In this study, reduced graphene oxide (RGO)/polymethyl methacrylate (PMMA) nanocomposites were prepared by employing in situ polymerization and solution blending methods. In terms of mechanical properties, RGO loading increased the Young's modulus but decreased the elongation at break for RGO/PMMA nanocomposites. Tensile strength for solution blended RGO/PMMA nanocomposites increased after adding 0.5 wt % RGO, which was attributed to the good dispersion of RGO in the nanocomposites as evidenced from SEM and TEM. Solar energy conversion efficiency measurement results showed that the optimum concentration of RGO in the RGO/PMMA nanocomposites was found to be 1.0 wt % in order to achieve the maximum solar energy conversion efficiency of 25%. In the present study, the solution blended nanocomposites exhibited better overall properties than in situ polymerized nanocomposites owing to the better dispersion of RGO in solution blending. These findings would contribute to future work in search of higher conversion efficiency using nanocomposites.
Discovery and use of biocompatible polymers offers great promise in the pharmaceutical field, particularly in drug delivery systems. Disulphide bonds, which commonly occur in peptides and proteins and have been used as drug-glutathione conjugates, are reductively cleaved in the colon. The intrinsic stability of a disulphide relative to thiol groups is determined by the redox potential of the environment. The objective of this study was to synthesise a trimesic acid-based disulphide cross-linked polymer that could potentially be used for targeted delivery to the colon. The monomer was synthesised by an amide coupling reaction between trimesic acid and (triphenylmethyl) thioethylamine using a two-step synthesis method. The s-trityl group was removed using a cocktail of trifluoroacetic acid and triethylsilane to expose the thiols in preparation for further polymerisation. The resulting polymers (P10, P15, P21, P25, and P51, generated using different molar ratios) were reduced after 1.5 h of reduction time. Scanning electron microscopy images of the polymers showed spherical, loose, or tight patterns depending on the molar ratio of polymerisation. These polymers also exhibited efficient dissolution under various gastrointestinal conditions. Of the five polymers tested, P10 and P15 appeared to be promising drug delivery vehicles for poorly soluble drugs, due to the hydrophobic nature of the polymers.
Halloysite nanotubes (HNTs)-polyester nanocomposites with four different concentrations were produced using solution casting technique and the biodegradation effect of short-term seawater exposure (120 h) was studied. Monolithic polyester was observed to have the highest seawater absorption with 1.37%. At 0.3 wt % HNTs reinforcement, the seawater absorption dropped significantly to the lowest value of 0.77% due to increase of liquid diffusion path. For samples tested in dry conditions, the Tg, storage modulus, tensile properties and flexural properties were improved. The highest improvement of Tg was from 79.3 to 82.4 °C (increase 3.1 °C) in the case of 0.3 wt % HNTs. This can be associated with the exfoliated HNTs particles, which restrict the mobility of polymer chains and thus raised the Tg. After seawater exposure, the Tg, storage modulus, tensile properties and flexural properties of polyester and its nanocomposites were decreased. The Young's modulus of 0.3 wt % HNTs-polyester dropped 20% while monolithic polyester dropped up to 24% compared to their values in dry condition. Apart from that, 29% flexural modulus reduction was observed, which was 18% higher than monolithic polyester. In contrast, fracture toughness and surface roughness increased due to plasticization effect. The presence of various microbial communities caused gradual biodegradation on the microstructure of the polyester matrix as also evidently shown by SEM images.
The aim was to explore the utilization of oil palm mesocarp fiber (OPMF) as a source for the production of cellulose nanocrystals (CNC). OPMF was first treated with alkali and then bleached before the production of CNC by acid hydrolysis (H₂SO₄). The produced materials were characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), a scanning electron microscope (SEM) and a transmission electron microscope (TEM). It was proven that acid hydrolysis can increase the crystallinity of bleached OPMF and reduce the dimension of cellulose to nano scale. Changes in the peaks of the FTIR spectrum at 2852 (C-H stretching), 1732 (C=O stretching) and 1234 cm-1 (C-O stretching) indicated that the alkali treatment completely removed hemicelluloses and lignin from the fiber surface. This can be seen from the thermogram obtained from the TGA characterization. Morphological characterization clearly showed the formation of rod-shaped CNCs. The promising results prove that OPMF is a valuable source for the production of CNC.
