Nanocrystalline SnO(x) (x = 1-2) thin films were prepared on glass substrates by a simple chemical bath deposition method. Triethanolamine was used as complexing agent to decrease time and temperature of deposition and shift the pH of the solution to the noncorrosive region. The films were characterized for composition, surface morphology, structure and optical properties. X-ray diffraction analysis confirms that SnO(x) thin films consist of a polycrystalline structure with an average grain size of 36 nm. Atomic force microscopy studies show a uniform grain distribution without pinholes. The elemental composition was evaluated by energy dispersive X-ray spectroscopy. The average O/Sn atomic percentage ratio is 1.72. Band gap energy and optical transition were determined from optical absorbance data. The film was found to exhibit direct and indirect transitions in the visible spectrum with band gap values of about 3.9 and 3.7 eV, respectively. The optical transmittance in the visible region is 82%. The SnO(x) nanocrystals exhibit an ultraviolet emission band centered at 392 nm in the vicinity of the band edge, which is attributed to the well-known exciton transition in SnO(x). Photosensitivity was detected in the positive region under illumination with white light.
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.
Natural fiber as reinforcement filler in polymer composites is an attractive approach due to being fully biodegradable and cheap. However, incompatibility between hydrophilic natural fiber and hydrophobic polymer matrix restricts the application. The current studies focus on the effects of incorporation of silane treated OPMF into polylactic acid (PLA)/polycaprolactone (PCL)/nanoclay/OPMF hybrid composites. The composites were prepared by melt blending technique and characterize the composites with Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). FTIR spectra indicated that peak shifting occurs when silane treated OPMF was incorporated into hybrid composites. Based on mechanical properties results, incorporation of silane treated OPMF enhances the mechanical properties of unmodified OPMF hybrid composites with the enhancement of flexural and impact strength being 17.60% and 48.43%, respectively, at 10% fiber loading. TGA thermogram shows that incorporation of silane treated OPMF did not show increment in thermal properties of hybrid composites. SEM micrographs revealed that silane treated OPMF hybrid composites show good fiber/matrix adhesion as fiber is still embedded in the matrix and no cavity is present on the surface. Water absorption test shows that addition of less hydrophilic silane treated OPMF successfully reduces the water uptake of hybrid composites.
Co-composting of poultry manure and rubber wood sawdust was performed with the ratio of 2:1 (V/V) for a period of 60 days. An investigation was carried out to study the extracellular enzymatic activities and structural degradation utilizing Fourier transform infrared spectroscopy (FT-IR), thermogravimetry and differential thermal analysis (TG/DTA) and scanning electron microscopy (SEM). The microbial succession was also determined by using denaturing gel gradient electrophoresis (DGGE). The compost was able to reach its highest temperature of 71°C at day 3 and stabilized between 30 and 40°C for 8 weeks. CMCase, FPase and β-glucosidase acted synergistically in order to degrade the cellulosic substrate. The xylanase activities increased gradually during the composting and reached the peak value of 11.637 U/g on day 35, followed by a sharp decline. Both LiP and MnP activities reached their peak values on day 35 with 0.431 and 0.132 U/g respectively. The FT-IR spectra revealed an increase in aromaticity and a decrease in aliphatic compounds such as carbohydrates as decomposition proceeded. TGA/DTG data exhibited significant changes in weight loss in compost samples, indicating degradation of organic matter. SEM micrographs showed higher amounts of parenchyma exposed on the surface of rubber wood sawdust at day 60, showing significant degradation. DGGE and 16S rDNA analyses showed that Burkholderia sp., Pandoraea sp., and Pseudomonas sp. were present throughout the composting process. Ornithinibacillus sp. and Castellaniella ginsengisoli were only found in the initial stage of the composting, while different strains of Burkholderia sp. also occurred in the later stage of composting.
In the present study, catalytic pyrolysis of Chlorella vulgaris biomass was conducted to analyse the kinetic and thermodynamic performances through thermogravimetric approach. HZSM-5 zeolite, limestone (LS), bifunctional HZSM-5/LS were used as catalysts and the experiments were heated from 50 to 900 °C at heating rates of 10-100 °C/min. Iso-conversional model-free methods such as Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), Starink's, and Vyazovkin (V) were employed to evaluate the kinetic parameters meanwhile the thermodynamic parameters were determined by using FWO and KAS methods. The calculated EA values of non-catalytic and catalytic pyrolysis of HZSM-5 zeolite, LS, and bifunctional HZSM-5/LS were determined to be in the range of 156.16-158.10 kJ/mol, 145.26-147.84 kJ/mol, 138.81-142.06 kJ/mol, and 133.26 kJ/mol respectively. The results have shown that catalytic pyrolysis with the presence of bifunctional HZSM-5/LS resulted to a lower average EA and ΔH compared to HZSM-5, and LS which indicated less energy requirement in the process.
