Boron removal capacity of multi-walled carbon nanotubes (MWCNTs) modified with tartaric acid was investigated in this study. Modification of MWCNTs with tartaric acid was confirmed by Boehm surface chemistry method and fourier transform infra-red (FT-IR) spectroscopy. Experiments were performed to determine the adsorption isotherm and adsorption thermodynamic parameters of boron adsorption on tartaric acid modified MWCNTs (TA-MWCNTs). The effect of variables including initial pH, dosage of adsorbent, contact time and temperature was investigated. Analysis of data showed that adsorption equilibrium could be better described by Freundlich isotherm and the maximum adsorption capacities obtained at the pH of 6.0 was 1.97 mg/g. The estimated thermodynamic values of free energy (ΔG°), entropy (ΔS°) and enthalpy (ΔH°) indicated a spontaneous and an endothermic process. Furthermore, the TA-MWCNTs was magnetized for separation of boron-contaminated adsorbent from aqueous solution by applying magnetic field. The results showed that magnetic TA-MWCNTs particles were separated effectively after adsorption from contaminated water.
Global warming has become a serious issue nowadays as the trend of CO2 emission is increasing by years. In Malaysia, the electricity and energy sector contributed a significant amount to the nation's CO2 emission due to fossil fuel use. Many research works have been carried out to mitigate this issue, including carbon capture and utilization (CCUS) technology and biological carbon fixation by microalgae. This study makes a preliminary effort to screen native microalgae species in the Malaysian coal-fired power plant's surrounding towards carbon fixation ability. Three dominant species, including Nannochloropsis sp., Tetraselmis sp., and Isochrysis sp. were identified and tested in the laboratory under ambient and pure CO2 condition to assess their growth and CO2 fixation ability. The results indicate Isochrysis sp. as the superior carbon fixer against other species. In continuation, the optimization study using Response Surface Methodology (RSM) was carried out to optimize the operating conditions of Isochrysis sp. using a customized lab-scale photobioreactor under simulated flue gas exposure. This species was further acclimatized and tested under actual flue gas generated by the power plant. Isochrysis sp. had shown its capability as a carbon fixer with CO2 fixation rate of 0.35 gCO2/L day under actual coal-fired flue gas exposure after cycles of acclimatization phase. This work is the first to demonstrate indigenous microalgae species' ability as a carbon fixer under Malaysian coal-fired flue gas exposure. Thus, the findings shall be useful in exploring the microalgae potential as a biological agent for carbon emission mitigation from power plants more sustainably.
Extensive employment of biomaterials in the areas of biomedical and microbiological applications is considered to be of prime importance. As expected, oil based polymer materials were gradually replaced by natural or synthetic biopolymers due to their well-known intrinsic characteristics such as biodegradability, non-toxicity and biocompatibility. Literature on this subject was found to be expanding, especially in the areas of biomedical and microbiological applications. Introduction of porosity into a biomaterial broadens the scope of applications. In addition, increased porosity can have a beneficial effect for the applications which exploit their exceptional ability of loading, retaining and releasing of fluids. Different applications require a unique set of pore characteristics in the biopolymer matrix. Various pore morphologies have different characteristics and contribute different performances to the biopolymer matrix. Fabrication methods for bio-based porous materials more related to the choice of material. By choosing the appropriate combination of fabrication technique and biomaterial employment, one can obtain tunable pore characteristic to fulfill the requirements of desired application. In our previous review, we described the literature related to biopolymers and fabrication techniques of porous materials. This paper we will focus on the biomedical and microbiological applications of bio-based porous materials.
