This study aimed to compare the performance of fabricated microbially induced precipitated calcium carbonate⁻ (MB⁻CaCO₃) based red seaweed (Kappaphycus alvarezii) bio-polymer film and commercial calcium carbonate⁻ (C⁻CaCO₃) based red seaweed bio-film with the conventional biodegradable mulch film. To the best of our knowledge, there has been limited research on the application of commercial CaCO₃ (C⁻CaCO₃) and microbially induced CaCO₃ (MB⁻CaCO₃) as fillers for the preparation of films from seaweed bio-polymer and comparison with biodegradable commercial plasticulture packaging. The results revealed that the mechanical, contact angle, and biodegradability properties of the polymer composite films incorporated with C⁻CaCO₃ and MB⁻CaCO₃ fillers were comparable or even superior than the conventional biodegradable mulch film. The seaweed polymer film incorporated with MB⁻CaCO₃ showed the highest contact angle of 100.94°, whereas conventional biodegradable mulch film showed a contact angle of 90.25°. The enhanced contact angle of MB⁻CaCO₃ resulted in high barrier properties, which is highly desired in the current scenario for plasticulture packaging application. The water vapor permeability of MB⁻CaCO₃ based seaweed films was low (2.05 ± 1.06 g·m/m²·s·Pa) when compared to conventional mulch film (2.68 ± 0.35 g·m/m²·s·Pa), which makes the fabricated film an ideal candidate for plasticulture application. The highest tensile strength (TS) was achieved by seaweed-based film filled with commercial CaCO₃ (84.92% higher than conventional mulch film). SEM images of the fractured surfaces of the fabricated films revealed the strong interaction between seaweed and fillers. Furthermore, composite films incorporated with MB⁻CaCO₃ promote brighter film, better water barrier, hydrophobicity, and biodegradability compared to C⁻CaCO₃ based seaweed polymer film and conventional mulch film. From this demonstrated work, it can be concluded that the fabricated MB⁻CaCO₃ based seaweed biopolymer film will be a promising candidate for plasticulture and agricultural application.
In this research work, we studied the microwave properties of multi-wall carbon nanotube (MWCNT) surface functionalized with metallic oxides composites. Three different concentrations (5%, 10%, and 20%) of metallic oxides were used, namely cobalt, iron, and cobalt ferrite. The surface-decorated CNTS were impregnated into polyurethane (PU) matrix. The surface-decorated MWCNTs and the MWCNTs-PU composites were characterized using electron microscopy. The dielectric properties of the samples are studied using an open-ended coaxial probe technique in a wide frequency range of (5-50 GHz). The metallic oxide-decorated surface MWCNTs-PU composites demonstrated different microwave-frequency absorption characteristics depending on the concentration of the metallic oxides.
The aim was to explore the utilization of tea leaf waste fibers (TLWF) as a source for the production of cellulose nanocrystals (CNC). TLWF was first treated with alkaline, followed by bleaching before being hydrolyzed with concentrated sulfuric acid. The materials attained after each step of chemical treatments were characterized and their chemical compositions were studied. The structure analysis was examined by Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD). From FTIR analysis, two peaks at 1716 and 1207 cm-1-which represent C=O stretching and C⁻O stretching, respectively-disappeared in the spectra after the alkaline and bleaching treatments indicated that hemicellulose and lignin were almost entirely discarded from the fiber. The surface morphology of TLWF before and after chemical treatments was investigated by scanning electron microscopy (SEM) while the dimension of CNC was determined by transmission electron microscopy (TEM). The extraction of CNC increased the surface roughness and the crystallinity index of fiber from 41.5% to 83.1%. Morphological characterization from TEM revealed the appearance of needle-like shaped CNCs with average diameter of 7.97 nm. The promising results from all the analyses justify TLWF as a principal source of natural materials which can produce CNC.
