According to the 12 principles of green chemistry, surface functionalization was performed using glutaric anhydride under solvent-free and catalyst-free conditions. FTIR spectra and DS analyses demonstrated the functionalization of HCl-hydrolyzed cellulose. The influence of two parameters, i.e., the glutaric anhydride concentration and the reaction time, on the functionalization of HCl-hydrolyzed cellulose was investigated. Protocol efficiency was studied by a degree of substitution (DS). It was found that higher concentrations of glutaric anhydride cause an enhancement of DS to 0.75 and 0.87 for GA3-12 and GA9-12, respectively. In addition, the longer reaction time increased zeta potential from -12.2 ± 1.7 for G9-6 to -34.57 ± 2.2 for GA9-12. Morphology analysis by SEM showed a decrease in fiber length for the functionalized cellulose. DSC profiles confirmed dehydration at a range of 17 to 134 °C. A glass transition was revealed at -30 to -20 °C for all studied samples. The fusion, the depolymerization of cellulose chains, the cleavage of glycosidic linkages, and the decomposition of the crystalline parts of cellulose occur at 195 to 374 °C. Therefore, an efficient and greener process was developed to functionalize the HCl-hydrolyzed cellulose by glutaric anhydride, a safe and non-toxic anhydride, in the absence of the solvent and catalyst.
The fractions of fatty acid methyl esters (FAME) i.e. crude palm oil methyl esters (CPOME), RBD palm olein methyl esters (RBD Palm Olein ME) and used frying oil methyl esters (UFOME) rich in unsaturated fatty esters were used to prepare alkenyl succinic anhydrides (ASA). The fractions were obtained via fractional distillation that separated the unsaturated fatty esters from the saturated fatty esters. The fractions with the highest content of unsaturated fatty esters were reacted with maleic anhydride (MA) for 8 hours at 240oC with the MA/FAME ratio of 1.5. The reaction was conducted without catalyst and solvent. The crude alkenyl succinic anhydride (ASA) obtained was purified by column chromatography. The purified compound was characterised by FTIR.
The rate of formation and disappearance of phthalic anhydride (PAn) intermediate in the aqueous cleavage of N-methoxyphthalamic acid (NMPA) under acidic pH was studied spectrophotometrically in mixed CH3CN-H2O solvents. The rate of formation of PAn from NMPA is almost independent of the change in acetonitrile content from 20 to 70% v/v in mixed aqueous solvents. The rate constants for the formation of PAn from NMPA are approximately 10-fold smaller than the corresponding rate constants for the formation of PAn from o-carboxybenzohydroxamic acid (OCBA). These observations are ascribed to the consequence of the occurrence of slightly different mechanisms in these reactions.
The properties of fibre-reinforced composites are dependent not only on the strength of the reinforcementfibre but also on the distribution of fibre strength and the composition of the chemicals or additivesaddition within the composites. In this study, the tensile properties of abaca fibre reinforced high impactpolystyrene (HIPS) composites, which had been produced with the parameters of fibre loading (30,40,50wt.%), coupling agent maleic anhydride (MAH) (1,2,3 wt%) and impact modifier (4,5,6 wt.%) weremeasured. The optimum amount of MAH is 3% and the impact modifier is 6% and these give the besttensile properties. Meanwhile, Differential Scanning Calorimetry (DSC) was used to study the thermalbehaviour within the optimum conditions of the composites. In this research, glass transitions temperature(Tg) of neat HIPS occurred below the Tg of the optimum condition of composites as the temperature ofan amorphous state. The endothermic peak of the composites was in the range of 430-4350C, includingneat HIPS. It was observed that enthalpy of the abaca fibre reinforced HIPS composites yielded belowthe neat HIPS of 748.79 J/g.
