The development of microwave absorbing materials based on recycled hematite (α-Fe2O3) nanoparticles and polycaprolactone (PCL) was the main focus of this study. α-Fe2O3 was recycled from mill scale and reduced to nanoparticles through high energy ball milling in order to improve its complex permittivity properties. Different compositions (5% wt., 10% wt., 15% wt. and 20% wt.) of the recycled α-Fe2O3 nanoparticles were melt-blended with PCL using a twin screw extruder to fabricate recycled α-Fe2O3/PCL nanocomposites. The samples were characterized for their microstructural properties through X - ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). The complex permittivity and microwave absorption properties were respectively measured using the open ended coaxial (OEC) probe and a microstrip in connection with a vector network analyzer in the 1-4 GHz frequency range. An average α-Fe2O3 nanoparticle size of 16.2 nm was obtained with a maximum imaginary (ε") part of permittivity value of 0.54 at 4 GHz. The complex permittivity and power loss values of the nanocomposites increased with recycled α-Fe2O3 nanofiller content. At 2.4 GHz, the power loss (dB) values obtained for all the nanocomposites were between 13.3 dB and 14.4 dB and at 3.4 GHz, a maximum value of 16.37 dB was achieved for the 20 % wt. nanocomposite. The recycled α-Fe2O3/PCL nanocomposites have the potential for use in noise reduction applications in the 1-4 GHz range.
A renewable resource, epoxidized jatropha oil (EJO), was used as a green plasticizer and added to poly(lactic acid) (PLA). EJO was compounded into PLA at different contents. The addition of 3 wt % EJO to the PLA demonstrates significant improvement in flexibility, which leads to a percentage increase of about 7000% in elongation at break. This tensile result was confirmed by surface morphology analysis with clear proof of plastic deformation in EJO-plasticized PLA. EJO imparts a good heat stabilization effect. Thermal stability of PLA was enhanced upon addition of EJO, which is due to their good interaction and plasticizer dispersion within the PLA matrix. This EJO-plasticized PLA has wide applications in various industries, such as packaging of food and non-food products.
Over the last decade, the progressive application of natural fibres in polymer composites has had a major effect in alleviating environmental impacts. Recently, there is a growing interest in the development of green materials in a woven form by utilising natural fibres from lignocellulosic materials for many applications such as structural, non-structural composites, household utilities, automobile parts, aerospace components, flooring, and ballistic materials. Woven materials are one of the most promising materials for substituting or hybridising with synthetic polymeric materials in the production of natural fibre polymer composites (NFPCs). These woven materials are flexible, able to be tailored to the specific needs and have better mechanical properties due to their weaving structures. Seeing that the potential advantages of woven materials in the fabrication of NFPC, this paper presents a detailed review of studies related to woven materials. A variety of factors that influence the properties of the resultant woven NFRC such as yarn characteristics, fabric properties as well as manufacturing parameters were discussed. Past and current research efforts on the development of woven NFPCs from various polymer matrices including polypropylene, polylactic acid, epoxy and polyester and the properties of the resultant composites were also compiled. Last but not least, the applications, challenges, and prospects in the field also were highlighted.
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.
Fibre reinforced composites have gained use in a variety of applications. The performances of these composites may suffer when the material is exposed to adverse environments for a long period of time. Kenaf fibre reinforced unsaturated polyester composites were subjected to water immersion tests in order to study the effects of water absorption on the mechanical properties. Composites specimens containing (10%, 20%, and 30%) weight percentages of fibre were prepared. Water absorption tests were conducted by immersing these specimens in a distilled water bath at 25oC for four months. The tensile properties of the specimens immersed in water were evaluated and compared with the dry composite specimens. A decrease in the tensile properties of the composites was demonstrated, indicating a great loss in the mechanical properties of the water-saturated samples compared to the dry samples. The percentage of moisture uptake was also increased as the percentage of the fibre weight increased due to the high cellulose content. The water absorption pattern of these composites was found to follow the Fickian behaviour.