Thermodynamic and kinetic parameters of catalytic pyrolysis of rice hull (RH) pyrolysis using two different types of renewable catalysts namely natural limestone (LS) and eggshells (ES) using thermogravimetric analysis (TG) approach at different heating rates of 10-100 K min-1 in temperature range of 323-1173 K are investigated. Catalytic pyrolysis mechanism of both catalysts had shown significant effect on the degradation of RH. Model free kinetic of iso-conversional method (Flynn-Wall-Ozawa) and multi-step reaction model (Distributed Activation Energy Model) were employed into present study. The average activation energy was found in the range of 175.4-177.7 kJ mol-1 (RH), 123.3-132.5 kJ mol-1 (RH-LS), and 96.1-100.4 kJ mol-1 (RH-ES) respectively. The syngas composition had increased from 60.05 wt% to 63.1 wt% (RH-LS) and 63.4 wt% (RH-ES). However, the CO2 content had decreased from 24.1 wt% (RH) to 20.8 wt% (RH-LS) and 19.9 wt% (RH-ES).
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.
Pyrolysis of agricultural biomass is a promising technique for producing renewable energy and effectively managing solid waste. In this study, groundnut shell (GNS) was processed at 500 °C in an inert gas atmosphere with a gas flow rate and a heating rate of 10 mL/min and 10 °C/min, respectively, in a custom-designed fluidized bed pyrolytic-reactor. Under optimal operating conditions, the GNS-derived pyrolytic-oil yield was 62.8 wt.%, with the corresponding biochar (19.5 wt.%) and biogas yields (17.7 wt.%). The GC-MS analysis of the GNS-based bio-oil confirmed the presence of (trifluoromethyl)pyridin-2-amine (18.814%), 2-Fluoroformyl-3,3,4,4-tetrafluoro-1,2-oxazetidine (16.23%), 5,7-dimethyl-1H-Indazole (11.613%), N-methyl-N-nitropropan-2-amine (6.5%) and butyl piperidino sulfone (5.668%) as major components, which are used as building blocks in the biofuel, pharmaceutical, and food industries. Furthermore, a 2 × 5 × 1 artificial neural network (ANN) architecture was developed to predict the decomposition behavior of GNS at heating rates of 5, 10, and 20 °C/min, while the thermodynamic and kinetic parameters were estimated using a non-isothermal model-free method. The Popescu method predicted activation energy (Ea) of GNS biomass ranging from 111 kJ/mol to 260 kJ/mol, with changes in enthalpy (ΔH), Gibbs-free energy (ΔG), and entropy (ΔS) ranging from 106 to 254 kJ/mol, 162-241 kJ/mol, and -0.0937 to 0.0598 kJ/mol/K, respectively. The extraction of high-quality precursors from GNS pyrolysis was demonstrated in this study, as well as the usefulness of the ANN technique for thermogravimetric analysis of biomass.
A controlled-release formulation of an antihistamine, cetirizine, was synthesized using zinc-layered hydroxide as the host and cetirizine as the guest. The resulting well-ordered nanolayered structure, a cetirizine nanocomposite "CETN," had a basal spacing of 33.9 Å, averaged from six harmonics observed from X-ray diffraction. The guest, cetirizine, was arranged in a horizontal bilayer between the zinc-layered hydroxide (ZLH) inorganic interlayers. Fourier transform infrared spectroscopy studies indicated that the intercalation takes place without major change in the structure of the guest and that the thermal stability of the guest in the nanocomposites is markedly enhanced. The loading of the guest in the nanocomposites was estimated to be about 49.4% (w/w). The release study showed that about 96% of the guest could be released in 80 hours by phosphate buffer solution at pH 7.4 compared with about 97% in 73 hours at pH 4.8. It was found that release was governed by pseudo-second order kinetics. Release of histamine from rat basophilic leukemia cells was found to be more sensitive to the intercalated cetirizine in the CETN compared with its free counterpart, with inhibition of 56% and 29%, respectively, at 62.5 ng/mL. The cytotoxicity assay toward Chang liver cells line show the IC₅₀ for CETN and ZLH are 617 and 670 μg/mL, respectively.
A new simple preparation method for a hippurate-intercalated zinc-layered hydroxide (ZLH) nanohybrid has been established, which does not need an anion-exchange procedure to intercalate the hippurate anion into ZLH interlayers.