The physical properties by natural fibre have a great importance, specifically in the structural of natural fibre which reinforces matrix. Response surface methodology with Box-Behnken (BB) design of experiment was utilized to study water absorption and melt flow index (MFI) of abaca fibre reinforced high impact polystyrene (HIPS) composites. The design utilizes fraction of weight abaca fibre, maleic anhydride (MAH), and impact modifier to develop models for characteristic behaviours of water absorption and MFI of composites. Abaca fibre reinforced high impact polystyrene (HIPS) composites were produced with different fibre loadings (30, 40, and 50 wt%), different compositions of coupling agent, maleic anhydried (MAH) (1, 2, and 3 wt%) and different compositions of impact modifier (4, 5, 6 wt%). The individual optimum of water absorption was found when loading abaca fibre close to 34.61 wt%, maleic anhydride 1 wt%, and impact modifier 4.01 wt%. The individual optimum of melt flow index dealt with loading abaca fibre 36.71 wt%, maleic anhydride 3 wt% and impact modifier 4.02 wt%. Meanwhile, the optimum condition for water absorption of abaca fibre reinforced HIPS composites was followed by a decreasing trend of the value of melt flow index.
Two different liquid assisted processing methods: internal melt-blending (IMB) and twin-screw extrusion (TWS) were performed to fabricate polyethylene (PE)/cellulose nanofiber (CNF) nanocomposites. The nanocomposites consisted maleic anhydride-grafted PE (PEgMA) as a compatibilizer, with PE/PEgMA/CNF ratio of 97/3/0.5-5 (wt./wt./wt.), respectively. Morphological analysis exhibited that CNF was well-dispersed in nanocomposites prepared by liquid-assisted TWS. Meanwhile, a randomly oriented and agglomerated CNF was observed in the nanocomposites prepared by liquid-assisted IMB. The nanocomposites obtained from liquid-assisted TWS exhibited the best mechanical properties at 3 wt.% CNF addition with an increment in flexural strength by almost 139%, higher than that of liquid-assisted IMB. Results from this study indicated that liquid feeding of CNF assisted the homogenous dispersion of CNF in PE matrix, and the mechanical properties of the nanocomposites were affected by compounding method due to the CNF dispersion and alignment.
Octenyl succinic anhydride (OSA) modified sago starch was prepared in order to improve the emulsification properties of native starch. In the present study, the major factors affecting esterification were investigated with respect to OSA concentration, pH and reaction time using response surface methodology (RSM) based on central composite rotatable design (CCRD) to obtain the highest value of degree of substitution (DS). Results shown that the optimum conditions for OSA concentration, pH and reaction time were 5.00%, pH 7.20 and 9.65 h, respectively. At optimum condition, the esterification of sago starch with OSA resulted in DS value of 0.0120. The DS increased linearly with the increase in amount of OSA, whilst pH and reaction time show a curvature trend on the value of DS. The value of DS was found to be significantly affected by all the three variables. The experimental values under optimum condition were in good consistent with the predicted values (0.0131), which suggested that the optimisation by RSM is more efficient process than conventional optimisation.
The use of chemical modification of cellulosic fibre is applied in order to increase the hydrophobicity, hence improving the compatibility between the fibre and matrix bonding. In this study, the effect of propionic anhydride modification of kenaf fibre was investigated to determine the role of bionanocarbon from oil palm shell agricultural wastes in the improvement of the functional properties of bionanocomposites. The vinyl esters reinforced with unmodified and propionic anhydride modified kenaf fibres bio nanocomposites were prepared using 0, 1, 3, 5 wt% of bio-nanocarbon. Characterisation of the fabricated bionanocomposite was carried out using FESEM, TEM, FT-IR and TGA to investigate the morphological analysis, surface properties, functional and thermal analyses, respectively. Mechanical performance of bionanocomposites was evaluated according to standard methods. The chemical modification of cellulosic fibre with the incorporation of bionanocarbon in the matrix exhibited high enhancement of the tensile, flexural, and impact strengths, for approximately 63.91%, 49.61% and 54.82%, respectively. The morphological, structural and functional analyses revealed that better compatibility of the modified fibre-matrix interaction was achieved at 3% bionanocarbon loading, which indicated improved properties of the bionanocomposite. The nanocomposites exhibited high degradation temperature which signified good thermal stability properties. The improved properties of the bionanocomposite were attributed to the effect of the surface modification and bionanocarbon enhancement of the fibre-matrix networks.
