.     

Biocomposites of Cellulose Acetate Butyrate with Modified Hemp Cellulose Fibres

Cellulose acetate butyrate biocomposites, plasticized with tributyl citrate at volume fraction V_f = 0.1–0.3, were prepared with modified hemp. Inclusion of modified hemp fibres at V_f = 0.4 enhanced the modulus and strength of the flexible plasticized cellulose acetate butyrate. Composites containing pectate lyase enzyme treated fibres showed a modulus greater than untreated or alkali treated fibres, when compared at a similar fibre length of 100 µm. Composites containing the shortest alkali treated fibres of 45 µm gave the greatest property improvement, while 500 µm fibres showed worsened properties. Ball‐milled fibres provided reduced values of properties due to cellulose structural disruption, while compression moulding gave better compaction by removing voids.

     

Synthesis and characterization of the new cellulose derivative films based on the hydroxyethyl cellulose prepared from esparto “stipa tenacissima” cellulose of Eastern Morocco. II. Esterification with acyl chlorides in a homogeneous medium

Esparto “Stipa tenacissima” cellulose esters derivatives: HECA‐COO? C₄H₈? COOC₂H₅, HECA‐COO? C₈H₁₆? COOC₂H₅, and HECA‐COO? C₆H₄? COOC₂H₅ were successfully prepared in Tetrahydrofuran (THF)/triethylamine system with a degree of substitution (DS), respectively, DS_AD‐Et=0.32, DS_SB‐Et=0.22, and DS_TRP‐Et=0.50 using hydroxyethyl cellulose acetate (HECA; DS_AC=0.50) as intermediate product, and we avoided the drawbacks of cellulose solubility. The structural modifications were investigated using Fourier transform infrared spectroscopy (FTIR), Proton nuclear magnetic resonance (¹H‐NMR), Carbon‐13 nuclear magnetic resonance (¹³C‐NMR), and Distortionless Enhancement by Polarization Transfer 135° (DEPT‐135). The results from these analyses revealed the presence of the characteristic groups indicating that the grafting reaction was successful. The crystallinity and the structure order changes during the esterification reactions were recorded by X‐ray diffraction (XRD), it is found that the crystallinity degree decrease from 63.1% for Esparto “Stipa tenacissima” cellulose to 27.74% for HECA. The thermal stability of the esterified and unmodified cellulose samples was studied by thermogravimetric analysis (TGA)‐differential thermal analysis (DTA); the modified HECA exhibits a decrease in thermal stability relatively to the unmodified HECA, and this may be related to the groups grafted. The resulted cellulose esters HECA‐P_x (x = 1, 2, or 3) were soluble in THF and present an amorphous structure justified by XRD spectra. It was noted by TGA‐DTA analysis that the cellulose esters with low melting range were proved as thermoplastic polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013