An ellagic acid (EA)-zinc layered hydroxide (ZLH) nanohybrid (EAN) was synthesized under a nonaqueous environment using EA and zinc oxide (ZnO) as the precursors. Powder X-ray diffraction showed that the basal spacing of the nanohybrid was 10.4 Å, resulting in the spatial orientation of EA molecules between the interlayers of 22.5° from z-axis with two negative charges at 8,8' position of the molecules pointed toward the ZLH interlayers. FTIR study showed that the intercalated EA spectral feature is generally similar to that of EA, but with bands slightly shifted. This indicates that some chemical bonding of EA presence between the nanohybrid interlayers was slightly changed, due to the formation of host-guest interaction. The nanohybrid is of mesopores type with 58.8% drug loading and enhanced thermal stability. The release of the drug active, EA from the nanohybrid was found to be sustained and therefore has good potential to be used as a drug controlled-release formulation. In vitro bioassay study showed that the EAN has a mild effect on the hepatocytes cells, similar to its counterpart, free EA.
Nystatin is a tetraene diene polyene antibiotic showing a broad spectrum of antifungal activity. In the present study, we prepared a nystatin nanocomposite (Nyst-CS-MNP) by loading nystatin (Nyst) on chitosan (CS) coated magnetic nanoparticles (MNPs). The magnetic nanocomposites were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry analysis (TGA), vibrating sample magnetometer (VSM), and scanning electron microscopy (SEM). The XRD results showed that the MNPs and nanocomposite are pure magnetite. The FTIR analysis confirmed the binding of CS on the surface of the MNPs and also the loading of Nyst in the nanocomposite. The Nyst drug loading was estimated using UV-Vis instrumentation and showing a 14.9% loading in the nanocomposite. The TEM size image of the MNPs, CS-MNP, and Nyst-CS-MNP was 13, 11, and 8 nm, respectively. The release profile of the Nyst drug from the nanocomposite followed a pseudo-second-order kinetic model. The antimicrobial activity of the as-synthesized Nyst and Nyst-CS-MNP nanocomposite was evaluated using an agar diffusion method and showed enhanced antifungal activity against Candida albicans. In this manner, this study introduces a novel nanocomposite that can decrease fungus activity on-demand for numerous medical applications.
Chitin ranks next to cellulose as the most important bio-polysaccharide which can primarily be extracted from crustacean shells. However, the emergence of new areas of the application of chitin and its derivatives are on the increase and there is growing demand for new chitin sources. In this study, therefore, an attempt was made to extract chitin from the house cricket (Brachytrupes portentosus) by a chemical method. The physicochemical properties of chitin and chitosan extracted from crickets were compared with commercial chitin and chitosan extracted from shrimps, in terms of proximate analysis in particular, of their ash and moisture content. Also, infrared spectroscopy, x-ray diffraction (XRD), scanning electron microscopy and elemental analysis were conducted. The chitin and chitosan yield of the house cricket ranges over 4.3%-7.1% and 2.4%-5.8% respectively. Chitin and chitosan from crickets compares favourably with those extracted from shrimps, and were found to exhibit some similarities. The result shows that cricket and shrimp chitin and chitosan have the same degree of acetylation and degree of deacetylation of 108.1% and 80.5% respectively, following Fourier transform infrared spectroscopy. The characteristic XRD strong/sharp peaks of 9.4 and 19.4° for α-chitin are common for both cricket and shrimp chitin. The percentage ash content of chitin and chitosan extracted from B. portentosus is 1%, which is lower than that obtained from shrimp products. Therefore, cricket chitin and chitosan can be said to be of better quality and of purer form than commercially produced chitin and chitosan from shrimp. Based on the quality of the product, chitin and chitosan isolated from B. portentosus can replace commercial chitin and chitosan in terms of utilization and applications. Therefore, B. portentosus is a promising alternative source of chitin and chitosan.
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.
The combustion characteristics of Malaysia oil palm biomass (palm kernel shell (PKS), palm mesocarp fibre (PMF) and empty fruit bunches (EFB)), sub-bituminous coal (Mukah Balingian) and coal/biomass blends via thermogravimetric analysis (TGA) were investigated. Six weight ratios of coal/biomass blends were prepared and oxidised under dynamic conditions from temperature 25 to 1100°C at four heating rates. The thermogravimetric analysis demonstrated that the EFB and PKS evolved additional peak besides drying, devolatilisation and char oxidation steps during combustion. Ignition and burn out temperatures of blends were improved in comparison to coal. No interactions were observed between the coal and biomass during combustion. The apparent activation energy during this process was evaluated using iso-conversional model free kinetics which resulted in highest activation energy during combustion of PKS followed by PMF, EFB and MB coal. Blending oil palm biomass with coal reduces the apparent activation energy value.