Most substrate for esterification has the inherent problem of low miscibility which requires addition of solvents into the reaction media. In this contribution, we would like to present an alternative and feasible option for an efficient solvent-free synthesis of menthyl butyrate using a novel thermostable crude T1 lipase. We investigated the effects of incubation time, temperature, enzyme loading and substrate molar ratio and determined the optimum conditions. The high conversion of menthyl butyrate catalyzed by crude T1 lipase in a solvent-free system is greatly affected by temperature and time of the reaction media. The highest yield of menthyl butyrate was 99.3% under optimized conditions of 60 °C, incubation time of 13.15 h, 2.53 mg, 0.43% (w/w) enzyme to substrate ratio and at molar ratio of butyric anhydride/menthol 2.7:1. Hence, the investigation revealed that the thermostable crude T1 lipase successfully catalyzed the high-yield production of menthyl butyrate in a solvent-free system. The finding suggests that the crude T1 lipase was a promising alternative to overcome shortcomings associated with solvent-assisted enzymatic reactions.
This work investigates a new interrogation method of a fiber Bragg grating (FBG) sensor based on longer and shorter wavelengths to distinguish between transversal forces and temperature variations. Calibration experiments were carried out to examine the sensor's repeatability in response to the transversal forces and temperature changes. An automated calibration system was developed for the sensor's characterization, calibration, and repeatability testing. Experimental results showed that the FBG sensor can provide sensor repeatability of 13.21 pm and 17.015 pm for longer and shorter wavelengths, respectively. The obtained calibration coefficients expressed in the linear model using the matrix enabled the sensor to provide accurate predictions for both measurements. Analysis of the calibration and experiment results implied improvements for future work. Overall, the new interrogation method demonstrated the potential to employ the FBG sensing technique where discrimination between two/three measurands is needed.
Thermal characterization of sugar palm fibre (SPF), reinforced high impact polystyrene (HIPS)
composites, was studied by means of thermogravimetric analysis. The effects of alkaline treatment and compatibilizing agent on the thermal stability of the composites were evaluated. Alkaline treatment was carried out by soaking the fibres in 4 and 6% of NaOH solution, while treatment with compatibilizing agent was employed by adding 2 and 3% maleic anhydride-graft-polystyrene (MA-g-PS) to the composites. Both the treatments were aimed to improve the mechanical performance of the composites. From the study, the thermal stability of the treated composites was found to be higher than that of untreated composites. It is shown that the incorporation of sugar palm fibre influences the degree of thermal stability of the composites. The treatments on composites also contributed to shifting the peak temperature of degradation of the composites. In other words, there are strong chemical reactions between the components of the treated composites. The thermal stability of the composites, with alkaline treatment and compatibilizing agent, was found to be better as compared to those of the untreated composites.
The bottleneck of conventional polymeric membranes applied in industry has a tradeoff between permeability and selectivity that deters its widespread expansion. This can be circumvented through a hybrid membrane that utilizes the advantages of inorganic and polymer materials to improve the gas separation performance. The approach can be further enhanced through the incorporation of amine-impregnated fillers that has the potential to minimize defects while simultaneously enhancing gas affinity. An innovative combination between impregnated Linde T with different numbers of amine-functional groups (i.e., monoamine, diamine, and triamine) and 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA)-derived polyimide has been elucidated to explore its potential in CO2/CH4 separation. Detailed physical properties (i.e., free volume and glass transition temperature) and gas transport behavior (i.e., solubility, permeability, and diffusivity) of the fabricated membranes have been examined to unveil the effect of different numbers of amine-functional groups in Linde T fillers. It was found that a hybrid membrane impregnated with Linde T using a diamine functional group demonstrated the highest improvement compared to a pristine polyimide with 3.75- and 1.75-fold enhancements in CO2/CH4 selectivities and CO2 permeability, respectively, which successfully lies on the 2008 Robeson's upper bound. The novel coupling of diamine-impregnated Linde T and 6FDA-derived polyimide is a promising candidate for application in large-scale CO2 removal processes.