In this paper, the adsorptive performance of synthesized thiourea (TU) modified poly(acrylonitrile-co-acrylic acid) (TU-P(AN-co-AA)) polymeric adsorbent for capturing p-nitrophenol (PNP) from aqueous solution was investigated. TU-P(AN-co-AA) was synthesized via the redox polymerization method with acrylonitrile (AN) and acrylic acid (AA) as the monomers, then modified chemically with thiourea (TU). Characterization analysis with Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), elemental microanalysis for CHNS, zeta potential measurement, Brunauer-Emmett-Teller (BET) surface analysis and thermal analyses were carried out to determine the morphology and physico-chemical properties of the synthesized polymer. The characterization results indicated successful surface modification of polymer with TU. The performance of TU-P(AN-co-AA) for the removal of PNP was investigated under various experimental parameters (adsorbent dosage, initial adsorbate concentration, contact time and temperature). The results demonstrated that the Freundlich isotherm model and pseudo-second-order kinetic model best described the equilibrium and kinetic data, respectively. Thermodynamic studies showed that the uptake of PNP by TU-P(AN-co-AA) was spontaneous and exothermic in nature. The results of the regeneration studies suggested that the TU-P(AN-co-AA) polymer is a reusable adsorbent with great potential for removing PNP from wastewater.
The aim was to isolate cellulose nanocrystals (CNC) from commercialized oil palm empty fruit bunch cellulose nanofibre (CNF) through sulphuric acid hydrolysis and explore its safeness as a potential nanocarrier. Successful extraction of CNC was confirmed through a field emission scanning electron microscope (FESEM) and attenuated total reflection Fourier transmission infrared (ATR-FTIR) spectrometry analysis. For subsequent cellular uptake study, the spherical CNC was covalently tagged with fluorescein isothiocyanate (FITC), resulting in negative charged FITC-CNC nanospheres with a dispersity (Ð) of 0.371. MTT assay revealed low degree cytotoxicity for both CNC and FITC-CNC against C6 rat glioma and NIH3T3 normal fibroblasts up to 50 µg/mL. FITC conjugation had no contribution to the particle's toxicity. Through confocal laser scanning microscope (CLSM), synthesized FITC-CNC manifested negligible cellular accumulation, indicating a poor non-selective adsorptive endocytosis into studied cells. Overall, an untargeted CNC-based nanosphere with less cytotoxicity that posed poor selectivity against normal and cancerous cells was successfully synthesized. It can be considered safe and suitable to be developed into targeted nanocarrier.
Ethylene glycol dimethacrylate (EGDMA) is used as a crosslinker in poly(acrylonitrile (AN)-co-vinylbenzyl chloride (VBC)) to investigate the effect of long-chain crosslinker to the porosity of the terpolymer system. Poly(AN-co-EGDMA-co-VBC) is synthesized by using precipitation polymerization method and further hypercrosslinked by Friedel-Crafts reaction. FT-IR spectra of poly(AN-co-EGDMA-co-VBC) show that the absorption bands at ~1290 cm-1 that are assigned to the C-Cl vibrations are almost disappeared in hypercrosslinked (HXL) poly(AN-co-EGDMA-co-VBC) polymers, confirming that the hypercrosslinking reaction is successful. SEM images show that the morphologies of the polymers are retained through the hypercrosslinking reactions. Brunauer-Emmett-Teller (BET) analysis shows that hypercrosslinked polymers had a specific surface area up to 59 m2·g-1. The preliminary performance of the terpolymer adsorbent to capture polar analyte is evaluated by adsorbing salicylic acid and mefenamic acid from aqueous solution in a batch system. The maximum adsorption capacity of salicylic acid and mefenamic acid were up to 416.7 mg·g-1 and 625 mg·g-1, respectively, and the adsorption kinetic data obeyed pseudo-second-order rate equation.
Nowadays, there is a significant trend away from solvent-based polyurethane systems towards waterborne polyurethane dispersions due to government regulations requiring manufacturers to lower total volatile organic compounds, as well as consumer preference for more environmentally friendly products. In this work, a renewable vegetable oil-based polyol derived from jatropha oil was polymerized with isophorone diisocyanate and dimethylol propionic acid to produce anionic waterborne polyurethane dispersion. Free standing films with up to 62 wt.% bio-based content were successfully produced after evaporation of water from the jatropha oil-based waterborne polyurethane (JPU) dispersion, which indicated good film formation. The chemical and thermo-mechanical properties of the JPU films were characterized. By increasing the OH numbers of polyol from 161 mgKOH/g to 217 mgKOH/g, the crosslinking density of the JPU was significantly increased, which lead to a better storage modulus and improved hydrophobicity. Overall, JPU produced from polyol having OH number of 217 mgKOH/g appears to be a promising product for application as a binder for wood and decorative coatings.