The viscosity of four new polymers was investigated for the effect of aging at high temperature, with varying degrees of salinity and hardness. The four sulfonated based polyacrylamide co-polymers were FLOCOMB C7035; AN132 VHM; SUPERPUSHER SAV55; and THERMOASSOCIATIF copolymers. All polymer samples were aged at 80 °C for varying times (from zero to at least 90 days) with and without isobutyl alcohol (IBA) as an antioxidant. To see the effect of divalent ions on the polymer solution viscosity, parallel experiments were performed in a mixture of CaCl₂-NaCl of the same ionic strength as 5 wt % NaCl. The polymers without IBA showed severe viscosity reduction after aging for 90 days in both types of preparation (5 wt % NaCl or CaCl₂-NaCl). In the presence of IBA, viscosity was increased when aging time was increased for 5 wt % NaCl. In CaCl₂-NaCl, on the other hand, a viscosity reduction was observed as aging time was increased. This behavior was observed for all polymers except AN132 VHM.
Valvular dysfunction as the prominent reason of heart failure may causes morbidity and mortality around the world. The inability of human body to regenerate the defected heart valves necessitates the development of the artificial prosthesis to be replaced. Besides, the lack of capacity to grow, repair or remodel of an artificial valves and biological difficulty such as infection or inflammation make the development of tissue engineering heart valve (TEHV) concept. This research presented the use of compound of poly-l-lactic acid (PLLA), thermoplastic polyurethane (TPU) and maghemite nanoparticle (γ-Fe₂O₃) as the potential biomaterials to develop three-dimensional (3D) aortic heart valve scaffold. Electrospinning was used for fabricating the 3D scaffold. The steepest ascent followed by the response surface methodology was used to optimize the electrospinning parameters involved in terms of elastic modulus. The structural and porosity properties of fabricated scaffold were characterized using FE-SEM and liquid displacement technique, respectively. The 3D scaffold was then seeded with aortic smooth muscle cells (AOSMCs) and biological behavior in terms of cell attachment and proliferation during 34 days of incubation was characterized using MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay and confocal laser microscopy. Furthermore, the mechanical properties in terms of elastic modulus and stiffness were investigated after cell seeding through macro-indentation test. The analysis indicated the formation of ultrafine quality of nanofibers with diameter distribution of 178 ± 45 nm and 90.72% porosity. In terms of cell proliferation, the results exhibited desirable proliferation (109.32 ± 3.22% compared to the control) of cells over the 3D scaffold in 34 days of incubation. The elastic modulus and stiffness index after cell seeding were founded to be 22.78 ± 2.12 MPa and 1490.9 ± 12 Nmm², respectively. Overall, the fabricated 3D scaffold exhibits desirable structural, biological and mechanical properties and has the potential to be used in vivo.
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.
This research aims to test four new polymers for their stability under high salinity/high hardness conditions for their possible use in polymer flooding to improve oil recovery from hydrocarbon reservoirs. The four sulfonated based polyacrylamide co-polymers were FLOCOMB C7035; SUPERPUSHER SAV55; THERMOASSOCIATIF; and AN132 VHM which are basically sulfonated polyacrylamide copolymers of AM (acrylamide) with AMPS (2-Acrylamido-2-Methylpropane Sulfonate). AN132 VHM has a molecular weight of 9⁻11 million Daltons with 32 mol % degree of sulfonation. SUPERPUSHER SAV55 mainly has about 35 mol % sulfonation degree and a molecular weight of 9⁻11 million Daltons. FLOCOMB C7035, in addition, has undergone post-hydrolysis step to increase polydispersity and molecular weight above 18 million Daltons but it has a sulfonation degree much lower than 32 mol %. THERMOASSOCIATIF has a molecular weight lower than 12 million Daltons and a medium sulfonation degree of around 32 mol %, and also contains LCST (lower critical solution temperature) type block, which is responsible for its thermoassociative characteristics. This paper discusses the rheological behavior of these polymers in aqueous solutions (100⁻4500 ppm) with NaCl (0.1⁻10 wt %) measured at 25 °C. The effect of hardness was investigated by preparing a CaCl₂-NaCl solution of same ionic strength as the 5 wt % of NaCl. In summary, it can be concluded that the rheological behavior of the newly modified co-polymers was in general agreement to the existing polymers, except that THERMOASSOCIATIF polymers showed unique behavior, which could possibly make them a better candidate for enhanced oil recovery (EOR) application in high salinity conditions. The other three polymers, on the other hand, are better candidates for EOR applications in reservoirs containing high divalent ions. These results are expected to be helpful in selecting and screening the polymers for an EOR application.