In this study, compatibilizing effects of caprolactam-maleic anhydride (CL-MAH) and
polyethylene-grafted-maleic anhydride (PE-g-MAH) with different blend compositions on polymer
blends of recycled high density polyethylene (RHDPE) and ethylene vinyl acetate (EVA) blends were
investigated by tensile properties and swelling behavior. The use of CL-MAH improved the
compatibility of RHDPE80/EVA20 blend composition, and tensile properties of the resultant blend
compared well with those of RHDPE/EVA blends. Addition of PE-g-MAH improved the tensile
properties of RHDPE/EVA/PE-g-MAH blends than RHDPE/EVA blends without compatibilizer. The
scanning electron microscopy (SEM) morphologies of fracture surface for RHDPE/EVA blends with
presence of compatibilizers showing better incorporation of two different phases of polymer matrix.
Linear density polyethylene (LDPE)/thermoplastic sago starch (TPSS), blended with and without the addition of compatibilizer [Polyethylene-grafted-Maleic Anhydride, (PE-g-MA)] were prepared for soil burial test. The test was conducted in the natural soil environment for 3 and 6 months. Different loading of TPSS (10, 20, 30, 40, and 50 wt. %) were used in this study. After soil burial, the blends were evaluated for their tensile properties and scanning electron microscopy (SEM) to observe the surface morphology properties after the test. For LDPE/TPSS, it was observed that the tensile strength decreased with the increase of soil burial time, as well as Young modulus and elongation at break (EB). The LDPE/TPSS/PE-g-MA also showed the same trend for the tensile properties, but with higher properties as compared to uncompatibilized blends. The tensile properties also decreased with the increase in the TPSS loading for both the LDPE/TPSS and LDPE/TPSS/PE-g-MA. Meanwhile,
the scanning electron microscopy (SEM) on the blend surfaces after the soil burial test showed that degradability increased with the increase in the exposure time as well as the TPSS loading.
Chitosan was chemically modified with bulky structure, cis-5-norbornene-2, 3-dicarboxylic anhydride and the characteristic of this modified chitosan was studied. The resulting material was analyzed by FTIR, TGA, DSC, XRD and SEM to study the effect of N-acylation to the polysaccharide structure. FTIR results show that the anhydride monomer was successfully bound to amine group of chitosan. Thermal analysis of the modified structure provides the chitosan fibers with thermal stability while XRD and SEM show the lost of crystallinity of modified chitosan. XRD of modified chitosan shows broader peak pattern and a considerable increase in a dimension while SEM of chitosan presented the single particle morphology while norbornene-chitosan shows aggromolarate behaviour due to the hydrophobic nature of norbornene pendant group which induced aggromolaration of the particles in modified structure.
In this research work, graphene nanoplatelets (GNP) were selected as alternative reinforcing nanofillers to enhance the properties of polypropylene (PP) using different compatibilizers called polypropylene grafted maleic anhydride (PP-g-MA) and ethylene-octene elastomer grafted maleic anhydride (POE-g-MA). A twin screw extruder was used to compound PP, GNP, and either the PP-g-MA or POE-g-MA compatibilizer. The effect of GNP loading on mechanical and thermal properties of neat PP was investigated. Furthermore, the influence and performance of different compatibilizers on the final properties, such as mechanical and thermal, were discussed and reported. Tensile, flexural, impact, melting temperature, crystallization temperature, and thermal stability were evaluated by using a universal testing system, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). For mechanical properties, it was found that increasing GNP content from 1 wt.% to 5 wt.% increased tensile strength of the neat PP up to 4 MPa. The influence of compatibilizers on the mechanical properties had been discussed and reported. For instance, the addition of PP-g-MA compatibilizer improved tensile strength of neat PP with GNP loading. However, the addition of compatibilizer POE-g-MA slightly decreased the tensile strength of neat PP. A similar trend of behavior was observed for flexural strength. For thermal properties, it was found that both GNP loading and compatibilizers have no significant influence on both crystallization and melting temperature of neat PP. For thermal stability, however, it was found that increasing the GNP loading had a significant influence on improving the thermal behavior of neat PP. Furthermore, the addition of compatibilizers into the PP/GNP nanocomposite had slightly improved the thermal stability of neat PP.
A new heterocyclic coupling agent has been produced from the reaction of maleic anhydride and p-aminophenol, namely N-(4-hydroxylpheneyl)maleimide. The coupling agent underwent azo coupling reaction with aromatic amine, which is p-aminophenol to produce a new heterocyclic azo pigment. The pigment was then subjected to solubility, hiding power and light fastness test. Fourier Transform Infrared Spectroscopy (FTIR), Ultraviolet/Visible (UV/Vis) Spectroscopy, and Nuclear Magnetic Resonance Spectroscopy (1H-NMR, 13C-NMR) were used to obtain the characteristics and structural features of the pigment.