Bamboo fibers are utilized for the production of various structures, building materials, etc. and is of great significance all over the world especially in southeast Asia. In this study, the extraction of microcrystalline cellulose (MCC) was performed using bamboo fibers through acid hydrolysis and subsequently different characterizations were carried out using various advanced techniques. Fourier transform infrared (FTIR) spectroscopy analysis has indicated the removal of lignin from MCC extracted from bamboo pulp. Scanning Electron Microscopy (SEM) revealed rough surface and minor agglomeration of the MCC. Pure MCC, albeit with small quantities of impurities and residues, was obtained, as revealed by Energy Dispersive X-ray (EDX) analysis. X-ray diffraction (XRD) indicates the increase in crystallinity from 62.5% to 82.6%. Furthermore, the isolated MCC has slightly higher crystallinity compared to commercial available MCC (74%). The results of thermal gravimetric analysis (TGA) demonstrate better thermal stability of isolated MCC compared to its starting material (Bamboo fibers). Thus, the isolated MCC might be used as a reinforcing element for the production of green composites and it can also be utilized as a starting material for the production of crystalline nanocellulose in future.
A membrane sequencing batch reactor (MSBR) treating hypersaline oily wastewater was modeled by artificial neural network (ANN). The MSBR operated at different total dissolved solids (TDSs) (35,000; 50,000; 100,000; 150,000; 200,000; 250,000mg/L), various organic loading rates (OLRs) (0.281, 0.563, 1.124, 2.248, and 3.372kg COD/(m(3)day)) and cyclic time (12, 24, and 48h). A feed-forward neural network trained by batch back propagation algorithm was employed to model the MSBR. A set of 193 operational data from the wastewater treatment with the MSBR was used to train the network. The training, validating and testing procedures for the effluent COD, total organic carbon (TOC) and oil and grease (O&G) concentrations were successful and a good correlation was observed between the measured and predicted values. The results showed that at OLR of 2.44kg COD/(m(3)day), TDS of 78,000mg/L and reaction time (RT) of 40h, the average removal rate of COD was 98%. In these conditions, the average effluent COD concentration was less than 100mg/L and met the discharge limits.
Oil palm empty fruit bunch (OPEFB) is considered the cheapest natural fiber with good properties and exists abundantly in Malaysia. It has great potential as an alternative main raw material to substitute woody plants. On the other hand, the well-known polymeric hydrogel has gathered a lot of interest due to its three-dimensional (3D) cross-linked network with high porosity. However, some issues regarding its performance like poor interfacial connectivity and mechanical strength have been raised, hence nanocellulose has been introduced. In this review, the plantation of oil palm in Malaysia is discussed to show the potential of OPEFB as a nanocellulose material in hydrogel production. Nanocellulose can be categorized into three nano-structured celluloses, which differ in the processing method. The most popular nanocellulose hydrogel processing methods are included in this review. The 3D printing method is taking the lead in current hydrogel production due to its high complexity and the need for hygiene products. Some of the latest advanced applications are discussed to show the high commercialization potential of nanocellulose hydrogel products. The authors also considered the challenges and future direction of nanocellulose hydrogel. OPEFB has met the requirements of the marketplace and product value chains as nanocellulose raw materials in hydrogel applications.