The issue of heavy metal contamination has caused a great deal of concern among water quality experts today, as it contributes to water pollution. Activated carbon nanofibers (ACNFs) showed a significant ability in removing heavy metals from the wastewater. In this study, polyacrylonitrile (PAN) was blended and electrospun with an abundant and inexpensive biopolymer, lignin and a water soluble polymer, poly(ethylene glycol) (PEG), by using an electrospinning technique to form nanofibers. The electrospun nanofibers were then investigated as a precursor for the production of porous ACNFs to study the removal of nickel(II) ions by adsorption technique. PEG was added to act as a porogen and to create the porous structure of carbon nanofibers (CNFs). CNFs were prepared by thermal treatment of the electrospun nanofibers and followed by activation of CNFs by thermal and acid treatment on CNFs. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) spectral analysis of the ACNFs showed a strong absorption peak of the C-O functional group, indicating the increase in the oxygenated compound. Field emission scanning electron microscopy (FESEM) images concluded that the ACNFs have more porous and compact fibers with a smaller fiber diameter of 263 ± 11 nm, while the CNFs are less compact and have slightly larger fiber diameter of 323 ± 6 nm. The adsorption study showed that the ACNFs possessed a much higher adsorption capacity of 18.09 mg/g compared with the CNFs, which the amount adsorbed was achieved only at 2.7 mg/g. The optimum adsorption conditions that gave the highest percentage of 60% for nickel(II) ions removal were 50 mg of adsorbent dosage, 100 ppm of nickel(II) solution, pH 3, and a contact time of 60 min. The study demonstrated that the fabrication of ACNFs from PAN/lignin/PEG electrospun nanofibers have potential as adsorbents for the removal of heavy metal contaminants.
In this study, polyacrylonitrile (PAN) was mixed with a renewable polymer, lignin, to produce electrospun nanofibers by using an electrospinning technique. Lignin was utilized as a soft template that was removed from the nanofibers by using a selective dissolution technique to create porous PAN nanofibers. These nanofibers were characterized with Fourier transform infrared (FTIR), field emission scanning electron microscopy (FESEM), thermogravimetry analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) to study their properties and morphology. The results showed that lignin can be homogeneously mixed into the PAN solution and successfully electrospun into nanofibers. FESEM results showed a strong relationship between the PAN: lignin ratio and the diameter of the electrospun fibers. Lignin was successfully removed from electrospun nanofibers by a selective chemical dissolution technique, which resulted in roughness and porousness on the surface of the nanofibers. Based on the BET result, the specific surface area of the PAN/lignin nanofibers was more than doubled following the removal of lignin compared to PAN nanofibers. The highest specific surface area of nanofibers after selective chemical dissolution was found at an 8:2 ratio of PAN/lignin, which was 32.42 m2g-1 with an average pore diameter of 5.02 nm. The diameter of electrospun nanofibers was also slightly reduced after selective chemical dissolution. Porous PAN nanofibers can be seen as the precursors to the production of highly porous carbon nanofibers.
The research included corn starch (CS) films using sorbitol (S), glycerol (G), and their combination (SG) as plasticizers at 30, 45, and 60 wt %, with a traditional solution casting technique. The introduction of plasticizer to CS film-forming solutions led to solving the fragility and brittleness of CS films. The increased concentration of plasticizers contributed to an improvement in film thickness, weight, and humidity. Conversely, plasticized films reduced their density and water absorption, with increasing plasticizer concentrations. The increase in the amount of the plasticizer from 30 to 60% showed a lower impact on the moisture content and water absorption of S-plasticized films. The S30-plasticized films also showed outstanding mechanical properties with 13.62 MPa and 495.97 MPa, for tensile stress and tensile modulus, respectively. Glycerol and-sorbitol/glycerol plasticizer (G and SG) films showed higher moisture content and water absorption relative to S-plasticized films. This study has shown that the amount and type of plasticizers significantly affect the appearances, physical, morphological, and mechanical properties of the corn starch biopolymer plastic.