Air pollution is a widely discussed topic amongst the academic and industrial spheres as it can bring adverse effects to human health and economic loss. As humans spend most of their time at the office and at home, good indoor air quality with enriched oxygen concentration is particularly important. In this study, polysulfone (PSF) hollow fiber membranes fabricated by dry-jet wet phase inversion method were coated by a layer of polydimethylsiloxane (PDMS) or poly(ether block amide) (PEBAX) at different concentrations and used to evaluate their performance in gas separation for oxygen enrichment. The surface-coated membranes were characterized using SEM and EDX to determine the coating layer thickness and surface chemical properties, respectively. Results from the gas permeation study revealed that the PSF membrane coated with PDMS offered higher permeance and selectivity compared to the membrane coated with PEBAX. The best performing PDMS-coated membrane demonstrated oxygen and nitrogen gas permeance of 18.31 and 4.01 GPU, respectively with oxygen/nitrogen selectivity of 4.56. Meanwhile, the PEBAX-coated membrane only showed 12.23 and 3.11 GPU for oxygen and nitrogen gas, respectively with a selectivity of 3.94. It can be concluded the PDMS coating is more promising for PSF hollow fiber membrane compared to the PEBAX coating for the oxygen enrichment process.
At present, polyhydroxyalkanoates (PHAs) have been considered as a promising alternative to conventional plastics due to their diverse variability in structure and rapid biodegradation. To ensure cost competitiveness in the market, thermoseparating aqueous two-phase extraction (ATPE) with the advantages of being mild and environmental-friendly was suggested as the primary isolation and purification tool for PHAs. Utilizing two-level full factorial design, this work studied the influence and interaction between four independent variables on the partitioning behavior of PHAs. Based on the experimental results, feed forward neural network (FFNN) was used to develop an empirical model of PHAs based on the ATPE thermoseparating input-output parameter. In this case, bootstrap resampling technique was used to generate more data. At the conditions of 15 wt % phosphate salt, 18 wt % ethylene oxide⁻propylene oxide (EOPO), and pH 10 without the addition of NaCl, the purification and recovery of PHAs achieved a highest yield of 93.9%. Overall, the statistical analysis demonstrated that the phosphate concentration and thermoseparating polymer concentration were the most significant parameters due to their individual influence and synergistic interaction between them on all the response variables. The final results of the FFNN model showed the ability of the model to seamlessly generalize the relationship between the input⁻output of the process.
Void-free electrospun SPEEK/Cloisite15A® densed (SP/e-spunCL) membranes are prepared. Different loadings of Cloisite15A® (0.10, 0.15, 0.20, 0.25 and 0.30 wt %) are incorporated into electrospun fibers. The physico-chemical characteristics (methanol permeability, water uptake and proton conductivity) of the membranes are observed. Thermal stability of all membranes is observed using Thermal Gravimetry Analysis (TGA). The thrree stages of degradation range between 163.1 and 613.1 °C. Differential Scanning Calorimetry (DSC) is used to study the wettability of the membranes. SP/e-spunCL15 shows the lowest freezing bound water of 15.27%, which contributed to the lowest methanol permeability. The non-freezing bound water that proportionally increased with proton conductivity of SP/e-spunCL15 membrane is the highest, 10.60%. It is suggested that the electrospinning as the fabricating method has successfully exfoliated the Cloisite in the membrane surface structure, contributing to the decrease of methanol permeability, while the retained water has led to the enhancement of proton conductivity. This new fabrication method of SP/e-spunCL membrane is said to be a desirable polymer electrolyte membrane for future application in direct methanol fuel cell field.
This paper investigated the effects of polytetrafluoroethylene (PTFE) micro-particles on mechanical properties of polyoxymethylene (POM) composites. Since PTFE is immiscible with most polymers, the surface was etched using sodium naphthalene salt in tetrahydrofuran to increase its surface energy. The effects of two variables, namely PTFE content and PTFE etch time, on the mechanical properties of the composite were studied. Experiments were designed in accordance to response surface methodology (RSM) using central composite design (CCD). Samples were prepared with different compositions of PTFE (1.7, 4.0, 9.5, 15.0, or 17.3 wt %) at different PTFE etch times (2.9, 5.0, 10.0, 15.0, or 17.1 min). Four mechanical properties of the POM/GF/PTFE composites, that is, strength, stiffness, toughness, and hardness, were characterized as a function of two studied variables. The dependency of these mechanical properties on the PTFE etch conditions was analyzed using analysis of variance (ANOVA). Overall desirability, D global index, was computed based on the combination of these mechanical properties for POM/GF/PTFE composites. The D global index was found to be 87.5%, when PTFE content and PTFE etch time were 6.5% and 10 min, respectively. Good correlation between experimental and RSM models was obtained using normal probability plots.