The combination of compounds with different classes (hydrophobic and hydrophilic characters) in single chitosan carrier is a challenge due to the hydrophilicity of chitosan. Utilization of l-ascorbic acid (LAA) and thymoquinone (TQ) compounds as effective antioxidants is marred by poor bioavailability and uptake. Nanoparticles (NPs) solved the problem by functioning as a carrier for them because they have high surface areas for more efficient delivery and uptake by cells. This research, therefore, synthesized chitosan NPs (CNPs) containing LAA and TQ, CNP-LAA-TQ via ionic gelation routes as the preparation is non-toxic. They were characterized using electron microscopy, zetasizer, UV⁻VIS spectrophotometry, and infrared spectroscopy. The optimum CNP-LAA-TQ size produced was 141.5 ± 7.8 nm, with a polydispersity index (PDI) of 0.207 ± 0.013. The encapsulation efficiency of CNP-LAA-TQ was 22.8 ± 3.2% for LAA and 35.6 ± 3.6% for TQ. Combined hydrophilic LAA and hydrophobic TQ proved that a myriad of highly efficacious compounds with poor systemic uptake could be encapsulated together in NP systems to increase their pharmaceutical efficiency, indirectly contributing to the advancement of medical and pharmaceutical sectors.
Iron and steel industries are among the contributors of CO2 emission in large volume into the atmosphere, causing detrimental effects to the environment and the ecosystem at large scale. These industries also generate solid wastes in the form of electric arc furnace (EAF) slag during operations which result in about 10-15% slag wastes per ton of steel produced. In this study, the EAF slags from an iron and steel-making factory in Klang, Malaysia was utilized for CO2 sequestration through direct aqueous mineral carbonation. According to the surface area analysis, the fresh EAF slag has a mesoporous structure, its elemental composition shows the presence of 20.91 wt.% of CaO that was used for the sequestration of CO2 through carbonation. The sequestration capacity was found to be 58.36 g CO2/kg of slag at ambient temperature in 3 h, with the liquid/solid (L/S) ratio of 5:1 and using <63μm particle size. Moreover, the shrinking core model (SCM) was used to analyze the solid-fluid reaction in a heterogeneous phase and the CO2 sequestration shows to be controlled by the product layer phase. The EAF slag is demonstrated to have the potential of CO2 sequestration at ambient temperature.
This study aims to formulate and fabricate the optimum condition of modified kenaf core (MKC) for the removal of targeted endocrine-disrupting compounds in a batch adsorption system. Kenaf core was chemically modified using phosphoric acid as an activating agent, which involved the pyrolysis step. Results indicated a significant difference (p T1KC > T3KC, whereas that in the binary mixture system leads to T2KC > T1KC > T3KC and T1KC > T2KC > T3KC for E2 and EE2 adsorption, respectively, through hydrogen bonding and the π-π interaction mechanism. Thus, the findings revealed T2KC at a moderate level of acid concentration (0.5 M H3PO4) to be a potential biochar, with an environmentally safe and sound profile for opposing emerging pollutant issues as well as for the attainment of sustainable development goals.
Persistent endocrine-disrupting compounds (EDCs) in bodies of water are a concern for human health and constitute an environmental issue, even if present in trace amounts. Conventional treatment systems do not entirely remove EDCs from discharge effluent. Due to the ultra-trace level of EDCs which affect human health and pose an environmental issue, developing new approaches and techniques to remove these micropollutants from the discharged effluent is vital. This review discusses the most common methods of eliminating EDCs through preliminary, primary, secondary and tertiary treatments. The adsorption process is favoured for EDC removal, as it is an economical and straightforward option. The NABC aspects, which are the need, approach, benefits and challenges, were analysed based on existing circumstances, highlighting biochar as a green and renewable adsorbent for the removal of organic contaminants. From the environmental point of view, the effectiveness of this method, which uses natural fibre from the kenaf plant as a porous and economical biochar material with a selected lignocellulosic biomass, provides insights into the advantages of biochar-derived adsorbents. Essentially, the improvement of the natural fibre as an adsorbent is a focus, using carbonisation, activation, and the physiochemical process to enhance the adsorption ability of the material for pollutants in bodies of water. This output will complement sustainable water management approaches presented in previous studies for combating the emerging pollutant crisis via novel green and environmentally safe options.
