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.
Palm empty fruit bunch ash (EFB-ash) was used as a natural catalyst, rich in potassium to enhance the CO2 gasification reactivity of palm shell char (PS-char). Various EFB-ash loadings (ranging from 0 to 12.5wt.%) were implemented to improve the reactivity of PS-char during CO2 gasification studies using thermogravimetric analysis. The achieved results explored that the highest gasification reactivity was devoted to 10% EFB-ash loaded char. The SEM-EDS and XRD analyses further confirmed the successful loading of EFB-ash on PS-char which contributed to promoting the gasification reactivity of char. Random pore model was applied to determine the kinetic parameters in catalytic gasification of char at various temperatures of 800-900°C. The dependence of char reaction rate on gasification temperature resulted in a straight line in Arrhenius-type plot, from which the activation energy of 158.75kJ/mol was obtained for the catalytic char gasification.
An active heterogeneous Al2O3 modified MgZnO (MgZnAlO) catalyst was prepared and the catalytic activity was investigated for the transesterification of different vegetable oils (refined palm oil, waste cooking palm oil, palm kernel oil and coconut oil) with methanol to produce biodiesel. The catalyst was characterized by using X-ray diffraction, Fourier transform infrared spectra, thermo gravimetric and differential thermal analysis to ascertain its versatility. Effects of important reaction parameters such as methanol to oil molar ratio, catalyst dosage, reaction temperature and reaction time on oil conversion were examined. Within the range of studied variability, the suitable transesterification conditions (methanol/oil ratio 16:1, catalyst loading 3.32 wt.%, reaction time 6h, temperature 182°C), the oil conversion of 98% could be achieved with reference to coconut oil in a single stage. The catalyst can be easily recovered and reused for five cycles without significant deactivation.
Carboxymethyl sago starch-acid hydrogel was prepared via irradiation technique to remove divalent metal ions (Pb, Cu and Cd) from their aqueous solution. The hydrogel was characterized by using Fourier Transform Infrared (FT-IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The removal of these metal ions was analyzed by using inductively coupled plasma-optic emission spectra (ICP-OES) to study the amount of metal uptake by the hydrogel. Parameters of study include effect of pH, amount of sample, contact time, initial concentration of metal solution and reaction temperature. FTIR spectroscopy shows the CMSS hydrogel absorption peaks at 1741cm(-1), 1605cm(-1) and 1430cm(-1) which indicates the substitution of carboxymethyl group of modified sago starch. The degradation temperature of CMSS hydrogel is higher compared to CMSS due to the crosslinking by electron beam radiation and formed a porous hydrogel. From the data obtained, about 93.5%, 88.4% and 85.5% of Pb, Cu and Cd ions has been respectively removed from their solution under optimum condition.
The aim of this work was to characterize the natural low transition temperature mixtures (LTTMs) as promising green solvents for biomass pretreatment with the critical characteristics of cheap, biodegradable and renewable, which overcome the limitations of ionic liquids (ILs). The LTTMs were derived from inexpensive commercially available hydrogen bond acceptor (HBA) and l-malic acid as the hydrogen bond donor (HBD) in distinct molar ratios of starting materials and water. The peaks involved in the H-bonding shifted and became broader for the OH groups. The thermal properties of the LTTMs were not affected by water while the biopolymers solubility capacity of LTTMs was improved with the increased molar ratio of water and treatment temperature. The pretreatment of oil palm biomass was consistence with the screening on solubility of biopolymers. This work provides a cost-effective alternative to utilize microwave hydrothermal extracted green solvents such as malic acid from natural fruits and plants.
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.
This study reports on the effects of unmodified autohydrolyzed ethanol organosolv lignin (AH EOL) and modified autohydrolyzed ethanol organosolv lignin on the structural characteristics and antioxidant properties upon incorporation of p-hydroxyacetophenone (AHP EOL). The lignin samples isolated from black liquor of oil palm fronds (OPF) were evaluated and compared using various complementary analyses; FTIR, 1H and 13C NMR spectroscopy, 2D-NMR spectroscopy (HMBC and HSQC), CHN, GPC, HPLC and thermal analyses (TGA and DSC). Chemically modified organosolv lignin (AHP EOL) provided lignin with lower molecular weight (Mw), which has smaller fragments that leads to higher solubility rate in water in comparison to unmodified organosolv lignin, AH EOL (DAHP EOL: 19.8% > DAH EOL: 14.0%). It was evident that the antioxidant properties of modified organosolv lignin has better reducing power in comparison to the unmodified organosolv lignin. Therefore, the functionalization of lignin polymers enhanced their antioxidant properties and structural features towards a various alternative approach in lignin-based applications.
