One of the most significant environmental problems in the world is the massive release of dye wastewater from the dyeing industry. Therefore, the treatment of dyes effluents has received significant attention from researchers in recent years. Calcium peroxide (CP) from the group of alkaline earth metal peroxides acts as an oxidizing agent for the degradation of organic dyes in water. It is known that the commercially available CP has a relatively large particle size, which makes the reaction rate for pollution degradation relatively slow. Therefore, in this study, starch, a non-toxic, biodegradable and biocompatible biopolymer, was used as a stabilizer for synthesizing calcium peroxide nanoparticles (Starch@CPnps). The Starch@CPnps were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Brunauer-Emmet-Teller (BET), dynamic light scattering (DLS), thermogravimetric analysis (TGA), energy dispersive X-ray analysis (EDX) and scanning electron microscopy (SEM). The degradation of organic dyes, methylene blue (MB), using Starch@CPnps as a novel oxidant was studied using three different parameters: initial pH of the MB solution, calcium peroxide initial dosage and contact time. The degradation of the MB dye was carried out via a Fenton reaction, and the degradation efficiency of Starch@CPnps was successfully achieved up to 99%. This study shows that the potential application of starch as a stabilizer can reduce the size of the nanoparticles as it prevents the agglomeration of the nanoparticles during synthesis.
The development of antimicrobial packaging has been growing rapidly due to an increase in awareness and demands for sustainable active packaging that could preserve the quality and prolong the shelf life of foods and products. The addition of highly efficient antibacterial nanoparticles, antifungals, and antioxidants to biodegradable and environmentally friendly green polymers has become a significant advancement trend for the packaging evolution. Impregnation of antimicrobial agents into the packaging film is essential for impeding or destroying the pathogenic microorganisms causing food illness and deterioration. Higher safety and quality as well as an extended shelf life of sustainable active packaging desired by the industry are further enhanced by applying the different types of antimicrobial packaging systems. Antimicrobial packaging not only can offer a wide range of advantages, but also preserves the environment through usage of renewable and biodegradable polymers instead of common synthetic polymers, thus reducing plastic pollution generated by humankind. This review intended to provide a summary of current trends and applications of antimicrobial, biodegradable films in the packaging industry as well as the innovation of nanotechnology to increase efficiency of novel, bio-based packaging systems.
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.
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.
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.
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.
In the present study, a sequence of experiments was performed to assess the influence of the key process parameters on the formation of a carbon nanofiber-coated monolith (CNFCM), using a four-level factorial design in response surface methodology (RSM). The effect of reaction temperature, hydrocarbon flow rate, catalyst and catalyst promoter were examined using RSM to enhance the formation yield of CNFs on a monolith substrate. To calculate carbon yield, a quadratic polynomial model was modified through multiple regression analysis and the best possible reaction conditions were found as follows: a reaction temperature of 800 °C, furfuryl alcohol flow of 0.08525 mL/min, ferrocene catalyst concentration of 2.21 g. According to the characterization study, the synthesized CNFs showed a high graphitization which were uniformly distributed on a monolith substrate. Besides this, the feasibility of carbon dioxide (CO2) adsorption from the gaseous mixture (N2/CO2) under a range of experimental conditions was investigated at monolithic column. To get the most out of the CO2 capture, an as-prepared sample was post-modified using ammonia. Furthermore, a deactivation model (DM) was introduced for the purpose of studying the breakthrough curves. The CO2 adsorption onto CNFCM was experimentally examined under following operating conditions: a temperature of 30-50 °C, pressure of 1-2 bar, flow rate of 50-90 mL/min, and CO2 feed amount of 10-40 vol.%. A lower adsorption capacity and shorter breakthrough time were detected by escalating the temperature. On the other hand, the capacity for CO2 adsorption increased by raising the CO2 feed amount, feed flow rate, and operating pressure. The comparative evaluation of CO2 uptake over unmodified and modified CNFCM adsorbents confirmed that the introduced modification procedure caused a substantial improvement in CO2 adsorption.
As Malaysia is one of the world's largest producer of palm oil, large amounts of palm oil mill effluent (POME) is generated. It was found that negatively charged components are accountable for POME color. An attempt was made to remove residual contaminants after conventional treatment using anion base resin. Adsorption experiments were carried out in fixed bed column. Various models such as the Thomas, the Yoon-Nelson, the Wolborska and BDST model were used to fit the experimental data. It was found that only the BDST model was fitted well at the initial breakthrough time. A wavelet neural network model (WNN) was developed to model the breakthrough curves in fixed bed column for multicomponent system. The results showed that the WNN model described breakthrough curves better than the commonly used models. The effects of pH, flow rate and bed depth on column performance were investigated. It was found that the highest uptake capacity was obtained at pH 3. The exhaustion time appeared to increase with increase in bed length and decrease in flow rate.
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.
A new sensing area for a sensor based on surface plasmon resonance (SPR) was fabricated to detect trace amounts of mercury and lead ions. The gold surface used for SPR measurements were modified with polypyrrole-chitosan (PPy-CHI) conducting polymer composite. The polymer layer was deposited on the gold surface by electrodeposition. This optical sensor was used for monitoring toxic metal ions with and without sensitivity enhancement by chitosan in water samples. The higher amounts of resonance angle unit (ΔRU) were obtained for PPy-CHI film due to a specific binding of chitosan with Pb(2+) and Hg(2+) ions. The Pb(2+) ion bind to the polymer films most strongly, and the sensor was more sensitive to Pb(2+) compared to Hg(2+). The concentrations of ions in the parts per million range produced the changes in the SPR angle minimum in the region of 0.03 to 0.07. Data analysis was done by Matlab software using Fresnel formula for multilayer system.