The fracture behaviour represents the most critical issue in the automotive and aerospace engine fields. Thus, the objective of this study was to estimate and analyze the crack criteria by using the
Mathematical laws that were limited in E 1820 standard and the results affirmed by applying the numerical solutions of ANSYS to estimate the fracture toughness value KIC, besides the energy release rate of biomass composite. The specimens were prepared from different percentage of kenaf mat (KM) and unsaturated polyester resin (UP) 20% KM – 80% UP and 40% KM – 60% UP, respectively, as well the other composite properties which were calculated using the stress-strain data. The fracture characterizations of this composite were carried out using the compact tension (CT) specimen that was commonly used to determine Mode-I fracture properties. The fracture toughness has been found to be independent of pre-crack length. Meanwhile, the tests were performed at room temperature. The numerical simulations of the ANSYS model results demonstrated a good agreement between the experiments computed results of the fracture toughness. The fracture toughness KIC of 20% KM – 80% UP and 40% KM – 60% UP was equivalent to 0.76 MPa√m and 2.0 MPa√m, respectively. Thus, the fracture propagation is dependent on the fibre percentage of the composite. On the other hand, there are unlimited mechanisms of crack paths derived from randomly kenaf mat packs, particularly in the frontal process zone of crack tip.
Vinyl esters combine the best of polyesters and epoxies in terms of properties and processing. Without
complicating presence of reinforcing fibres, this study investigated the effects of catalyst amount, preheating time, molding temperature, and pressure on flexural and water absorption properties of cast vinyl ester (VE) using a factorial experiment. Longer preheating time enhanced the stiffness of VE, while higher molding pressure reduced the flexural modulus. All the four factors did not affect the flexural strength and elongation at the break of molded VE significantly. Using a high molding pressure also caused molded VE to have higher water absorption for a long water exposure period. Meanwhile, greater water absorption at bigger amount of catalyst and higher preheating temperature indicate possible interactions between these factors. The results suggest possible negative effects of high molding pressure through the increase in the network of micro-cracks, and thus lowering the integrity of cast VE sheets. Judicious selection of the process parameters was required in order to obtain good quality molded VE sheets and by extension fibre-reinforced VE composites. Molded VE-unsaturated polyester (UP) blend is a significantly different material which is 1.49 times stronger, 2.38 times more flexible, but it is 0.69 less stiff than neat VE and with significantly higher water absorption. The results obtained warrant for a further investigation in process optimization of VE molding and the use of VE-UP blend as a matrix for natural fibre-reinforced composites.
The purpose of this study is to compare the tensile strength between additional polystyrene into coconut meat husk reinforced fiber composite. Composite were produced by using hand layup technique. It is seen that with the additional of polystyrene into the coconut meat husk reinforced polyester composites showed the increment tensile strength value compared to the non-added polystyrene which indicates that effective stress transfer between the fiber, matrix and polystyrene.
To date, the mechanical performance of kenaf composites is still unsatisfied in term of its mechanical performance. Therefore, research focuses on kenaf composites fabrication through the selection of polymer resin, including epoxy, polypropylene, and polylactic acid. The incorporated kenaf fibre at 10 wt % to 40 wt % loadings was conducted using injection and a compression moulding process. The compressed materials indicated high tensile strength at 240 MPa compared to inject materials (60 MPa). Significant improvement on impact strength (9 kJ/m2) was due to the unpulled-out fibre that dispersed homogenously and hence minimize the microcrack acquire. Meanwhile, high flexural strength (180 MPa) obtained by kenaf/epoxy composites due to the fibre orientate perpendicular to the loading directions, which improve its mechanical properties. The findings indicate that the kenaf fibre reinforced thermoset materials exhibit better mechanical properties as a function to the battery tray applications.
Dry sliding wear of polyester hybrid composites containing carboxylic functionalized multi-walled carbon nanotubes (cNT) and microparticles, silica (Si02) was studied at different sliding distances. An attempt has been made to produce uniform dispersion of nano- and micro- particles in the test samples by ultrasonication. The tribological properties of the hybrid composites were performed by using pin-on-disc (POD) tester against grey cast iron countersurface. The dry sliding wear tests were carried out under pressure-velocity (pv) condition of 0.4 MPa and 4 m/s for total sliding distance of 28800 m and at an interval of every sliding distance of 3600 m, wear properties and behavior were studied. The samples containing 10 wt.% silica (microparticles) with and without CNT always show increase in coefficient of friction at the expense of wear rate. However, samples containing only ci'rr have the lowest wear rate with the increase in coefficient of friction. Sliding distance studies also provide the information on wear rates which were ever changing at different sliding distances whereas average coefficient of friction did not vary throughout the tests. SEM observations of wear surfaces showed different wear morphologies when reinforcement (cNT or Si02) incorporated into the composites either alone or in combination.