In this study, a novel cellulose/Ag/TiO2 nanocomposite was successfully synthesized via the hydrothermal method. The cellulose extracted from oil palm empty fruit bunch (OPEFB) could address the disposal issue created by OPEFB biomass. Characterization studies such as FESEM, EDX, HRTEM, XRD, FTIR, UV-Vis DRS, PL, XPS, and surface analysis were conducted. It was observed that the incorporation of cellulose could hinder the agglomeration, reduce the band gap energy to 3 eV, increase the specific surface area to 150.22 m3/g, and lower the recombination rate of the generated electron-hole pairs compared to Ag/TiO2 nanoparticles. The excellent properties enhance the sonocatalytic degradation efficiency of 10 mg/L Congo red (up to 81.3% after 10 min ultrasonic irradiation) in the presence of 0.5 g/L cellulose/Ag/TiO2 at 24 kHz and 280 W. The improvement of catalytic activity was due to the surface plasmon resonance effect of Ag and numerous hydroxyl groups on cellulose that capture the holes, which delay the recombination rate of the charge carriers in TiO2. This study demonstrated an alternative approach in the development of an efficient sonocatalyst for the sonocatalytic degradation of Congo red.
Biomass-derived cellulose hybrid composite materials are promising for application in the field of photocatalysis due to their excellent properties. The excellent properties between biomass-derived cellulose and photocatalyst materials was induced by biocompatibility and high hydrophilicity of the cellulose components. Biomass-derived cellulose exhibited huge amount of electron-rich hydroxyl group which could promote superior interaction with the photocatalyst. Hence, the original sources and types of cellulose, synthesizing methods, and fabrication cellulose composites together with applications are reviewed in this paper. Different types of biomasses such as biochar, activated carbon (AC), cellulose, chitosan, and chitin were discussed. Cellulose is categorized as plant cellulose, bacterial cellulose, algae cellulose, and tunicate cellulose. The extraction and purification steps of cellulose were explained in detail. Next, the common photocatalyst nanomaterials including titanium dioxide (TiO2), zinc oxide (ZnO), graphitic carbon nitride (g-C3N4), and graphene, were introduced based on their distinct structures, advantages, and limitations in water treatment applications. The synthesizing method of TiO2-based photocatalyst includes hydrothermal synthesis, sol-gel synthesis, and chemical vapor deposition synthesis. Different synthesizing methods contribute toward different TiO2 forms in terms of structural phases and surface morphology. The fabrication and performance of cellulose composite catalysts give readers a better understanding of the incorporation of cellulose in the development of sustainable and robust photocatalysts. The modifications including metal doping, non-metal doping, and metal-organic frameworks (MOFs) showed improvements on the degradation performance of cellulose composite catalysts. The information and evidence on the fabrication techniques of biomass-derived cellulose hybrid photocatalyst and its recent application in the field of water treatment were reviewed thoroughly in this review paper.
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 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.
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 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.
Poly(ethylene-vinyl acetate) (PEVA) nanocomposite incorporating dual clay nanofiller (DCN) of surface modified montmorillonite (S-MMT) and bentonite (Bent) was studied for biomedical applications. In order to overcome agglomeration of the DCN, the S-MMT and Bent were subjected to a physical treatment prior to being mixed with the copolymer to form nanocomposite material. The S-MMT and Bent were physically treated to become S-MMT(P) and Bent(pH-s), respectively, that could be more readily dispersed in the copolymer matrix due to increments in their basal spacing and loosening of their tactoid structure. The biocompatibility of both nanofillers was assessed through a fibroblast cell cytotoxicity assay. The mechanical properties of the neat PEVA, PEVA nanocomposites, and PEVA-DCN nanocomposites were evaluated using a tensile test for determining the best S-MMT(P):Bent(pH-s) ratio. The results were supported by morphological studies by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Biostability evaluation of the samples was conducted by comparing the ambient tensile test data with the in vitro tensile test data (after being immersed in simulated body fluid at 37 °C for 3 months). The results were supported by surface degradation analysis. Our results indicate that the cytotoxicity level of both nanofillers reduced upon the physical treatment process, making them safe to be used in low concentration as dual nanofillers in the PEVA-DCN nanocomposite. The results of tensile testing, SEM, and TEM proved that the ratio of 4:1 (S-MMT(P):Bent(pH-s)) provides a greater enhancement in the mechanical properties of the PEVA matrix. The biostability assessment indicated that the PEVA-DCN nanocomposite can achieve much better retention in tensile strength after being subjected to the simulated physiological fluid for 3 months with less surface degradation effect. These findings signify the potential of the S-MMT(P)/Bent(pH-s) as a reinforcing DCN, with simultaneous function as biostabilizing agent to the PEVA copolymer for implant application.