The present study aims to develop a biodegradable polymer blend that is environmentally friendly and has comparable tensile and thermal properties with synthetic plastics. In this work, microcrystalline cellulose (MCC) extracted from bamboo-chips-reinforced poly (lactic acid) (PLA) and poly (butylene succinate) (PBS) blend composites were fabricated by melt-mixing at 180 °C and then hot pressing at 180 °C. PBS and MCC (0.5, 1, 1.5 wt%) were added to improve the brittle nature of PLA. Field emission scanning electron microscopy (FESEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), thermogravimetric analysis (TGA), differential thermogravimetry (DTG), differential scanning calorimetry (DSC)), and universal testing machine were used to analyze morphology, crystallinity, physiochemical, thermal, and tensile properties, respectively. The thermal stability of the PLA-PBS blends enhanced on addition of MCC up to 1wt % due to their uniform dispersion in the polymer matrix. Tensile properties declined on addition of PBS and increased with MCC above (0.5 wt%) however except elongation at break increased on addition of PBS then decreased insignificantly on addition of MCC. Thus, PBS and MCC addition in PLA matrix decreases the brittleness, making it a potential contender that could be considered to replace plastics that are used for food packaging.
The degradation and mechanical properties of potential polymeric materials used for green manufacturing are significant determinants. In this study, cellulose nanofibre was prepared from Schizostachyum brachycladum bamboo and used as reinforcement in the PLA/chitosan matrix using melt extrusion and compression moulding method. The cellulose nanofibre(CNF) was isolated using supercritical carbon dioxide and high-pressure homogenisation. The isolated CNF was characterised with transmission electron microscopy (TEM), FT-IR, zeta potential and particle size analysis. The mechanical, physical, and degradation properties of the resulting biocomposite were studied with moisture content, density, thickness swelling, tensile, flexural, scanning electron microscopy, thermogravimetry, and biodegradability analysis. The TEM, FT-IR, and particle size results showed successful isolation of cellulose nanofibre using this method. The result showed that the physical, mechanical, and degradation properties of PLA/chitosan/CNF biocomposite were significantly enhanced with cellulose nanofibre. The density, thickness swelling, and moisture content increased with the addition of CNF. Also, tensile strength and modulus; flexural strength and modulus increased; while the elongation reduced. The carbon residue from the thermal degradation and the glass transition temperature of the PLA/chitosan/CNF biocomposite was observed to increase with the addition of CNF. The result showed that the biocomposite has potential for green and sustainable industrial application.
Genipin, a natural and non-toxic cross linker, was used to prepare cross linked floating kappa carrageenan/sodium carboxymethyl cellulose hydrogels and the effect of genipin on hydrogels characterization was investigated. Calcium carbonates were employed as gas forming agents. Ranitidine hydrochloride was used as drug. Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were carried out to study the changes in the characteristics of hydrogels. Furthermore, scanning electron microscope (SEM) was performed to study microstructure of hydrogels. The result showed that all formulated hydrogels had excellent floating behavior. It was discovered that the cross linking reaction showed significant effect on gel strength, porosity and swelling ratio compared to non-cross linked hydrogels. It was found that the drug release was slower and lesser after being cross linked. Microstructure study shows that cross linked hydrogels exhibited hard and rough surface. Therefore, genipin can be an interesting cross linking agent for controlled drug delivery in gastrointestinal tract.
The mechanical, thermal, and morphological properties of a 3D porous Pennisetum purpureum (PP)/polylactic acid (PLA) based scaffold were investigated. In this study, a scaffold containing P. purpureum and PLA was produced using the solvent casting and particulate leaching method. P. purpureum fibre, also locally known as Napier grass, is composed of 46% cellulose, 34% hemicellulose, and 20% lignin. PLA composites with various P. purpureum contents (10%, 20%, and 30%) were prepared and subsequently characterised. The morphologies, structures and thermal behaviours of the prepared composite scaffolds were characterised using field-emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). The morphology was studied using FESEM; the scaffold possessed 70-200μm-sized pores with a high level of interconnectivity. The moisture content and mechanical properties of the developed porous scaffolds were further characterised. The P. purpureum/PLA scaffold had a greater porosity factor (99%) and compression modulus (5.25MPa) than those of the pure PLA scaffold (1.73MPa). From the results, it can be concluded that the properties of the highly porous P. purpureum/PLA scaffold developed in this study can be controlled and optimised. This can be used to facilitate the construction of implantable tissue-engineered cartilage.