The treatment of skin and soft tissue infections caused by methicillin-resistant Staphylococcus aureus (MRSA) remains a challenge, partly due to localization of the bacteria inside the host's cells, where antimicrobial penetration and efficacy is limited. We formulated the cationic polymer polyhexamethylene biguanide (PHMB) with the topical antibiotic nadifloxacin and tested the activities against intracellular MRSA in infected keratinocytes. The PHMB/nadifloxacin nanoparticles displayed a size of 291.3 ± 89.6 nm, polydispersity index of 0.35 ± 0.04, zeta potential of +20.2 ± 4.8 mV, and drug encapsulation efficiency of 58.25 ± 3.4%. The nanoparticles killed intracellular MRSA, and relative to free polymer or drugs used separately or together, the nanoparticles displayed reduced toxicity and improved host cell recovery. Together, these findings show that PHMB/nadifloxacin nanoparticles are effective against intracellular bacteria and could be further developed for the treatment of skin and soft tissue infections.
Metal oxide-polymer nanocomposite has been proven to have selective bactericidal effects against the main and common pathogens (Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli)) that can cause harmful infectious diseases. As such, this study looked into the prospect of using TiO₂/ZnO with linear low-density polyethylene (LLDPE) to inactivate S. aureus and E. coli. The physical, structural, chemical, mechanical, and antibacterial properties of the nanocomposite were investigated in detail in this paper. The production of reactive species, such as hydroxyl radicals (•OH), holes (h⁺), superoxide anion radicals (O₂•¯), and zinc ion (Zn2+), released from the nanocomposite were quantified to elucidate the underlying antibacterial mechanisms. LLDPE/25T75Z with TiO₂/ZnO (1:3) nanocomposite displayed the best performance that inactivated S. aureus and E. coli by 95% and 100%, respectively. The dominant reactive active species and the zinc ion release toward the superior antibacterial effect of nanocomposite are discussed. This work does not only offer depiction of the effective element required for antimicrobial biomedical appliances, but also the essential structural characteristics to enhance water uptake to expedite photocatalytic activity of LLDPE/metal oxide nanocomposite for long term application.
The brittleness of polylactic acid (PLA) has always limited its usage, although it has good mechanical strength. In this study, flexibility of PLA/starch (PSt) blend was enhanced using epoxidized palm oil (EPO) as the green plasticizer. The PLA/starch/EPO (PSE) blends were prepared while using the solution casting method by fixing the content of starch and varying ratio of EPO. The thermal properties, such as glass transition temperature (Tg), melting temperature (Tm), and crystallization temperature (Tcc) were decreased by increasing the amount of EPO into PSt, indicating that EPO increases the chain mobility. Thermogravimetric analysis (TGA) showed that thermal degradation resistance of PSE was higher when compared to PSt. The mechanical testing revealed that EPO at all contents improved the mechanical properties, such as increment of the elongation-at-break and impact strength. Whereas, dynamic mechanical analysis showed that the addition of filler into PLA decreased the storage modulus of PLA. The carbonyl group of the aliphatic ester remained the same in the PSE blends. The morphological study verified the ductility of PSE blends surface when compared to the brittle surface of PSt. As for the soil burial tests, EPO accelerated the degradation of blends. From these results, it can be concluded that EPO improved the flexibility of PLA blends.
The current work is an attempt to reduce friction coefficient of the treated betelnut fibre reinforced polyester (T-BFRP) composites by aging them in twelve different solutions with different kinematic viscosities. The test will be performed on a pin on disc (POD) wear test rig using different applied loads (5⁻30 N), different sliding distances (0⁻6.72 km) at sliding speed of 2.8 m/s subjected to a smooth stainless steel counterface (AISI-304). Different orientations of the fibre mats such as anti-parallel (AP) and parallel (P) orientations subjected to the rotating counterface will be considered. The worn surfaces were examined through optical microscopy imaging and it was found that the aged specimens had significantly lower damages as compared to neat polyester (NP) and the unaged samples. Besides, P-O samples revealed lower friction coefficients as compared to AP-O, i.e., reduction was about 24.71%. Interestingly, aging solutions with lower kinematic viscosities revealed lower friction coefficients of the aged T-BFRP composites when compared to the ones aged in higher kinematic viscosities.