Toxic metals in the industrial wastewaters have been liable for drastic pollution hence a powerful and economical treatment technology is needed for water purification. For this reason, some pure cellulosic materials were derived from waste fiber to obtain an economical adsorbent for wastewater treatment. Conversion of cellulose into grafting materials such as poly(methyl acrylate)-grafted cellulose was performed by free radical grafting process. Consequently, poly(hydroxamic acid) ligand was produced from the grafted cellulose. The intermediate products and poly(hydroxamic acid) ligand were analyzed by FT-IR, FE-SEM, TEM, EDX, and XPS spectroscopy. The adsorption capacity (qe) of some toxic metals ions by the polymer ligand was found to be excellent, e.g., copper capacity (qe) was 346.7 mg·g-1 at pH 6. On the other hand, several metal ions such as cobalt chromium and nickel also demonstrated noteworthy sorption capacity at pH 6. The adsorption mechanism obeyed the pseudo second-order rate kinetic model due to the satisfactory correlated experimental sorption values (qe). Langmuir model isotherm study showed the significant correlation coefficient with all metal ions (R2 > 0.99), indicating that the single or monolayer adsorption was the dominant mode on the surface of the adsorbent. This polymer ligand showed good properties on reusability. The result shows that the adsorbent may be recycled for 6 cycles without any dropping of starting sorption capabilities. This polymeric ligand showed outstanding toxic metals removal magnitude, up to 90-99% of toxic metal ions can be removed from industrial wastewater.
This report presents a facile and efficient methodology for the fabrication of plasticized polyvinyl alcohol (PVA):chitosan (CS) polymer electrolytes using a solution cast technique. Regarding characterizations of electrical properties and structural behavior, the electrochemical impedance spectroscopy (EIS) and X-ray diffraction (XRD) are used, respectively. Crystalline peaks appear in the XRD pattern of the PVA:CS:NH4I while no peaks can be seen in the XRD pattern of plasticized systems. The degree of crystallinity is calculated for all the samples from the deconvoluted area of crystalline and amorphous phases. Considering the EIS measurements, the most conductive plasticized system shows a relatively high conductivity of (1.37 × 10-4) S/cm, which is eligible for applications in energy storage devices. The analysis of the EIS spectra reveals a decrease in bulk resistance which indicates an increase in free ion carriers. The electrical equivalent circuit (EEC) model is used in the analysis of EIS plots. Dielectric properties are modified with the addition of glycerol as a plasticizer. It is proved that the addition of glycerol as a plasticizer lowers ion association. It also shows, at the low-frequency region, a large value of a dielectric constant which is correlated with electrode polarization (EP). The distribution of relaxation times is associated with conducting ions.
Citric acid (CA) can be found naturally in fruits and vegetables, particularly citrus fruit. CA is widely used in many fields but its usage as a green modifying agent and binder for wood is barely addressed. Esterification is one of the most common chemical reactions applied in wood modification. CA contains three carboxyl groups, making it possible to attain at least two esterification reactions that are required for crosslinking when reacting with the hydroxyl groups of the cell wall polymers. In addition, the reaction could form ester linkages to bring adhesivity and good bonding characteristics, and therefore CA could be used as wood binder too. This paper presents a review concerning the usage of CA as a wood modifying agent and binder. For wood modification, the reaction mechanism between wood and CA and the pros and cons of using CA are discussed. CA and its combination with various reactants and their respective optimum parameters are also compiled in this paper. As for the major wood bonding component, the bonding mechanism and types of wood composites bonded with CA are presented. The best working conditions for the CA in the fabrication of wood-based panels are discussed. In addition, the environmental impacts and future outlook of CA-treated wood and bonded composite are also considered.