Feather keratin is a biomass generated in excess from various livestock industries. With appropriate processing, it holds potential as a green source for degradable biopolymer that could potentially replace current fossil fuel based materials. Several processing methods have been developed, but the use of ultrasonication has not been explored. In this study, we focus on (i) comparing and optimizing the dissolution process of turkey feather keratin through sonication and conventional processes, and (ii) generating a biodegradable polymer material, as a value added product, from the dissolved keratin that could be used in packaging and other applications. Sonication of feather keratin in pure ionic liquids (ILs) and a mixture containing ILs and different co-solvents was conducted under different applied acoustic power levels. It was found that ultrasonic irradiation significantly improved the rate of dissolution of feather keratin as compared to the conventional method, from about 2 h to less than 20 min. The amount of ILs needed was also reduced by introducing a suitable co-solvent. The keratin was then regenerated, analyzed and characterized using various methods. This material holds the potential to be reused in various appliances.
This study has investigated complexation of fisetin, a natural flavonoid, with three types of cyclodextrins to improve its solubility. Sulfobutylether-β-cyclodextrin (SBE-β-CD) showed the highest complexation efficiency while maintaining the in vitro antioxidant activity of fisetin. Addition of 20%v/v ethanol in water improved the amount of solubilized fisetin in the complex 5.9-fold compared to the system containing water alone. Spray drying of fisetin-SBE-β-CD complex solution in the presence of ethanol produced a dry powder with improved aerosolization properties when delivered from a dry powder inhaler, indicated by a 2-fold increase in the fine particle fraction (FPF) compared to the powder produced from the complex solution containing water alone. The pitted morphological surface of these particles suggested a more hollow internal structure, indicating a lighter and less dense powder. Incorporation of 20%w/w leucine improved the particle size distribution of the powder and further increased the FPF by 2.3-fold. This formulation also showed an EC50 value equivalent to fisetin alone in the A549 cell line. In conclusion, an inhalable dry powder containing fisetin-SBE-β-CD complex was successfully engineered with an improved aqueous solubility of fisetin. The dry powder may be useful to deliver high amounts of fisetin to the deep lung region for therapeutic purposes.
Many wounds are unresponsive to currently available treatment techniques and therefore there is an immense need to explore suitable materials, including biomaterials, which could be considered as the crucial factor to accelerate the healing cascade. In this study, we fabricated polyhydroxyalkanoate-based antibacterial mats via an electrospinning technique. One-pot green synthesized graphene-decorated silver nanoparticles (GAg) were incorporated into the fibres of poly-3 hydroxybutarate-co-12 mol.% hydroxyhexanoate (P3HB-co-12 mol.% HHx), a co-polymer of the polyhydroxyalkanoate (PHA) family which is highly biocompatible, biodegradable, and flexible in nature. The synthesized PHA/GAg biomaterial has been characterized by field emission scanning electron microscopy (FESEM), elemental mapping, thermogravimetric analysis (TGA), UV-visible spectroscopy (UV-vis), and Fourier transform infrared spectroscopy (FTIR). An in vitro antibacterial analysis was performed to investigate the efficacy of PHA/GAg against gram-positive Staphylococcus aureus (S. aureus) strain 12,600 ATCC and gram-negative Escherichia coli (E. coli) strain 8739 ATCC. The results indicated that the PHA/GAg demonstrated significant reduction of S. aureus and E. coli as compared to bare PHA or PHA- reduced graphene oxide (rGO) in 2 h of time. The p value (p < 0.05) was obtained by using a two-sample t-test distribution.
The current study is motivated by the strict environmental regulations regarding the utilization and consumption of ecofriendly materials. In this context, the aim of this study has been to prepare and characterize different date palm tree (Phoenix dactylifera L.) fibers processed through the conventional water retting method. The chemical, elemental, crystallinity, thermal and morphological characterization of trunk (DPTRF), leaf stalk (DPLST), sheath or leaf sheath (DPLSH) and fruit bunch stalk (DPFBS) fibers was carried out. Chemical analysis revealed that the four types of date palm fibers display noteworthy differences in the content of cellulose, hemicellulose and lignin. Also, the amount of calcium is relatively high in all the date palm fibers; besides this, DPTRF exhibited 69.2% crystallinity, which is lower than that of DPLSH with 72.4% crystallinity. Moreover, DPLST and DPFBS fibers are more thermally stable (higher thermal degradation temperature) than DPTRF and DPLSH samples. Morphological analysis revealed that the fracture surface of DPFBS was relatively rougher, which would probably lead to increased bonding strength with polymers in composites. Overall, we conclude that DPFBS would be promising alternative sustainable and biomass material for the isolation of respective cellulose nanofibers and cellulose nanocrystals as potential reinforcement in polymer composites.