Crude jatropha oil (JO) was modified to form jatropha oil-based polyol (JOL) via two steps in a chemical reaction known as epoxidation and hydroxylation. JOL was then reacted with isocyanates to produce JO-based polyurethane resin. In this study, two types of isocyanates, 2,4-toluene diisocyanate (2,4-TDI) and isophorone diisocyanate (IPDI) were introduced to produce JPUA-TDI and JPUA-IPDI respectively. 2,4-TDI is categorised as an aromatic isocyanate whilst IPDI is known as a cycloaliphatic isocyanate. Both JPUA-TDI and JPUA-IPDI were then end-capped by the acrylate functional group of 2-hydroxyethyl methacrylate (HEMA). The effects of that isocyanate structure were investigated for their physico, chemical and thermal properties. The changes of the functional groups during each synthesis step were monitored by FTIR analysis. The appearance of urethane peaks was observed at 1532 cm-1, 1718 cm-1 and 3369 cm-1 while acrylate peaks were detected at 815 cm-1 and 1663 cm-1 indicating that JPUA was successfully synthesised. It was found that the molar mass of JPUA-TDI was doubled compared to JPUA-IPDI. Each resin showed a similar degradation pattern analysed by thermal gravimetric analysis (TGA). For the mechanical properties, the JPUA-IPDI-based coating formulation exhibited a higher hardness value but poor adhesion compared to the JPUA-TDI-based coating formulation. Both types of jatropha-based polyurethane acrylate may potentially be used in an ultraviolet (UV) curing system specifically for clear coat surface applications to replace dependency on petroleum-based chemicals.
Jatropha oil-based polyol (JOL) was prepared from crude Jatropha oil via an epoxidation and hydroxylation reaction. During the isocyanation step, two different types of diisocyanates; 2,4-toluene diisocyanate (2,4-TDI) and isophorone diisocyanate (IPDI), were introduced to produce Jatropha oil-based polyurethane acrylates (JPUA). The products were named JPUA-TDI and JPUA-IPDI, respectively. The success of the stepwise reactions of the resins was confirmed using 1H nuclear magnetic resonance (NMR) spectroscopy to support the Fourier-transform infrared (FTIR) spectroscopy analysis that was reported in the previous study. For JPUA-TDI, the presence of a signal at 7.94 ppm evidenced the possible side reactions between urethane linkages with secondary amine that resulted in an aryl-urea group (Ar-NH-COO-). Meanwhile, the peak of 2.89 ppm was assigned to the α-position of methylene to the carbamate (-CH2NHCOO) group in the JPUA-IPDI. From the rheological study, JO and JPUA-IPDI in pure form were classified as Newtonian fluids, while JPUA-TDI showed non-Newtonian behaviour with pseudoplastic or shear thinning behaviour at room temperature. At elevated temperatures, the JO, JPUA-IPDI mixture and JPUA-TDI mixture exhibited reductions in viscosity and shear stress as the shear rate increased. The JO and JPUA-IPDI mixture maintained Newtonian fluid behaviour at all temperature ranges. Meanwhile, the JPUA-TDI mixture showed shear thickening at 25 °C and shear thinning at 40 °C, 60 °C and 80 °C. The master curve graph based on the shear rate for the JO, JPUA-TDI mixture and JPUA-IPDI mixture at 25 °C, 40 °C, 60 °C and 80 °C was developed as a fluid behaviour reference for future storage and processing conditions during the encapsulation process. The encapsulation process can be conducted to fabricate a self-healing coating based on a microcapsule triggered either by air or ultra-violet (UV) radiation.
