In this work, biodegradable composites from poly(lactic acid) (PLA) and oil palm empty fruit bunch (OPEFB) fiber were prepared by melt blending method. Prior to mixing, the fiber was modified through bleaching treatment using hydrogen peroxide. Bleached fiber composite showed an improvement in mechanical properties as compared to untreated fiber composite due to the enhanced fiber/matrix interfacial adhesion. Interestingly, fiber bleaching treatment also improved the physical appearance of the composite. The study was extended by blending the composites with commercially available masterbatch colorant.
The preparation of magnetic nanoparticles coated with chitosan-prindopril erbumine was accomplished and confirmed by X-ray diffraction, TEM, magnetic measurements, thermal analysis and infrared spectroscopic studies. X-ray diffraction and TEM results demonstrated that the magnetic nanoparticles were pure iron oxide phase, having a spherical shape with a mean diameter of 6 nm, compared to 15 nm after coating with chitosan-prindopril erbumine (FCPE). Fourier transform infrared spectroscopy study shows that the coating of iron oxide nanoparticles takes place due to the presence of some bands that were emerging after the coating process, which belong to the prindopril erbumine (PE). The thermal stability of the PE in an FCPE nanocomposite was remarkably enhanced. The release study showed that around 89% of PE could be released within about 93 hours by a phosphate buffer solution at pH 7.4, which was found to be of sustained manner governed by first order kinetic. Compared to the control (untreated), cell viability study in 3T3 cells at 72 h post exposure to both the nanoparticles and the pure drug was found to be sustained above 80% using different doses.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
In this work, poly(lactic acid) (PLA) a fully biodegradable thermoplastic polymer matrix was melt blended with three different epoxidized palm oil (EPO). The aim of this research was to enhance the flexibility, mechanical and thermal properties of PLA. The blends were prepared at various EPO contents of 1, 2, 3, 4 and 5 wt% and characterized. The SEM analysis evidenced successful modification on the neat PLA brittle morphology. Tensile tests indicate that the addition of 1 wt% EPO is sufficient to improve the strength and flexibility compared to neat PLA. Additionally, the flexural and impact properties were also enhanced. Further, DSC analysis showed that the addition of EPO results in a decrease in T(g), which implies an increase in the PLA chain mobility. In the presence of 1 wt% EPO, TGA results revealed significant increase in the thermal stability by 27%. Among the three EPOs used, EPO(3) showed the best mechanical and thermal properties compared to the other EPO's, with an optimum loading of 1 wt%. Conclusively, EPO showed a promising outcome to overcome the brittleness and improve the overall properties of neat PLA, thus can be considered as a potential plasticizer.
Polyimide/SiO(2) composite films were prepared from tetraethoxysilane (TEOS) and poly(amic acid) (PAA) based on aromatic diamine (4-aminophenyl sulfone) (4-APS) and aromatic dianhydride (3,3,4,4-benzophenonetetracarboxylic dianhydride) (BTDA) via a sol-gel process in N-methyl-2-pyrrolidinone (NMP). The prepared polyimide/SiO(2) composite films were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and thermogravimetric analysis (TGA). The FTIR results confirmed the synthesis of polyimide (4-APS/BTDA) and the formation of SiO(2) particles in the polyimide matrix. Meanwhile, the SEM images showed that the SiO(2) particles were well dispersed in the polyimide matrix. Thermal stability and kinetic parameters of the degradation processes for the prepared polyimide/SiO(2) composite films were investigated using TGA in N(2) atmosphere. The activation energy of the solid-state process was calculated using Flynn-Wall-Ozawa's method without the knowledge of the reaction mechanism. The results indicated that thermal stability and the values of the calculated activation energies increased with the increase of the TEOS loading and the activation energy also varied with the percentage of weight loss for all compositions.
Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn(3)Al LDH. A solution casting method was used to prepare PLA/stearate-Zn(3)Al LDH nanocomposites. The anionic clay Zn(3)Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn(3)Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn(3)Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn(3)Al LDH nanocomposites showed that the presence of around 1.0-3.0 wt % of the stearate-Zn(3)Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn(3)Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA.
This study focuses on the synthesis and characterization of the inclusion complex of β-Cyclodextrin (β-CD) with dicationic ionic liquid, 3,3'-(1,4-Phenylenebis [methylene]) bis(1-methyl-1H-imidazol-3-ium) di(bromide) (PhenmimBr). The inclusion complex was prepared at room temperature utilizing conventional kneading technique. Proton ((1)H) NMR and 2D ((1)H-(1)H) COSY NMR were the primary characterization tools employed to verify the formation of the inclusion complex. COSY spectra showed strong correlations between protons of imidazolium and protons of β-CD which indicates that the imidazolium ring of PhenmimBr has entered the cavity of β-CD. UV absorption indicated that β-CD reacts with PhenmimBr to form a 2:1 β-CD-PhenmimBr complex with an apparent formation constant of 2.61 × 10(5) mol&(-2) L(2). Other characterization studies such as UV, FT-IR, XRD, TGA, DSC and SEM studies were also used to further support the formation of the β-CD-PhenmimBr inclusion complex.