This study reports the influence of ZrO2/β-TCP hybridization on the thermal, mechanical, and physical properties of polyamide 12 composites to be suited for bone replacement. Amount of 15 wt% of nano-ZrO2 along with 5,10,15,20 and 25 wt% of micro-β-TCP was compounded with polyamide 12 via a twin-screw extruder. The hybrid ZrO2/β-TCP filled polyamide 12 exhibited higher thermal, mechanical and physical properties in comparison to unfilled polyamide 12 at certain filler loading; which is attributed to the homogenous dispersion of ZrO2/β-TCP fillers particle in polyamide 12 matrix. The hybrid ZrO2/β-TCP filled PA 12 demonstrated an increment of tensile strength by up to 1%, tensile modulus of 38%, flexural strength of 15%, flexural modulus of 45%, and surface roughness value of 93%, as compared to unfilled PA 12. With enhanced thermal, mechanical and physical properties, the newly developed hybrid ZrO2/β-TCP filled PA 12 could be potentially utilized for bone replacement.
A green regenerated superabsorbent hydrogel was fabricated with mixtures of dissolved oil palm empty fruit bunch (EFB) cellulose and sodium carboxymethylcellulose (NaCMC) in NaOH/urea system. The formation of hydrogel was aided with epichlorohydrin (ECH) as a crosslinker. The resultant regenerated hydrogel was able to swell >80,000% depending on the NaCMC concentrations. The hydrogel absorbed water rapidly upon exposure to water up to 48 h and gradually declined after 72 h. The crosslinked of covalent bond of COC between dissolved EFB cellulose (EFBC) with NaCMC was confirmed with Attenuated total reflectance Fourier transform infrared (ATR-FT-IR) spectroscopy. Crystallinity and thermal stability of the hydrogel samples were depended on the concentrations of NaCMC, crosslinking, and swelling process. The strength and stability of crosslinked network was studied by examining the gel fraction of hydrogel. This study explored the swelling ability and probable influenced factors towards physical and chemical properties of hydrogel.
In this study, poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) dual-layer membranes filled with 0-3 wt% cellulose nanowhisker (CNWs) were fabricated with aim to remove metal ions from wastewater. An integrated method was employed in the membrane fabrication process by combining water vapor-induced and crystallization-induced phase inversions. The membrane thickness was measured in between 11 and 13 μm, which did not pose significant flux deviation during filtration process. The 3% CNW filled membrane showed prominent and well-laminated two layers structure. Meanwhile, the increase in CNWs from 0 to 3% loadings could improve the membrane porosity (43-74%) but reducing pore size (2.45-0.54 μm). The heat resistance of neat membrane enhanced by 1% CNW but decreased with loadings of 2-3% CNWs due to flaming behavior of sulphated nanocellulose. Membrane with 3% CNW displayed the tensile strength (23.5 MPa), elongation at break (7.1%), and Young's modulus (0.75 GPa) as compared to other samples. For wastewater filtration performance, the continuous operation test showed that 3% CNW filled membrane exhibited the highest removal efficiency for both cobalt and nickel metal ions reaching to 83% and 84%, respectively. We concluded that CNWs filled dual-layer membranes have potential for future development in the removal of heavy metal ions from wastewater streams.
Cassava starch has acquired many attentions owing to its ability to be developed as thermoplastic cassava starch (TPCS) where it can be obtained in low cost, making it to be one of alternatives to substitute petroleum-based plastic. An attempt was made to investigate the thermal, mechanical and moisture absorption properties of thermoplastic cassava starch blending with beeswax (TPCS-BW) fabricated using hot moulding compression method in the range of beeswax loading from 0, 2.5, 5 to 10 wt%. Addition of beeswax has significantly reduced tensile strength, elongation and flexural strength while improving tensile modulus and flexural modulus until 5 wt% beeswax. Incorporation of 10 wt% beeswax has successfully produced the lowest value of moisture absorption and water solubility among the bio-composite which might be attributed to the beeswax's hydrophobic properties in improving water barrier of the TPCS-BW bio-composite. Furthermore, the addition of beeswax resulted in the appearance of irregular and rough fractured surface. Meanwhile, fourier transform infrared (FT-IR) spectroscopy presented that incorporation of beeswax in the mixture has considerably improve hydrogen bonding of blends indicating good interaction between starch and beeswax. Hence, beeswax with an appropriate loading value able to improve the functional properties of TPCS-BW bio-composite.