In this work, to fabricate a novel composite consisting of chitosan/poly-lactic acid doped with graphene oxide (CS/PLA-GO), composites were prepared via solution blending method to create various compositions of CS and PLA (90/10, 70/30 and 50/50CS/PLA-GO). Graphene oxide (GO) was added into a PLA solution prior to blending it with chitosan (CS). The surface morphology and structural properties of synthesized composites were characterized using FT-IR, SEM and XRD analysis. The performances of synthesized composites on thermal strength, mechanical strength, water absorption, and microbial activity were also evaluated through standard testing methods. The morphology of 70/30CS/PLA-GO became smoother with the addition of GO due to enhanced interfacial adhesion between CS, PLA and GO. The presence of GO has also improved the miscibility of CS and PLA and has superior properties compared to CS/PLA composites. Moreover, the addition of GO has boosted the thermal stability of the composite, with a significant enhancement of Td and Tg. The highest Td and Tg were accomplished at 389 °C and 76.88 °C, respectively, for the 70/30CS/PLA-GO composite in comparison to the CS and PLA that recorded Td at 272 °C and 325 °C and Tg at 61 °C and 60 °C, respectively. In addition, as reinforcement, GO provided a significant influence on the tensile strength of composites where the tensile modulus showed remarkable improvement compared to pure CS and CS/PLA composites. Furthermore, CS/PLA-GO composites showed excellent water-barrier properties. Among other compositions, 70/30CS/PLA revealed the greatest decrement in water absorption. From the antibacterial results, it was observed that 90/10CS/PLA-GO and 70/30CS/PLA-GO showed an inhibitory effect and had wide inhibition zones which were 8.0 and 8.5 mm, respectively, against bacteria Bacillus Subtillis B29.
The properties of a composite material depend on its constituent materials such as natural biopolymers or synthetic biodegradable polymers and inorganic or organic nanomaterials or nano-scale minerals. The significance of bio-based and synthetic polymers and their drawbacks on coating film application is currently being discussed in research papers and articles. Properties and applications vary for each novel synthetic bio-based material, and a number of such materials have been fabricated in recent years. This review provides an in-depth discussion on the properties and applications of biopolymer-based nanocomposite coating films. Recent works and articles are cited in this paper. These citations are ubiquitous in the development of novel bionanocomposites and their applications.
Recently, surface functionality and thermal property of the green nanomaterials have received wide attention in numerous applications. In this study, microcrystalline cellulose (MCC) was used to prepare the nanocrystalline celluloses (NCCs) using acid hydrolysis method. The NCCs was treated with TEMPO [(2,2,6,6-tetramethylpiperidin-1-yl)oxy radical]-oxidation to prepare TEMPO-oxidized NCCs. Cellulose nanofibrils (CNFs) also prepared from MCC using TEMPO-oxidation. The effects of rapid cooling and chemical treatments on the thermo-structural property studies of the prepared nanocelluloses were investigated through FTIR, thermogravimetric analysis-derivative thermogravimetric (TGA-DTG), and XRD. A posteriori knowledge of the FTIR and TGA-DTG analysis revealed that the rapid cooling treatment enhanced the hydrogen bond energy and thermal stability of the TEMPO-oxidized NCC compared to other nanocelluloses. XRD analysis exhibits the effect of rapid cooling on pseudo 2Ihelical conformation. This was the first investigation performed on the effect of rapid cooling on structural properties of the nanocellulose.
In this research work, carbon nanofibers (CNFs) were synthesized on honeycomb monolith substrates using injection chemical vapor deposition (ICVD) technique. The effect of various wash-coated materials and catalyst promoter on the growth rate of CNFs on monolith substrates were examined. The characteristics of the synthesized CNFs-coated monolith composites were examined using Raman spectroscopy, Brunauer-Emmett-Teller (BET), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and Transmission electron microscopy (TEM) techniques. According to the textural characterization study, the specific surface area and pore volume of CNFs-coated monolith composites were significantly improved as compared to bare monolith which might be attributed to the growth of highly pure and aligned CNFs over monolith substrate. Besides that, the synthesized CNFs-coated monolith possessed extremely well thermal stability up to the temperature of 550 °C which was corresponded to the strong attachment of highly graphitized CNFs over monolith substrates.