Polyurethane acrylate (PUA) from vegetable oil has been synthesized and prepared for solid polymer electrolyte. Polyol has been end-capped with Toluene 2,4-Diisocyanate (TDI) followed by hydroxylethylmethylacrylate (HEMA) in a urethanation process to produce PUA. The mixtures were cured to make thin polymeric films under UV radiation to produce excellent cured films which exhibit good thermal stability and obtain high ionic conductivity value. 3 to 15 wt. % of ethylene carbonate (EC) mixed with 25 wt. % LiClO₄ was added to PUA to obtain PUA electrolyte systems. PUA modified with plasticizer EC 9 wt. % achieved the highest conductivity of 7.86 × 10-4 S/cm, and relatively improved the linear sweep voltammetry, transference number and dielectric properties. Fourier Transform Infrared Spectroscopy (FTIR) and dielectric analysis were presented. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), followed by X-ray Diffraction (XRD) and morphology have been studied. The addition of plasticizer to the polyurethane acrylate shows significant improvement in terms of the conductivity and performance of the polymer electrolyte.
In this study, polybutylene succinate (PBS) was blended with five types of modified tapioca starch to investigate the effect of modified tapioca starch in PBS blends for food packaging by identifying its properties. Tensile and flexural properties of blends found deteriorated for insertion of starch. This is due to poor interface, higher void contents and hydrolytic degradation of hydrophilic starch. FTIR results show all starch/PBS blends are found with footprints of starch except OH stretching vibration which is absent in B40 blends. Besides, Broad O⁻H absorption in all specimens show that these are hydrogen bonded molecules and no free O⁻H bonding was found. SEM testing shows good interfacial bonding between PBS and starch except E40 blends. Therefore, poor results of E40 blends was expected. In TGA, a slightly weight loss found between 80 to 100 °C due to free water removal. Apart from this, insertion of all types of starch reduces thermal stability of blend. However, high crystallinity of starch/PBS blend observed better thermal stability but lower char yield. Starch A and B blends are suggested to be used as food wrap and food container materials while starch D blend is suitable for grocery plastic bags according to observed results.
Natural rubber is one of the most important renewable biopolymers used in many applications due to its special properties that cannot be easily mimicked by synthetic polymers. To sustain the existence of natural rubber in industries, modifications have been made to its chemical structure from time to time in order to obtain new properties and to enable it to be employed in new applications. The chemical structure of natural rubber can be modified by exposure to ultraviolet light to reduce its molecular weight. Under controlled conditions, the natural rubber chains will be broken by photodegradation to yield low-molecular-weight natural rubber. The aim of this work was to obtain what is known as liquid natural rubber via photodegradation, with titanium dioxide nanocrystals as the catalyst. Titanium dioxide, which was firstly synthesized using the sol⁻gel method, was confirmed to be in the form of an anatase, with a size of about 10 nm. In this work, the photodegradation was carried out in latex state and yielded low-molecular-weight natural rubber latex of less than 10,000 g/mol. The presence of hydroxyl and carbonyl groups on the liquid natural rubber (LNR) chains was observed, resulting from the breaking of the chains. Scanning electron microscopy of the NR latex particles showed that titanium dioxide nanocrystals were embedded on the latex surface, but then detached during the degradation reaction.
Natural fiber composites have been widely used for various applications such as automotive components, aircraft components and sports equipment. Among the natural fibers Typha spp have gained considerable attention to replace synthetic fibers due to their unique nature. The untreated and alkali-treated fibers treated in different durations were dried under the sun for 4 h prior to the fabrication of Typha fiber reinforced epoxy composites. The chemical structure and crystallinity index of composites were examined via FT-IR and XRD respectively. The tensile, flexural and impact tests were conducted to investigate the effect of the alkali treated Typha fibers on the epoxy composite. From the microscopy analysis, it was observed that the fracture mechanism of the composite was due to the fiber and matrix debonding, fiber pull out from the matrix, and fiber damage. The tensile, flexural and impact strength of the Typha fiber reinforced epoxy composite were increased after 5% alkaline immersion compared to untreated Typha fiber composite. From these results, it can be concluded that the alkali treatment on Typha fiber could improve the interfacial compatibility between epoxy resin and Typha fiber, which resulted in the better mechanical properties and made the composite more hydrophobic. So far there is no comprehensive report about Typha fiber reinforcing epoxy composite, investigating the effect of the alkali treatment duration on the interfacial compatibility, and their effect on chemical and mechanical of Typha fiber reinforced composite, which plays a vital role to provide the overall mechanical performance to the composite.