Electrospinning is a promising approach to fabricate desirable electropsun nanofibrous scaffold that could be applied in the medical fields. In this study, bacterial copolymer poly(3-hydroxybutyrate-co-68 mol% 4-hydroxybutyrate) [P(3HB-co-68mol% 4HB)] copolymer produced was fabricated into electrospun nanofibers using various combination of electrospinning parameters including the polymer solution, applied voltage and injection speed. The morphology of the fabricated scaffolds were observed using scanning electron microscope (SEM). The SEM images were analysed for the fibre diameter distribution of the scaffolds using Image Analyser. The results revealed that the 8 wt% of polymer solution, 25 kV/cm of the applied voltage and 1.5 mL/h of the injection speed was the most suitable combination. This electrospinning parameters combination fabricated nanofibrous P(3HB-co-4HB) scaffold with smooth, beadles and uniform nanofibers with small fibre diameter distribution.
A halophilic bacterium isolated from mangrove soil sample in Northern Vietnam, Yangia sp. ND199 was found capable of producing homopolymer poly(3-hydroxybutyrate) [P(3HB)], copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)], and copolymer poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] from different carbon sources. The presence of 3HB, 3HV, and 4HB monomers were confirmed by gas chromatography and nuclear magnetic resonance analysis. Only P(3HB) was produced using carbon sources such as fructose or by a combination of fructose with 1,5-pentanediol, 1,6-hexanediol, sodium hexanoate, or sodium octanoate. The biosynthesis of P(3HB-co-3HV) was achieved by adding cosubstrates such as sodium valerate and sodium heptanoate. When 1,4-butanediol, γ-butyrolactone or sodium 4-hydroxybutyrate was added to the culture medium, P(3HB-co-4HB) containing 4.0-7.1mol% 4HB fraction was accumulated. The molecular weights and thermal properties of polyesters were determined by gel permeation chromatography and differential scanning calorimeter, respectively. The results showed that Yangia sp. ND199 is able to produce polyester with high weight average molecular weight ranging from 1.3×10(6) to 2.2×10(6) Dalton and number average molecular weight ranging from 4.2×10(5) to 6.9×10(5) Dalton. The molecular weights, glass transition temperature as well as melting temperature of homopolymer P(3HB) are higher than those of copolymer P(3HB-co-3HV) or P(3HB-co-4HB).
This work reviews the stripping off, role of water molecules in activity, and flexibility of immobilized Candida antarctica lipase B (CALB). Employment of CALB in ring opening polyester synthesis emphasizing on a polylactide is discussed in detail. Execution of enzymes in place of inorganic catalysts is the most green alternative for sustainable and environment friendly synthesis of products on an industrial scale. Robust immobilization and consequently performance of enzyme is the essential objective of enzyme application in industry. Water bound to the surface of an enzyme (contact class of water molecules) is inevitable for enzyme performance; it controls enzyme dynamics via flexibility changes and has intensive influence on enzyme activity. The value of pH during immobilization of CALB plays a critical role in fixing the active conformation of an enzyme. Comprehensive selection of support and protocol can develop a robust immobilized enzyme thus enhancing its performance. Organic solvents with a log P value higher than four are more suitable for enzymatic catalysis as these solvents tend to strip away very little of the enzyme surface bound water molecules. Alternatively ionic liquid can work as a more promising reaction media. Covalent immobilization is an exclusively reliable technique to circumvent the leaching of enzymes and to enhance stability. Activated polystyrene nanoparticles can prove to be a practical and economical support for chemical immobilization of CALB. In order to reduce the E-factor for the synthesis of biodegradable polymers; enzymatic ring opening polyester synthesis (eROPS) of cyclic monomers is a more sensible route for polyester synthesis. Synergies obtained from ionic liquids and immobilized enzyme can be much effective eROPS.
Ultrasonic irradiation greatly improved the Candida antarctica lipase B mediated ring opening polymerization of ε-caprolactone to poly-6-hydroxyhexanoate in the ionic liquid 1-ethyl-3-methylimidazolium tetraflouroborate. Compared to the conventional nonsonicated reaction, sonication improved the monomer conversion by 63% and afforded a polymer product of a narrower molecular weight distribution and a higher degree of crystallinity. Under sonication, the polydispersity index of the product was ~1.44 compared to a value of ~2.55 for the product of the conventional reaction. With sonication, nearly 75% of the monomer was converted to product, but the conversion was only ~16% for the reaction carried out conventionally. Compared to conventional operation, sonication enhanced the rate of polymer propagation by >2-fold and the turnover number of the lipase by >3-fold.