In this paper, Polyimide/Montmorillonite Nanocomposites (PI/MMT NCs), based on aromatic diamine (4-Aminophenyl sulfone) (APS) and aromatic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride) (BTDA) were prepared using in situ polymerization and solution-dispersion techniques. The prepared PI/MMT NCs films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The XRD results showed that at the content of 1.0 wt % Organo Montmorillonite (OMMT) for two techniques and 3.0 wt % OMMT for the in situ polymerization technique, the OMMT was well-intercalated, exfoliated and dispersed into polyimide matrix. The OMMT agglomerated when its amount exceeded 10 wt % and 3.0 wt % for solution-dispersion and in situ polymerization techniques respectively. These results were confirmed by the TEM images of the prepared PI/MMT NCs. The TGA thermograms indicated that thermal stability of prepared PI/MMT NCs were increased with the increase of loading that, the effect is higher for the samples prepared by in situ polymerization technique.
ZnO nanostructures were synthesized by hydrothermal method using different molar ratios of cetyltrimethylammonium bromide (CTAB) and Sodium dodecyl sulfate (SDS) as structure directing agents. The effect of surfactants on the morphology of the ZnO crystals was investigated by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) techniques. The results indicate that the mixture of cationic-anionic surfactants can significantly modify the shape and size of ZnO particles. Various structures such as flakes, sheets, rods, spheres, flowers and triangular-like particles sized from micro to nano were obtained. In order to examine the possible changes in other properties of ZnO, characterizations like powder X-ray diffraction (PXRD), thermogravimetric and differential thermogravimetric analysis (TGA-DTG), FTIR, surface area and porosity and UV-visible spectroscopy analysis were also studied and discussed.
This work reports a new method to covalently attach calix[4]arene derivatives onto MCM-41, using a diisocyanate as a linker. The modified mesoporous silicates were characterized by fourier transform infrared spectroscopy (FTIR), thermal analysis (TGA) and elemental analysis. The FTIR spectra and TGA analysis verified that the calix[4]arene derivates are covalently attached to the mesoporous silica. The preservation of the MCM-41 channel system was checked by X-ray diffraction and nitrogen adsorption analysis.
Determination of the thermal characteristics and temperature-dependent rheological properties of the magnetorheological elastomers (MREs) is of paramount importance particularly with regards to MRE applications. Hitherto, a paucity of temperature dependent analysis has been conducted by MRE researchers. In this study, an investigation on the thermal and rheological properties of epoxidized natural rubber (ENR)-based MREs was performed. Various percentages of carbonyl iron particles (CIPs) were blended with the ENR compound using a two roll-mill for the preparation of the ENR-based MRE samples. The morphological, elemental, and thermal analyses were performed before the rheological test. Several characterizations, as well as the effects of the strain amplitude, temperature, and magnetic field on the rheological properties of ENR-based MRE samples, were evaluated. The micrographs and elemental results were well-correlated regarding the CIP and Fe contents, and a uniform distribution of CIPs was achieved. The results of the thermal test indicated that the incorporation of CIPs enhanced the thermal stability of the ENR-based MREs. Based on the rheological analysis, the storage modulus and loss factor were dependent on the CIP content and strain amplitude. The effect of temperature on the rheological properties revealed that the stiffness of the ENR-based MREs was considered stable, and they were appropriate to be employed in the MRE devices exposed to high temperatures above 45 °C.
Radiation processing has been employed successfully for value addition of food and agricultural products. Preliminary studies were undertaken to evaluate the changes induced by ionizing radiation (up to 30 kGy), in the form of gamma irradiation and electron beam irradiation, on some quality attributes and nutritive values of nutraceutically valued lotus seeds. Significant loss in seed firmness was recorded between control and irradiated seeds, irrespective of radiation source. Similarly, the specific viscosity of irradiated lotus seeds decreased significantly up to a dose of 7.5 kGy. Starch increased after exposure to gamma or electron beam irradiation, whereas the total phenolic contents were decreased. Gamma irradiation revealed an enhancement in protein, while the electron beam showed a decrease. Partial oxidation of the seeds during radiation treatments might have occurred as evidenced from the decomposition profiles (thermogravimetry) during heating. It is evident that ionizing radiation brought about significant and variable changes in the quality and nutritive values of lotus seed. Further exploration of this technology for safety and quality is warranted.