This study aims to investigate the behaviour of Malaysian sub-bituminous coal (Mukah Balingian), oil palm biomass (empty fruit bunches (EFB), kernel shell (PKS) and mesocarp fibre (PMF)) and their respective blends during pyrolysis using thermogravimetric analysis (TGA). The coal/palm biomass blends were prepared at six different weight ratios and experiments were carried out under dynamic conditions using nitrogen as inert gas at various heating rates to ramp the temperature from 25 degrees C to 900 degrees C. The derivative thermogravimetric (DTG) results show that thermal decomposition of EFB, PMF and PKS exhibit one, two and three distinct evolution profiles, respectively. Apparently, the thermal profiles of the coal/oil palm biomass blends appear to correlate with the percentage of biomass added in the blends, thus, suggesting lack of interaction between the coal and palm biomass. First-order reaction model were used to determine the kinetics parameters for the pyrolysis of coal, palm biomass and their respective blends.
The synthesis of kojic acid derivative (KAD) from kojic and palmitic acid (C16:0) in the presence of immobilized lipase from Rhizomucor miehei (commercially known as Lipozyme RMIM), was studied using a shake flask system. Kojic acid is a polyfunctional heterocycles that acts as a source of nucleophile in this reaction allowing the formation of a lipophilic KAD. In this study, the source of biocatalyst, Lipozyme RMIM, was derived from the lipase of Rhizomucor miehei immobilized on weak anion exchange macro-porous Duolite ES 562 by the adsorption technique. The effects of solvents, enzyme loading, reaction temperature, and substrate molar ratio on the reaction rate were investigated. In one-factor-at-a-time (OFAT) experiments, a high reaction rate (30.6 × 10-3 M·min-1) of KAD synthesis was recorded using acetone, enzyme loading of 1.25% (w/v), reaction time of 12 h, temperature of 50 °C and substrate molar ratio of 5:1. Thereafter, a yield of KAD synthesis was optimized via the response surface methodology (RSM) whereby the optimized molar ratio (fatty acid: kojic acid), enzyme loading, reaction temperature and reaction time were 6.74, 1.97% (w/v), 45.9 °C, and 20 h respectively, giving a high yield of KAD (64.47%). This condition was reevaluated in a 0.5 L stirred tank reactor (STR) where the agitation effects of two impellers; Rushton turbine (RT) and pitch-blade turbine (PBT), were investigated. In the STR, a very high yield of KAD synthesis (84.12%) was achieved using RT at 250 rpm, which was higher than the shake flask, thus indicating better mixing quality in STR. In a rheological study, a pseudoplastic behavior of KAD mixture was proposed for potential application in lotion formulation.
The pyrolysis of karanj fruit hulls (KFH) and karanj fruit hull hydrothermal carbonization (KFH-HTC) hydrochar was thermogravimetrically investigated under a nitrogen environment at 5 °C/min, 10 °C/min, and 20 °C/min. The pyrolysis decomposition of KFH biomass was faster than that of KFH-HTC hydrochar because of the high volatility and fixed carbon of KFH biomass. Weight loss percentage was also affected by the heating rates. The kinetic data were evaluated with the Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods. The activation energy values obtained with these two methods were 61.06 and 68.53 kJ/mol for KFH biomass and 130.49 and 135.87 kJ/mol for KFH-HTC hydrochar, respectively. The analysis of kinetic process mechanisms was verified with the Coats-Redfern method. KFH-HTC hydrochar may play a potential role in transforming biomass to energy-rich feedstock for thermochemical applications because of its high heating value, high fixed carbon, and low ash and sulfur contents.
The combustion characteristics of Karanj fruit hulls char (KFH-char) was investigated with thermogravimetry analysis (TGA). The TGA outlined the char combustion thermographs at a different heating rate and isoconversional methods expressed the combustion kinetics. The Kissinger-Akahira-Sunose (KAS) and Flynn-Wall-Ozawa (FWO) methods authenticated the char average activation energy at 62.13 and 68.53kJ/mol respectively, enough to derive the char to burnout. However, the Coats-Redfern method verified the char combustion via complex multi-step mechanism; the second stage mechanism has 135kJ/mol average activation energy. The TGA thermographs and kinetic parameters revealed the adequacy of the KFH-char as fuel substrate than its precursor, Karanj fruit hulls (KFH).
This study examined the combustion profile and kinetics of hydrochar produced from hydrothermal carbonisation (HTC) of Karanj fruit hulls (KFH). The HTC-KFH hydrochar combustion kinetics was investigated at 5, 10, and 20°C/min by thermogravimetric analysis. The kinetics model, Kissinger-Akahira-Sunose revealed the combustion kinetics parameters for the extent of conversion from 0.1 to 0.8; the activation energy varies from 114 to 67 kJ/mol respectively. The hydrochar combustion followed multi-steps kinetics; the Coats-Redfern models predicted the activation energies and pre-exponential constants for the hydrochar combustion zones. The diffusion models are the effective mechanism in the second and third zone.