Among the various biomaterials available for tissue engineering and therapeutic applications, microbial polyhydroxyalkanoates offer the most diverse range of thermal and mechanical properties. In this study, the biocompatibility of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB); containing 50 mol % of 4-hydroxybutyrate] copolymer produced by Delftia acidovorans was evaluated. The cytotoxicity, mode of cell death, and genotoxicity of P(3HB-co-4HB) extract against V79 and L929 fibroblast cells were assessed using MTT assay, acridine orange/propidium iodide staining, and alkaline comet assay, respectively. Our results demonstrate that P(3HB-co-4HB) treated on both cell lines were comparable with clinically-used Polyglactin 910, where more than 60% of viable cells were observed following 72-h treatment at 200 mg/mL. Further morphological investigation on the mode of cell death showed an increase in apoptotic cells in a time-dependent manner in both cell lines. On the other hand, P(3HB-co-4HB) at 200 mg/mL showed no genotoxic effects as determined by alkaline comet assay following 72-h treatment. In conclusion, our study indicated that P(3HB-co-4HB) compounds showed good biocompatibility in fibroblast cells suggesting that it has potential to be used for future medical applications.
Four different lipases were compared for ultrasound-mediated synthesis of the biodegradable copolymer poly-4-hydroxybutyrate-co-6-hydroxyhexanoate. The copolymerization was carried out in chloroform. Of the enzymes tested, Novozym 435 exhibited the highest copolymerization rate, in fact the reaction rate was observed to increase with about 26-fold from 30 to 50°C (7.9×10(-3)Ms(-1)), sonic power intensity of 2.6×10(3)Wm(-2) and dissipated energy of 130.4Jml(-1). Copolymerization rates with the Candida antarctica lipase A, Candida rugosa lipase, and Lecitase Ultra™ were lower at 2.4×10(-4), 1.3×10(-4) and 3.5×10(-4)Ms(-1), respectively. The catalytic efficiency depended on the enzyme. The efficiency ranged from 4.15×10(-3)s(-1)M(-1) for Novozym 435-1.48×10(-3)s(-1)M(-1) for C. rugosa lipase. Depending on the enzyme and sonication intensity, the monomer conversion ranged from 8.2% to 48.5%. The sonication power, time and temperature were found to affect the rate of copolymerization. Increasing sonication power intensity from 1.9×10(3) to 4.5×10(3)Wm(-2) resulted in an increased in acoustic pressure (P(a)) from 3.7×10(8) to 5.7×10(8)Nm(-2) almost 2.4-3.7 times greater than the acoustic pressure (1.5×10(8)Nm(-2)) that is required to cause cavitation in water. A corresponding acoustic particle acceleration (a) of 9.6×10(3)-1.5×10(4)ms(-2) was calculated i.e. approximately 984-1500 times greater than under the action of gravity.
Guided bone regeneration (GBR) scaffolds are futile in many clinical applications due to infection problems. In this work, we fabricated GBR with an anti-infective scaffold by ornamenting 2D single crystalline bismuth-doped nanohydroxyapatite (Bi-nHA) rods onto segmented polyurethane (SPU). Bi-nHA with high aspect ratio was prepared without any templates. Subsequently, it was introduced into an unprecedented synthesized SPU matrix based on dual soft segments (PCL-b-PDMS) of poly(ε-caprolactone) (PCL) and poly(dimethylsiloxane) (PDMS), by an in situ technique followed by electrospinning to fabricate scaffolds. For comparison, undoped pristine nHA rods were also ornamented into it. The enzymatic ring-opening polymerization technique was adapted to synthesize soft segments of PCL-b-PDMS copolymers of SPU. Structure elucidation of the synthesized polymers is done by nuclear magnetic resonance spectroscopy. Sparingly, Bi-nHA ornamented scaffolds exhibit tremendous improvement (155%) in the mechanical properties with excellent antimicrobial activity against various human pathogens. After confirmation of high osteoconductivity, improved biodegradation, and excellent biocompatibility against osteoblast cells (in vitro), the scaffolds were implanted in rabbits by subcutaneous and intraosseous (tibial) sites. Various histological sections reveal the signatures of early cartilage formation, endochondral ossification, and rapid bone healing at 4 weeks of the critical defects filled with ornamented scaffold compared to SPU scaffold. This implies osteogenic potential and ability to provide an adequate biomimetic microenvironment for mineralization for GBR of the scaffolds. Organ toxicity studies further confirm that no tissue architecture abnormalities were observed in hepatic, cardiac, and renal tissue sections. This finding manifests the feasibility of fabricating a mechanically adequate nanofibrous SPU scaffold by a biomimetic strategy and the advantages of Bi-nHA ornamentation in promoting osteoblast phenotype progression with microbial protection (on-demand) for GBR applications.