Polylactic acid (PLA) nanocomposites reinforced with hybrid montmorillonite/cellulose nanowhiskers [MMT/CNW(SO4)] were prepared by solution casting. The CNW(SO4) nanofiller was first isolated from microcrystalline cellulose using acid hydrolysis treatment. PLA/MMT/CNW(SO4) hybrid nanocomposites were prepared by the addition of various amounts of CNW(SO4) [1-9 parts per hundred parts of polymer (phr)] into PLA/MMT nanocomposite at 5 phr MMT content, based on highest tensile strength values as reported previously. The biodegradability, thermal, tensile, morphological, water absorption and transparency properties of PLA/MMT/CNW(SO4) hybrid nanocomposites were investigated. The Biodegradability, thermal stability and crystallinity of hybrid nanocomposites increased compared to PLA/MMT nanocomposite and neat PLA. The highest tensile strength of hybrid nanocomposites was obtained by incorporating 1 phr CNW(SO4) [∼ 36 MPa]. Interestingly, the ductility of hybrid nanocomposites increased significantly by 87% at this formulation. The Young's modulus increased linearly with increasing CNW(SO4) content. This is due to the relatively good dispersion of nanofillers in the hybrid nanocomposites, as revealed by transmission electron microscopy. Fourier transform infrared spectroscopy indicated the formation of some polar interactions. In addition, water resistance of the hybrid nanocomposites improved and the visual transparency of neat PLA film did not affect by addition of CNW(SO4).
In this study, hybrid montmorillonite/cellulose nanowhiskers (MMT/CNW) reinforced polylactic acid (PLA) nanocomposites were produced through solution casting. The CNW filler was first isolated from microcrystalline cellulose by chemical swelling technique. The partial replacement of MMT with CNW in order to produce PLA/MMT/CNW hybrid nanocomposites was performed at 5 parts per hundred parts of polymer (phr) fillers content, based on highest tensile strength values as reported in our previous study. MMT were partially replaced with various amounts of CNW (1, 2, 3, 4 and 5phr). The tensile, thermal, morphological and biodegradability properties of PLA hybrid nanocomposites were investigated. The highest tensile strength of hybrid nanocomposites was obtained with the combination of 4phr MMT and 1phr CNW. Interestingly, the ductility of hybrid nanocomposites increased significantly by 79% at this formulation. The Young's modulus increased linearly with increasing CNW content. Thermogravimetric analysis illustrated that the partial replacement of MMT with CNW filler enhanced the thermal stability of the PLA. This is due to the relatively good dispersion of fillers in the hybrid nanocomposites samples as revealed by transmission electron microscopy. Interestingly, partial replacements of MMT with CNW improved the biodegradability of hybrid nanocomposites compared to PLA/MMT and neat PLA.
The aim of this study is to investigate natural cellulosic fibers extracted from Tridax procumbens plants. The obtained fibers were alkali treated for their effective usage as reinforcement in composites. The physical, chemical, crystallinity, thermal, wettability and surface characteristics were analyzed for raw, and alkali treated Tridax procumbens fibers (TPFs). The test results conclude that there was an increase in cellulose content with a reduction in hemicellulose, lignin, and wax upon alkali treatment. This enhanced the thermal stability, tensile strength, crystallinity, and surface roughness characteristics. The contact angle was also lesser for treated TPFs which prove its better wettability with the liquid phase. The Weibull distribution analysis was adopted for the analysis of the fiber diameter and tensile properties. Thus the considerable improvement in the properties of alkali treated TPFs would be worth for developing high-performance polymer composites.
In this study, biodegradable composite films were prepared by using thermoplastic cornstarch matrix and corn husk fiber as a reinforcing filler. The composite films were manufactured via a casting technique using different concentrations of husk fiber (0-8%), and fructose as a plasticizer at a fixed amount of 25% for starch weight. The Physical, thermal, morphological, and tensile characteristics of composite films were investigated. The findings indicated that the incorporation of husk fiber, in general, enhanced the performance of the composite films. There was a noticeable reduction in the density and moisture content of the films, and soil burial assessment showed less resistance to biodegradation. The morphological images presented a consistent structure and excellent compatibility between matrix and reinforcement, which reflected on the improved tensile strength and young modulus as well as the crystallinity index. The thermal stability of composite films has also been enhanced, as evidenced by the increased onset decomposition temperature of the reinforced films compared to neat film. Fourier transform infrared analysis revealed increasing in intermolecular hydrogen bonding following fiber loading. The composite materials prepared using corn husk residues as reinforcement responded to community demand for agricultural and polymeric waste disposal and added more value to waste management.