Oil and gas field wastewater or produced water is a significant waste stream in the oil and gas industries. In this study, the performance of a membrane sequencing batch reactor (MSBR) and membrane sequencing batch reactor/reverse osmosis (MSBR/RO) process treating produced wastewater were investigated and compared. The MSBR was operated in different hydraulic residence time (HRT) of 8, 20 and 44 h. Operation results showed that for a HRT of 20 h, the combined process effluent chemical oxygen demand (COD), total organic carbon (TOC) and oil and grease (O&G) removal efficiencies were 90.9%, 92% and 91.5%, respectively. The MSBR effluent concentration levels met the required standard for oil well re-injection. The RO treatment reduced the salt and organic contents to acceptable levels for irrigation and different industrial re-use. Foulant biopsy demonstrated that the fouling on the membrane surface was mainly due to inorganic (salts) and organic (microorganisms and their products, hydrocarbon constituents) matters.
Produced water is the largest waste stream generated in oil and gas industries. It is a mixture of different organic and inorganic compounds. Due to the increasing volume of waste all over the world in the current decade, the outcome and effect of discharging produced water on the environment has lately become a significant issue of environmental concern. Produced water is conventionally treated through different physical, chemical, and biological methods. In offshore platforms because of space constraints, compact physical and chemical systems are used. However, current technologies cannot remove small-suspended oil particles and dissolved elements. Besides, many chemical treatments, whose initial and/or running cost are high and produce hazardous sludge. In onshore facilities, biological pretreatment of oily wastewater can be a cost-effective and environmental friendly method. As high salt concentration and variations of influent characteristics have direct influence on the turbidity of the effluent, it is appropriate to incorporate a physical treatment, e.g., membrane to refine the final effluent. For these reasons, major research efforts in the future could focus on the optimization of current technologies and use of combined physico-chemical and/or biological treatment of produced water in order to comply with reuse and discharge limits.
In this study, simultaneous adsorption of cationic dyes was investigated by using binary component solutions. Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TMPAA) polymer was used as an adsorbent for uptake of cationic dyes (malachite green, MG and methylene blue, MB) from aqueous solution in a binary system. Adsorption tests revealed that TMPAA presented high adsorption of MG and MB at higher pH and higher dye concentrations. It suggested that there are strong electrostatic attractions between the surface functional groups of the adsorbent and cationic dyes. The equilibrium analyses explain that both extended Langmuir and extended models are suitable for the description of adsorption data in the binary system. An antagonistic effect was found, probably due to triangular (MG) and linear (MB) molecular structures that mutually hinder the adsorption of both dyes on TMPAA. Besides, the kinetic studies for sorption of MG and MB dyes onto adsorbent were better represented by a pseudo-second-order model, which demonstrates chemisorption between the polymeric TMPAA adsorbent and dye molecules. According to experimental findings, TMPAA is an attractive adsorbent for treatment of wastewater containing multiple cationic dyes.
Methyl ester sulphonates (MES) have been considered as an alternative green surfactant for the detergent market. Investigation on the purification of methyl ester sulphonates (MES) with various carbon chains of C12, C14, C16 and C16-18 derived from palm methyl ester is of great interest. These MES powders have been repeatedly crystallized with ethanol and the purity of MES has increased to a maximum of 99% active content and 96% crystallinity index without changing the structure. These crystallized MES with high active content have 1.0% to 2.3% moisture content and retained its di-salt content in the range of 5%. The crystallized MES C16 and C16-18 attained excellent flow characteristics. Morphology, structural and its crystallinity analyses showed that the crystals MES had good solubility properties, stable crystal structure (β polymorphic) and triclinic lateral structure when it is in high active content. The brittleness of MES crystals increased from a β' to a β subcell. Crystal with high brittleness has the potential to ease production of powder, which leads to a reduction in the cost of production and improves efficiency.
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.
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.
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.
In this review, the potential of natural fiber and kenaf fiber (KF) reinforced PLA composite filament for fused deposition modeling (FDM) 3D-printing technology is highlighted. Additive manufacturing is a material-processing method in which the addition of materials layer by layer creates a three-dimensional object. Unfortunately, it still cannot compete with conventional manufacturing processes, and instead serves as an economically effective tool for small-batch or high-variety product production. Being preformed of composite filaments makes it easiest to print using an FDM 3D printer without or with minimum alteration to the hardware parts. On the other hand, natural fiber-reinforced polymer composite filaments have gained great attention in the market. However, uneven printing, clogging, and the inhomogeneous distribution of the fiber-matrix remain the main challenges. At the same time, kenaf fibers are one of the most popular reinforcements in polymer composites. Although they have a good record on strength reinforcement, with low cost and light weight, kenaf fiber reinforcement PLA filament is still seldom seen in previous studies. Therefore, this review serves to promote kenaf fiber in PLA composite filaments for FDM 3D printing. To promote the use of natural fiber-reinforced polymer composite in AM, eight challenges must be solved and carried out. Moreover, some concerns arise to achieve long-term sustainability and market acceptability of KF/PLA composite filaments.
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.