Incorporation of nanocellulose could improve wear resistance of ultra-high molecular weight polyethylene (UHMWPE) for an artificial joint application. Yet, the extremely high melt viscosity of the polymer may constrict the mixing, leading to fillers agglomeration and poor mechanical properties. This study optimized the processing condition of UHMWPE/cellulose nanofiber (CNF) bionanocomposite fabrication in triple screw kneading extruder by using response surface methodology (RSM). The effect of the process parameters-temperature (150-190 °C), rotational speed (30-60 rpm), and mixing time (30-45 min)-on mechanical properties of the bionanocomposites was investigated. Homogenous filler distribution, as confirmed by scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analysis, was obtained through the optimal processing condition of 150 °C, 60 rpm, and 45 min. The UHMWPE/CNF bionanocomposites exhibited improved mechanical properties in terms of Young's and flexural modulus by 11% and 19%, respectively, as compared to neat UHMWPE. An insignificant effect was observed when maleic anhydride-grafted-polyethylene (MAPE) was added as compatibilizer. The obtained results proved that homogenous compounding of high melt viscosity UHMWPE with CNF was feasible by optimizing the melt blending processing condition in triple screw kneading extruder, which resulted in improved stiffness, a contributing factor for wear resistance.
Enzyme immobilization has been known to be one of the methods to improve the stability and reusability of enzyme. In this study, a strategy to optimize laccase immobilization on polyethylene terephthalate grafted with maleic anhydride electrospun nanofiber mat (PET-g-MAH ENM) was developed. The development involves the screening and optimization processes of the crucial factors that influence the immobilization yield such as enzyme concentration, pH values, covalent bonding (CV) time, CV temperature, crosslinking (CL) time, CL temperature and glutaraldehyde concentration using two-level factorial design and Box-Behnken design (BBD), respectively. It was found that laccase concentration, pH values and glutaraldehyde concentration play important role in enhancing the immobilization yield of laccase on PET-g-MAH ENM in the screening process. Subsequently, the optimization result showed at 0.28 mg/ml laccase concentration, pH 3 and 0.45% (v/v) glutaraldehyde concentrations gave the highest immobilization yield at 87.64% which was 81.2% increment from the immobilization yield before optimization. Under the optimum condition, the immobilized laccase was able to oxidize 2, 2-azino-bis 3-ethylbenzothiazoline-6- sulfonic acid (ABTS) in a broad range of pH (pH 3-6) and temperature (20- 70 °C). Meanwhile, the kinetic parameters for Km and Vmax were 1.331 mM and 0.041 mM/min, respectively. It was concluded that the optimization of immobilized laccase on PET-g-MAH ENM enhance the performance of this biocatalyst.
Recently, drug functionalized biodegradable polymers have been appreciated to be imperative to fabricate multi-drug delivery nanosystems for sustainable drug release. In this work, amphiphilic chitosan-grafted-(cetyl alcohol-maleic anhydride-pyrazinamide) (CS-g-(CA-MA-PZA)) was synthesized by multi-step reactions. The incorporation of rifampicin (RF) and entrapment of silver nanoparticles (Ag NPs) on CS-g-(CA-MA-PZA) polymer was carried out by dialysis technique. From the FT-IR experiment, the polymer modification, incorporation of drugs and the entrapment of Ag NPs on micelles were confirmed. The surface morphology of Ag NPs, polymeric system and drug loaded micelles was described by SEM, TEM and AFM techniques. In addition, the controlled release behaviour of CS-g-(CA-MA-PZA) micelles was studied by UV-Vis spectroscopy. In vitro cell viability, cell apoptosis and cellular uptake experiments shows that multi-drug delivery system could enhance the biocompatibility and higher the cytotoxicity effect on the cells. Since the prepared amphiphilic polymeric micelles exhibit spotty features and the system is a promising strategy for a novel candidate for immediate therapeutically effects for alveolar macrophages.