The use of polymeric material in heavy metal removal from wastewater is trending. Heavy metal removal from wastewater of the industrial process is of utmost importance in green/sustainable manufacturing. Production of absorbent materials from a natural source for industrial wastewater has been on the increase. In this research, polyurethane foam (PUF), an adsorbent used by industries to adsorb heavy metal from wastewater, was prepared from a renewable source. Castor oil-based polyurethane foam (COPUF) was produced and modified for improved adsorption performance using fillers, analyzed with laser-induced breakdown spectroscopy (LIBS). The fillers (zeolite, bentonite, and activated carbon) were added to the COPUF matrix allowing the modification on its surface morphology and charge. The materials were characterized using Fourier-transform infrared (FTIR), scanning electron microscopy (SEM), and thermal gravimetry analysis (TGA), while their adsorption performance was studied by comparing the LIBS spectra. The bentonite-modified COPUF (B/COPUF) gave the highest value of the normalized Pb I (405.7 nm) line intensity (2.3), followed by zeolite-modified COPUF (Z/COPUF) (1.9), and activated carbon-modified COPUF (AC/COPUF) (0.2), which indicates the adsorption performance of Pb2+ on the respective materials. The heavy metal ions' adsorption on the B/COPUF dominantly resulted from the electrostatic attraction. This study demonstrated the potential use of B/COPUF in adsorption and LIBS quantitative analysis of aqueous heavy metal ions.
Global pollution from toxic metal waste has resulted in increased research on toxic metal adsorption. A cellulose acetate-polyurethane (CA-PU) film adsorbent was successfully prepared in this research. The cellulose acetate-polyurethane film adsorbent was prepared with a polycondensation reaction between cellulose acetate and methylene diphenyl diisocyanate. The CA-PU bond formation was confirmed by functional group analysis obtained from Fourier transform infrared (FTIR) spectroscopy. The obtained film was characterized for improved tensile and thermal properties with the addition of methylene diphenyl diisocyanate (MDI). The adsorption ability of the obtained film was evaluated with laser-induced breakdown spectroscopy (LIBS). The best film adsorbent from the LIBS was selected and studied for adsorption isotherm. The FTIR analysis confirmed the formation of the CA-PU bond from the polycondensation between cellulose acetate and the methylene diphenyl diisocyanate. The result showed that the addition of methylene diphenyl diisocyanate (MDI) resulted in the urethane network's growth. The characterization result showed an improvement in the morphology, thermal stability, and tensile strength of the film. The LIBS studies showed improvement in the adsorption of Pb2+ with CA-PU compared with the neat CA. The isotherm studies revealed that Pb2+ adsorption by cellulose acetate-polyurethane film adsorbent was heterogeneously dependent on the Freundlich isotherm model (R2 = 0.97044). Overall, the polycondensation method proposed by this study enhanced the Pb2+ removal, and was comparable to those reported in previous studies.
In this study, tannin-based natural coagulant was used to treat stabilized landfill leachate. Tannin modified with amino group was utilized for the treatment process. Central composite design (CCD) was used to investigate and optimize the effect of tannin dosage and pH on four responses. The treatment efficiency was evaluated based on the removal of four selected (responses) parameters; namely, chemical oxygen demand (COD), color, NH3-N and total suspended solids (TSS). The optimum removal efficiency for COD, TSS, NH3-N and color was obtained using a tannin dosage of 0.73 g at a pH of 6. Moreover, the removal efficiency for selected heavy metals from leachate; namely, iron (Fe2+), zinc (Zn2+), copper (Cu2+), chromium (Cr2+), cadmium (Cd2+), lead (Pb2+), arsenic (As3+), and cobalt (Co2+) was also investigated. The results for removal efficiency for COD, TSS, NH3-N, and color were 53.50%, 60.26%, and 91.39%, respectively. The removal of selected heavy metals from leachate for Fe2+, Zn2+, Cu2+, Cr2+, Cd2+, Pb2+, As3+ and cobalt Co2+ were 89.76%, 94.61%, 94.15%, 89.94%, 17.26%, 93.78%, 86.43% and 84.19%, respectively. The results demonstrate that tannin-based natural coagulant could effectively remove organic compounds and heavy metals from stabilized landfill leachate.