A locally isolated soil microorganism identified as Erwinia sp. USMI-20 has been found to produce poly(3-hydroxybutyrate), P(3HB), from either palm oil or glucose and its copolymer poly(3-hydroxybutyrate-co-3-hydroxyvalerate), P(3HB-co-3HV), from a combination of palm oil and a second carbon source of either one of the following compounds: propionic acid, n-propanol, valeric acid and n-pentanol. It was found that Erwinia sp. USMI-20 could produce P(3HB) up to 69 wt.% polymer content with a dry cell weight of 4.4 g/l from an initial amount of 14.5 g/l of glucose followed by a feeding rate of glucose at 0.48 g/h glucose. On the other hand, the bacteria can achieve 46 wt.% of P(3HB) and a dry cell weight of 3.6 g/l from a batch fermentation in a 10-l fermentor from an initial concentration of 4.6 g/l of palm oil. Further characterisation of the polymer production was also carried out by using different types of palm oil. Among the different palm oils that were used, crude palm oil was the best lipid source for P(3HB) production as compared to palm olein and palm kernel oil. In the production of the copolymer, P(3HB-co-3HV), the highest mole fraction of 3-HV units could be as high as 47 mol% from a single feeding of valeric acid upon initial growth on palm oil.
Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] copolymer is noted for its high biocompatibility, which makes it an excellent candidate for biopharmaceutical applications. The wild-type Cupriavidus sp. USMAA1020 strain is able to synthesize P(3HB-co-4HB) copolymers with different 4HB monomer compositions (up to 70mol%) in shaken flask cultures. Combinations of 4HB carbon precursors consisting of 1,6-hexanediol and γ-butyrolactone were applied for the production of P(3HB-co-4HB) with different 4HB molar fraction. A sharp increase in 4HB monomer composition was attained by introducing additional copies of PHA synthase gene (phaC), responsible for P(3HB-co-4HB) polymerization. The phaC of Cupriavidus sp. USMAA1020 and Cupriavidus sp. USMAA2-4 were cloned and heterologously introduced into host, wild-type Cupriavidus sp. USMAA1020. The gene dosage treatment resulted in the accumulation of 93mol% 4HB by the transformant strains when grown in similar conditions as the wild-type USMAA1020. The PHA synthase activities for both transformants were almost two-fold higher than the wild-type. The ability of the transformants to produce copolymers with high 4HB monomer composition was also tested in large scale production system using 5L and 30L bioreactors with a constant oxygen mass transfer rate. The 4HB monomer composition could be maintained at a range of 83-89mol%. The mechanical and thermal properties of copolymers improved with increasing 4HB monomer composition. The copolymers produced could be tailored for specific biopharmaceutical applications based on their properties.
This study reports the production of P(3HB-co-4HB) [Poly(3-hydroxybutyrate-co-4-hydroxybutyrate)] in possession of high molecular weight and elastomeric properties by Cupriavidus sp. USMAA1020 in single-stage mixed-substrate cultivation system. 1,4-butanediol and 1,6-hexanediol are found to be efficient substrate mixture that has resulted in high copolymer yield, occupying a maximum of 70wt% of the total biomass and producing higher 4HB monomer composition ranging from 31mol% to 41mol%. In substrate mixtures involving 1,6-hexanediol, cleavage of the 6-hydroxyhexanoyl-CoA produces Acetyl-CoA and 4-hydroxybutyryl-CoA. Acetyl-CoA is instrumental in initiating the cell growth in the single-stage fermentation system, preventing 4-hydroxybutyryl-CoA from being utilized via β-oxidation and retained the 4HB monomer at higher ratios. Macroscopic kinetic models of the bioprocesses have revealed that the P(3HB-co-4HB) formation appears to be in the nature of mixed-growth associated with higher formation rate during exponential growth phase; evidenced by higher growth associated constants, α, from 0.0690g/g to 0.4615g/g compared to non-growth associated constants, β, from 0.0092g/g/h to 0.0459g/g/h. The P(3HB-co-31mol% 4HB) produced from the substrate mixture exhibited high weight-average molecular weight, Mwof 927kDa approaching a million Dalton, and possessed elongation at break of 1637% upon cultivation at 0.56wt% C. This is the first report on such properties for the P(3HB-co-4HB) copolymer. The copolymer is highly resistant to polymer deformation after being stretched.