Cellulose nanowhisker (NWC) was extracted by hydrolysing Pennisetum purpureum (PP) fibres with acid and alkali. They were subjected to different periods of acid hydrolysis; 30, 45, and 60 min. NWC morphology and physicochemical properties were characterised by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), particle size analyser, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and thermogravimetric analysis. NWC3, which underwent the longest hydrolysis time, showed the smallest width and length, under TEM. All samples presented a needle-like shape under TEM and AFM; uneven lengths and irregular shapes under FESEM; and a broad range of distribution, with the particle size analyser. All samples exhibited a good crystallinity index (CrI)-72.0 to 74.6%. The highest CrI% corresponded to 60 min of acid hydrolysis. Thermogravimetric analysis showed thermal stability between 310.72 °C and 336.28 °C. Thus, cellulose nanowhisker from PP fibres, have high potential as bio-nanocomposites.
Olive fiber is a renewable natural fiber which has potential as an alternative biomass for extraction of microcrystalline cellulose (MCC). MCC has been widely applied in various industries owing to its small dimensional size for ease of reactive fabrication process. At present study, a serial treatments of bleaching, alkaline and acid hydrolysis was employed to extract OL-BLF, OL-PUF, and OL-MCC respectively from olive stem fiber. In morphology examination, a feature of short micro-crystallite particles was obtained for OL-MCC. The particle size was found gradually reducing from OL-PUF (305.31 μm) to OL-MCC (156.06 μm) due to the disintegration of cellulose fibrils. From physicochemical analysis, most lignin and hemicellulose components had been removed from OL-BLF to form OL-PUF with individually fibril structure. The elemental analysis revealed that highly pure cellulose component was obtained for OL-MCC. Also, the rigidity had been improved from OL-BLF to OL-PUF, while with the highest for OL-MCC with 74.2% crystallinity, endowing it as a reliable load-bearing agent. As for thermal analysis, OL-MCC had the most stable heat resistance in among the chemically-treated fibers. Therefore, olive MCC could act as a promising reinforcing agent to withstand harsh conditions for variety fields of composite applications.
Chitosan-deep eutectic solvent (DES) beads were prepared from chitosan and DESs. The DESs used were choline chloride-urea (DES A) and choline chloride-glycerol (DES B). Both chitosan-DES beads were used to remove malachite green (MG) dye from an aqueous solution. The optimum pH for chitosan-DES A was recorded at pH 8.0 while optimum pH for chitosan-DES B was pH 9.0. The maximum adsorption capacity obtained for chitosan-DES A and chitosan-DES B were 6.54 mg/g and 8.64 mg/g, respectively. The optimum conditions for both chitosan-DES beads to remove MG were 0.08 g of adsorbent and 20 min of agitation time. Five kinetic models were applied to analyse the data and the results showed that the pseudo-second-order and intraparticle diffusion model fitted best with R2 > 0.999. For the adsorption capacity, results show that the Freundlich and Langmuir adsorption isotherms fitted well with chitosan-DES A and chitosan-DES B, respectively. The maximum adsorption capacities (qmax) obtained from chitosan-DES A and chitosan-DES B were 1.43 mg/g and 17.86 mg/g, respectively. Desorption indicated good performance in practical applications.
A study was carried out to determine the effectiveness of lignin, extracted from oil palm (Elaeis guineensis) biomass as water-in-oil (W/O) emulsifying agent. To achieve this goal, soda lignin (SL) was extracted via soda pulping process and a series of nanosized soda lignin (NSL) were prepared using homogenizer at three different speed i.e. 10,400 rpm (NSL 10), 11,400 rpm (NSL 11) and 12,400 rpm (NSL 12) for one hour. All prepared samples were characterized by FT-IR, UV-Vis spectroscopy, thermogravimetric analysis (TGA), zeta potential analyser, Transmission Electron Microscope (TEM) and Extreme High Resolution Field Emission Scanning Electron Microscope (XHR-FESEM). The result of FTIR showed that there is no prominent change occurred in spectra of all samples while a good stability was reflected by TGA curves. The percentage of creaming index and visual observations of all samples demonstrated that NSL 12 and dosage 2 g (out of 1 g, 1.5 g and 2 g) were found to be the best among all samples. Furthermore, the results of IFT indicate that NSL 12 was proven to be more stable than the commercial product. Therefore, NSL 12 is selected for toxicological studies and was found safe in both, in vitro and in vivo studies.